Two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material as well as preparation method and application thereof
By using a two-dimensional layered silicate/hyperbranched metal phthalocyanine/polyarylene ether nitrile ketone dielectric composite material, the problem of low dielectric constant of polymer dielectric materials has been solved, enabling the application of thin film capacitors with high energy density, low dielectric loss and high breakdown strength.
Patent Information
- Application Number
- CN202511814920.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-04
- Publication Date
- 2026-01-09
AI Technical Summary
Existing polymer dielectric materials have low dielectric constants, which limits their practical application in capacitors, and their high dielectric loss makes it difficult to meet the requirements of high energy density, low cost, easy processing and stability.
A two-dimensional layered silicate/hyperbranched metal phthalocyanine/polyarylether nitrile ketone dielectric composite material was prepared by using hyperbranched metal phthalocyanine and two-dimensional layered silicate as fillers, which were then combined with a polyarylether nitrile ketone matrix and prepared by a layer-by-layer coating method. This method enhances interfacial compatibility and conductivity, and improves the dielectric constant.
A composite material with high dielectric constant, low dielectric loss, high temperature resistance and impact resistance was achieved, which extended the breakdown path and improved the breakdown strength and material flexibility.
Smart Images
Figure CN121293716A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer dielectric materials technology, specifically relating to a two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material, its preparation method, and its application. Background Technology
[0002] With the continuous growth of energy demand and the increasing consumption of non-renewable energy, people are paying more and more attention to exploring new energy sources, while also seeking sustainable and renewable resources. Therefore, renewable resources such as wind, tidal, and solar energy are receiving increasing attention, and maximizing the utilization of these resources and converting them into electricity is a common strategy today. Dielectric capacitors can well fulfill this responsibility, becoming a focus of increasing attention due to their convenience, efficiency, and environmental friendliness. As the demand for clean and efficient capacitive energy storage systems grows, the demand for high-energy-density dielectric materials is also increasing. Dielectric capacitors, due to their ability to generate polarized energy storage in an external electric field, are widely used in energy storage devices. Compared to currently used batteries and electrochemical capacitors, they have the advantage of extremely fast charging speed, low cost, and minimal environmental impact, meeting the current development needs of the energy sector. However, their relatively low energy density compared to batteries and electrochemical capacitors significantly limits their application, making the design and fabrication of low-cost, high-energy-density, low-dielectric-loss, flexible, easy-to-process, and highly stable dielectric capacitors one of the research frontiers.
[0003] Among the many candidates for dielectric materials, polymer dielectric materials have attracted much attention due to their inherent advantages such as low dielectric loss, high electrical breakdown strength, and ease of processing for energy storage capacitors. However, their relatively low dielectric constant limits their practical application in capacitors. Summary of the Invention
[0004] The purpose of this invention is to overcome the aforementioned shortcomings of the prior art and provide a two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylene ether nitrile ketone dielectric composite material, its preparation method, and its applications. This composite material exhibits a high dielectric constant and can be practically applied in film capacitors, thereby improving the performance of film capacitors.
[0005] To achieve the above-mentioned objectives, in a first aspect, the present invention provides a two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material, comprising: Using polyarylene ether nitrile ketone as the matrix, hyperbranched metal phthalocyanine and two-dimensional layered silicate are used as fillers, with the mass ratio of hyperbranched metal phthalocyanine less than or equal to 2% and the mass ratio of two-dimensional layered silicate filler less than or equal to 9%.
[0006] Second aspect, the present invention provides a method for preparing the above-mentioned two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material, including: (1) Preparation of polyarylether nitrile ketone: Using 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile, 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone and a diphenolic compound as copolymerization monomers, under the catalysis of potassium carbonate, a nucleophilic substitution polycondensation reaction is carried out using a composite solvent system composed of one of N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide and toluene. After the viscosity no longer increases, it is cooled. After cooling, the product is precipitated, washed and purified to obtain the polyarylether nitrile ketone; (2) Preparation of hyperbranched metal phthalocyanine: First, dissolve phloroglucinol, 4-nitrophthalonitrile and potassium carbonate in the organic solvent N,N-dimethylformamide, and prepare a multi-functional phthalonitrile through a constant temperature water bath reaction. Then, heat and reflux the multi-functional phthalonitrile and metal salt under mechanical stirring to prepare hyperbranched metal phthalocyanine; (3) Delamination of two-dimensional layered silicate: The two-dimensional layered silicate is delaminated by heating / vaporization method; (4) Solution blending: First, disperse the hyperbranched metal phthalocyanine and the delaminated two-dimensional layered silicate in a solvent to form a blended solution, and then add the polyarylether nitrile ketone to the blended solution to obtain a mixed solution; (5) Preparation of dielectric composite material: Using the layer-by-layer scraping film method, the mixed solution is made into a composite film; the solvent in the composite film is removed, and after removal, it is cooled and peeled off, and then hot pressing treatment is carried out to prepare the two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material.
[0007] In one embodiment, in step (1), the molar ratio of the 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile, the diphenolic compound and the 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone is n:(n + m):m, where 0 < n / (n + m) ≤ 50%, and the diphenolic compound is one or more of phenolphthalein, biphenol, hydroquinone, resorcinol and bisphenol S; the volume ratio of N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide to toluene is 3:1; the molar ratio of potassium carbonate to 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile is 3:1; the solid content of the nucleophilic substitution polycondensation reaction system is 30% to sixty%.
[0008] In one embodiment, in step (2), the molar ratio of the phloroglucinol, the 4-nitrophthalonitrile, and the potassium carbonate is 1:3:4.5; the total mass concentration of the three components—phloroglucinol, the 4-nitrophthalonitrile, and the potassium carbonate—in the organic solvent N,N-dimethylformamide is 128.4 g / 150 mL; the molar ratio of the polyfunctional phthalonitrile to the metal salt is 3:1, and the metal salt includes at least one of zinc acetate, ferric chloride, and cuprous chloride.
[0009] In one embodiment, in step (3), 2-5g of two-dimensional layered silicate material is placed in a beaker; heated at 100°C for 10-20min, then 50-100mL of liquid nitrogen is poured in, and after it evaporates naturally, this step is repeated three times; then the obtained sample is dried in an oven at 60°C for 8h to obtain the delaminated two-dimensional layered silicate, wherein the two-dimensional layered silicate filler includes at least one of montmorillonite, muscovite and talc.
[0010] In one embodiment, in step (4), 0.02g-0.04g of hyperbranched metal phthalocyanine and 0.02g-0.18g of exfoliated two-dimensional layered silicate filler are first dissolved in 12-24mL of solvent, and ultrasonicated for 5min at a stirring speed of 200-300r / min and 160℃, and stirred for 1-2h. Then, 1-2g of polyarylether nitrile ketone is added, and the mixture is stirred until the matrix resin is completely dissolved and the filler is evenly mixed to prepare a mixed solution.
[0011] In one embodiment, hyperbranched metal phthalocyanine and stripped two-dimensional layered silicate are dispersed in N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.
[0012] In one embodiment, in step (5), the dispersed mixed solution is poured evenly onto a horizontal glass plate in an oven in multiple batches, and the film is scraped layer by layer to a preset thickness to obtain a composite film; then the solvent in the composite film is removed by gradient heating; after removing the solvent, it is naturally cooled to room temperature, and the composite film is peeled off from the glass plate. After hot pressing at a temperature of 140-200℃ and a pressure of 15-25MPa, a two-dimensional layered silicate filler / hyperbranched metal phthalocyanine / polyarylene ether nitrile ketone composite film is obtained.
[0013] In one embodiment, removing the solvent from the composite membrane by gradient heating involves heating the composite membrane at 80°C for 1 hour, at 100°C for 1 hour, at 120°C for 1 hour, at 160°C for 2 hours, at 200°C for 2 hours, and at 220°C for 2 hours to remove the solvent from the composite membrane.
[0014] Thirdly, the present invention provides an application of the two-dimensional layered silicate filler / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material prepared by the above preparation method in the preparation of thin film capacitors.
[0015] The advantages and beneficial effects of this invention compared to the prior art are as follows: 1. In this invention, hyperbranched metal phthalocyanine and two-dimensional layered silicate are used as fillers. Hyperbranched metal phthalocyanine can be mixed with two-dimensional layered silicate to increase the surface roughness of the two-dimensional layered silicate, enhance its interfacial compatibility with the polymer matrix, and reduce dielectric loss. It can also be used together with two-dimensional layered silicate as a conductive material to significantly improve the dielectric constant, thereby obtaining a two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylene ether nitrile ketone dielectric composite material with high dielectric constant, low dielectric loss, high strength, high temperature resistance and impact resistance.
[0016] 2. In this invention, a two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylene ether nitrile ketone dielectric composite material is prepared by a layer-by-layer scraping method, so that the two-dimensional layered silicate filler is parallel to the film plane. The composite material has stronger interfacial polarization, effectively blocking the growth of electrical trees, thereby extending the breakdown path and improving the breakdown strength. Attached Figure Description
[0017] To clearly illustrate the technical solutions or prior art involved in this invention, the relevant drawings will be briefly described below. It should be noted that the drawings are merely embodiments of this invention, and those skilled in the art can derive other related schematic diagrams based on the drawings without any creative effort.
[0018] Figure 1 Fourier transform infrared spectra of the polyarylene ether nitrile ketone, peeled montmorillonite, hyperbranched zinc phthalocyanine, and the dielectric composite material of peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether nitrile ketone prepared in Example 1. Figure 2 Scanning electron microscope (SEM) images of the polyarylene ether nitrile ketone (PAHK), peeled montmorillonite, hyperbranched zinc phthalocyanine (BCP), and the PAHK / hyperbranched zinc phthalocyanine (BCP) / polyarylene ether nitrile ketone (PAHK) dielectric composite materials prepared in Example 1 and Examples 1-6, with mass fractions of 0%, 1%, 2%, 3%, 6%, and 9%, respectively.
[0019] Figure 3 The graph shows the dielectric constant versus frequency of the polyarylene ether nitrile ketone prepared in Example 1 and the peeled montmorillonite filler mass fractions of 0%, 1%, 2%, 3%, 6%, and 9% prepared in Examples 1-6, respectively.
[0020] Figure 4The dielectric constant versus frequency relationship is shown for the polyarylene ether nitrile ketone prepared in Comparative Example 1 and the peeled montmorillonite filler mass fractions of 0%, 1%, 2%, 3%, 6%, and 9% prepared in Comparative Examples 1-6.
[0021] Figure 5 The figure shows the results of the flexibility test of the stripped montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone filler with a mass content of 9% prepared in Example 1. Detailed Implementation
[0022] To make the technical problem to be solved, the technical solution, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
[0023] In a first aspect, the present invention provides a two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material, comprising: Using polyarylene ether nitrile ketone as the matrix, hyperbranched metal phthalocyanine and two-dimensional layered silicate are used as fillers, with the mass ratio of hyperbranched metal phthalocyanine less than or equal to 2% and the mass ratio of two-dimensional layered silicate filler less than or equal to 9%.
[0024] The mass ratio of hyperbranched metal phthalocyanine is its percentage of the total mass of the composite material. The optimal mass ratio of hyperbranched zinc phthalocyanine is 2%, at which the material has the highest dielectric constant. The mass ratio of two-dimensional layered silicate filler is also its percentage of the total mass of the composite material. Secondly, the present invention provides a method for preparing the above-mentioned two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material, comprising: (1) Preparation of polyarylether nitrile ketone: 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile, 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone and diphenolic compounds are used as comonomers. Under the catalysis of potassium carbonate, a nucleophilic substitution polycondensation reaction is carried out in a composite solvent system composed of N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide and toluene. After the viscosity no longer increases, the mixture is cooled. After cooling, the product is precipitated, washed and purified to obtain the polyarylether nitrile ketone. (2) Preparation of hyperbranched metal phthalocyanine: First, phloroglucinol, 4-nitrophthalonitrile and potassium carbonate are dissolved in the organic solvent N,N-dimethylformamide and reacted in a constant temperature water bath to prepare multifunctional phthalonitrile. Then, the multifunctional phthalonitrile and metal salt are heated and refluxed under mechanical stirring to prepare hyperbranched metal phthalocyanine. (3) Exfoliation of two-dimensional layered silicate: exfoliating two-dimensional layered silicate by heating / vaporization method; (4) Solution blending: First, disperse hyperbranched metal phthalocyanine and exfoliated two-dimensional layered silicate in a solvent to form a blended solution, and then add polyarylether nitrile ketone to the blended solution to obtain a mixed solution; (5) Preparation of dielectric composite material: Using the layer-by-layer scraping film method, make the mixed solution into a composite film; remove the solvent in the composite film, cool and exfoliate after removal, and then perform hot pressing treatment to prepare the two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material.
[0025] Further, in step (1), the molar ratio of the 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile, the diphenolic compound and the 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone is n:(n + m):m, where 0 < n / (n + m) ≤ 50%, and the diphenolic compound is one or more of phenolphthalein, biphenol, hydroquinone, resorcinol and bisphenol S; the volume ratio of N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide to toluene is 3:1, ensuring that the azeotropic temperature of the composite solvent is stable at 150 °C; the molar ratio of potassium carbonate to 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile is 3:1; the solid content of the nucleophilic substitution polycondensation reaction system is 30% to 60%.
[0026] Further, in step (2), the molar ratio of phloroglucinol, 4-nitrophthalonitrile and potassium carbonate is 1:3:4.5; the total mass concentration of phloroglucinol, 4-nitrophthalonitrile and potassium carbonate in the organic solvent N,N-dimethylformamide is 128.4 g / 150 mL; the molar ratio of the multifunctional phthalonitrile to the metal salts is 3:1, and the metal salts include at least one of zinc acetate, ferric trichloride and cuprous chloride.
[0027] Further, in step (3), place 2-5 g of two-dimensional layered silicate material in a beaker; heat at 100 °C for 10-20 min, then pour 50-100 mL of liquid nitrogen, wait for it to volatilize naturally, and then repeat this step three times; then dry the obtained sample in an oven at 60 °C for 8 h to obtain exfoliated two-dimensional layered silicate, and the two-dimensional layered silicate filler includes at least one of montmorillonite, muscovite and talc.
[0028] Further, in step (4), 0.02g-0.04g of hyperbranched metal phthalocyanine and 0.02g-0.18g of two-dimensional layered silicate filler are first dissolved in 12-24mL of solvent, and ultrasonicated for 5min at a stirring speed of 200-300r / min and 160℃, and stirred for 1-2h. Then, 1-2g of polyarylether nitrile ketone is added and stirred until the matrix resin is completely dissolved and the filler is mixed evenly to prepare a mixed solution.
[0029] Furthermore, hyperbranched metal phthalocyanine and exfoliated two-dimensional layered silicates are dispersed in N-methylpyrrolidone, N,N-dimethylformamide, or N,N-dimethylacetamide.
[0030] Further, in step (5), the dispersed mixed solution is poured evenly onto a horizontal glass plate in an oven in multiple batches, and the film is scraped layer by layer to a preset thickness to obtain a composite film; then the solvent in the composite film is removed by gradient heating; after removing the solvent, it is naturally cooled to room temperature, and the composite film is peeled off from the glass plate. After hot pressing at a temperature of 140-200℃ and a pressure of 15-25MPa, a two-dimensional layered silicate filler / hyperbranched metal phthalocyanine / polyarylene ether nitrile ketone composite film is obtained.
[0031] Furthermore, the solvent in the composite membrane is removed by gradient heating by heating the composite membrane at 80°C for 1 hour, 100°C for 1 hour, 120°C for 1 hour, 160°C for 2 hours, 200°C for 2 hours, and 220°C for 2 hours.
[0032] Thirdly, the present invention provides an application of the two-dimensional layered silicate filler / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material prepared by the above preparation method in the preparation of thin film capacitors.
[0033] This invention has undergone numerous experiments, and some of the experimental results are presented here for reference to further describe the invention in detail. The following is a detailed description in conjunction with specific embodiments.
[0034] Example 1 Example 1 discloses a method for preparing the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone composite dielectric material of the present invention, specifically as follows: S1. Preparation of polyarylene ether nitrile ketone: 0.064 mol of 2,6-dichlorobenzonitrile, 0.128 × 1.01 mol of phenolphthalein, 0.064 mol of 4,4'-difluorobenzophenone, and 0.128 × 1.5 mol of potassium carbonate were added to a 250 mL three-necked flask containing 75 mL of N-methylpyrrolidone and 25 mL of toluene. The mixture was stirred and heated to 150 °C at 180 rpm for 2 h to dehydrate. The temperature was then increased to 170 °C over 30 min and held for 2 h. The temperature was then increased to 180 °C and held for 1 h until the viscosity no longer changed. The mixture was cooled to 150 °C, and the product was poured into a 15% hydrochloric acid solution to precipitate the product. The precipitate was soaked for 12 hours. After washing with deionized water and crushing, the crude product was dried in an oven at 100°C for 3 hours. Then, the crude product was boiled in deionized water for 30 minutes and filtered, repeated three times (boiling and filtration were repeated three times). After drying in an oven at 100°C for 3 hours, the first-purified polyarylether ketone was obtained. A second purification was then performed. The first-purified polyarylether ketone was added to NMP and heated and stirred to dissolve. The solid-liquid mass ratio of the first-purified polyarylether ketone to NMP was 1:5. After dissolution, the precipitate was poured into deionized water and soaked for 12 hours. The precipitate was then washed with deionized water and crushed, and the obtained product was dried in an oven at 100°C for 3 hours. Then, the product was boiled in deionized water for 30 minutes and filtered, repeated three times (boiling and filtration were repeated three times). After drying in an oven at 100°C for 3 hours, the second-purified polyarylether ketone was obtained.
[0035] S2. Preparation of hyperbranched zinc phthalocyanine: Phloroglucinol (0.1 mol), 4-nitrophthalonitrile (0.3 mol), and potassium carbonate (0.45 mol) were added to a 250 mL three-necked flask containing 150 mL of DMF solvent. The mixture was reacted at room temperature for 24 h at 400 rpm. The resulting pale yellow solid powder was obtained by filtration and washed sequentially with deionized water, acetone, and ethanol. After washing, the powder was filtered again to obtain a white solid powder. The white solid powder was then dried in an oven at 80 °C for 24 h to obtain purified multifunctional phthalonitrile (TPh). The purified TPh (3 mmol) and zinc acetate (1 mmol) were then added to a mixture containing 40 mL of DMAc solvent. In a 100 mL three-necked flask containing 1 mL of solvent, the mixture was reacted in a water bath at a stirring rate of 300 r / min and a temperature of 160 °C for 24 h. After the solution cooled to room temperature, it was poured into 1000 mL of deionized water. After filtration, the product was washed sequentially with deionized water, methanol, and ethanol, respectively. The resulting dark blue solid powder was then dried in an oven at 60 °C for 24 h to obtain purified hyperbranched zinc phthalocyanine.
[0036] S3. Delamination of montmorillonite: Place 2g of montmorillonite in a beaker; heat at 100℃ for 10min, then quickly pour in 60mL of liquid nitrogen, and allow it to evaporate naturally. Repeat this step 3 times (repeat the step of heating at 100℃ for 10min, then quickly pouring in 60mL of liquid nitrogen, and allowing it to evaporate naturally 3 times); then dry the obtained sample in an oven at 60℃ for 8h to obtain exfoliated montmorillonite.
[0037] S4. Solution blending: 0.04 g of hyperbranched zinc phthalocyanine and 0.18 g of stripped montmorillonite were dissolved in 24 mL of NMP solvent. The mixture was sonicated for 5 min at a stirring speed of 300 r / min and a temperature of 160 °C, and stirred for 1 h. Then, 1.96 g of polyarylether ketone was added and stirred for 2 h to prepare a mixed solution of stripped montmorillonite / hyperbranched zinc phthalocyanine / polyarylether ketone with a mass fraction of 9 wt%.
[0038] S5. Preparation of dielectric composite materials: A layer-by-layer coating method was used to uniformly pour a mixed solution of peelable montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone onto a clean, level glass plate in an oven. Layers were then coated with a scraper to a final thickness of 0.05 mm. After drying and curing, a composite film was obtained. A gradient heating method was employed, heating the composite film at 80℃ for 1 hour, 100℃ for 1 hour, 120℃ for 1 hour, 160℃ for 2 hours, 200℃ for 2 hours, and 220℃ for 2 hours to remove the solvent. After natural cooling to room temperature, the composite film was peeled off from the glass plate and hot-pressed at 140℃ and 25 MPa to obtain a 9 wt% peelable montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composite material.
[0039] Examples 2-6 This embodiment discloses an investigation of composite materials with different contents of stripped montmorillonite filler.
[0040] Compared with Example 1, the preparation methods of the exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composites in Examples 2-6 differed in the filler content, specifically the content of exfoliated montmorillonite in step S4. Example 2 added 0g of exfoliated montmorillonite; Example 3 added 0.02g of exfoliated montmorillonite; Example 4 added 0.04g of exfoliated montmorillonite; Example 5 added 0.06g of exfoliated montmorillonite; and Example 6 added 0.12g of exfoliated montmorillonite, while other parameters remained unchanged. Examples 2-6 yielded exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composites with exfoliated montmorillonite mass fractions of 0%, 1%, 2%, 3%, and 6%, respectively.
[0041] Comparative Example 1 Compared with Example 1, this comparative example uses a casting film-forming method to prepare the composite material in step S5. The preparation method of the composite material in this comparative example is as follows: S1-S4 are the same as in Example 1; S5 uses a casting film-forming method, where the mixed solution is evenly poured onto a clean, level glass plate in an oven, naturally spread, and then dried and cured to form a composite film; other steps remain unchanged.
[0042] Comparative Examples 2-6 This comparative example provides an investigation of composite materials with different contents of stripped montmorillonite filler.
[0043] Compared with Comparative Example 1, the preparation methods of the exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composites in Comparative Examples 2-6 differed in the filler content. Specifically, in step S4, 0 g of exfoliated montmorillonite was added in Comparative Example 2; 0.02 g of exfoliated montmorillonite was added in Comparative Example 3; 0.04 g of exfoliated montmorillonite was added in Comparative Example 4; 0.06 g of exfoliated montmorillonite was added in Comparative Example 5; and 0.12 g of exfoliated montmorillonite was added in Comparative Example 6. Other parameters remained unchanged. Exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composites with exfoliated montmorillonite mass fractions of 0%, 1%, 2%, 3%, and 6% were obtained in Comparative Examples 2-6, respectively.
[0044] Experimental Example 1 This experimental example will characterize the Fourier transform infrared spectra of the polyarylene ether nitrile ketone, peeled montmorillonite, hyperbranched zinc phthalocyanine, and the dielectric composite material of peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether nitrile ketone prepared in Example 1, as shown in the following figures. Figure 1 As shown in the figure, a is polyarylene ether nitrile ketone, b is exfoliated montmorillonite, c is hyperbranched zinc phthalocyanine, and d is a dielectric composite material of exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether nitrile ketone.
[0045] Depend on Figure 1 It can be seen that in the Fourier transform infrared spectrum of polyarylether nitrile ketone, 3064 cm⁻¹ -1 and 1500cm -1 The characteristic absorption peak of the C≡C vibration of the benzene ring skeleton is present at 2230 cm⁻¹. -1 The peak value is attributed to the vibration of the symmetrically stretched nitrile group -CN, 1768 cm⁻¹. -1 The ester bond in the phenolphthalein structure of the molecular chain is represented by the 1655 cm⁻¹ absorption band, which is the stretching vibration peak of the ketone hydroxyl group. The 1109 cm⁻¹ absorption band represents the ester bond in the phenolphthalein structure. -1 and 1209cm -1 The characteristic peak of aryl ethers; in the Fourier transform infrared spectrum of exfoliated montmorillonite, 1643 cm⁻¹ -1 The vibration peak at 1033 cm⁻¹ is attributed to the HOH bending vibration of adsorbed water. -1 The peak at 794 cm⁻¹ belongs to the stretching vibration of Si-O. -1The characteristic absorption peak at 1596 cm⁻¹ is the stretching vibration peak of Al-O and Si-O; in the Fourier transform infrared spectrum of hyperbranched zinc phthalocyanine, the peak at 1596 cm⁻¹ is... -1 1220cm -1 744cm -1 These are characteristic absorption peaks of the phthalocyanine ring in hyperbranched zinc phthalocyanine. From Figure 1 It was found that the dielectric composite material of exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylether nitrile ketone at 2230 cm⁻¹... -1 1643 cm -1 1596 cm -1 744 cm -1 Characteristic peak values for peeled montmorillonite and hyperbranched zinc phthalocyanine were observed in various locations, except for polyarylether nitrile ketone, proving the successful preparation of the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylether nitrile ketone dielectric composite material.
[0046] Experimental Example 2 This experimental example will use scanning electron microscopy to characterize the polyarylene ether ketone, exfoliated montmorillonite, hyperbranched zinc phthalocyanine prepared in Example 1, and the exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composites prepared in Examples 1-6 with mass fractions of 0%, 1%, 2%, 3%, 6%, and 9%, respectively. The results are as follows: Figure 2 As shown in the figure, a is hyperbranched zinc phthalocyanine, b is delaminated montmorillonite, c is polyarylene ether ketone, and di is a delaminated montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composite material with filler mass fractions of 0%, 1%, 2%, 3%, 6%, and 9%, respectively.
[0047] As shown in the figure, hyperbranched zinc phthalocyanine is granular; the peeled montmorillonite is stacked in a lamellar structure with a lamellar diameter greater than 15 micrometers; the cross-section of the polyarylether nitrile ketone pure film exhibits typical ductile fracture with a herringbone ridge pattern and a rough fracture surface; in Figure d, the hyperbranched zinc phthalocyanine is dispersed in the polyarylether nitrile ketone matrix without obvious aggregation; as the mass fraction of the peeled montmorillonite filler increases, the lamellar montmorillonite is evenly distributed in the matrix without obvious agglomeration.
[0048] Experimental Example 3 This experiment will use a dielectric constant analyzer to investigate the relationship between the dielectric constant and frequency of the polyarylene ether nitrile ketone (PAHK) composite films prepared by the layer-by-layer scraping method in Example 1, and the PAHK / hyperbranched zinc phthalocyanine / PAHK composite films prepared in Examples 1-6 with filler mass fractions of 0%, 1%, 2%, 3%, 6%, and 9%, respectively. The results are as follows: Figure 3 As shown.
[0049] The dielectric constant of the exfoliated montmorillonite / hyperbranched zinc phthalocyanine / polyarylether ketone dielectric composite material filled with exfoliated montmorillonite and hyperbranched zinc phthalocyanine significantly improved, and the dielectric constant increased with increasing filler content. At a frequency of 1 kHz, the dielectric constant of the polyarylether ketone-based composite dielectric material filled with 9 wt% montmorillonite was 7.4, which was 2.17 times that of the polyarylether ketone matrix under the same conditions, representing an increase of 217%.
[0050] Test Example 4 This experiment investigates the relationship between the dielectric constant and frequency of polyarylene ether nitrile ketone (PAHK) prepared by the casting method in Comparative Example 1, and the peeled montmorillonite / hyperbranched zinc phthalocyanine / PAHK dielectric composite materials prepared in Comparative Examples 1-6 with filler mass fractions of 0%, 1%, 2%, 3%, 6%, and 9 wt%, respectively. The results are as follows: Figure 4 As shown.
[0051] Compared to the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composite material prepared by the layer-by-layer film-casting method in the examples, the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composite material prepared by the casting film-casting method has a lower dielectric constant. Because the layer-by-layer film-casting method controls the thickness, the montmorillonite sheets are laterally laid flat within the layers of film, which can block the growth of electrical trees, thereby extending the breakdown path and improving the breakdown strength. The filler can also be arranged in a direction perpendicular to the electric field, exhibiting stronger interfacial polarization than other arrangements, thus resulting in a higher dielectric constant.
[0052] Experimental Example 5 This experimental example will characterize the flexibility of the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylethernitrile ketone composite film prepared in Example 1. Figure 5 The images show actual photos of a 9% (by mass) stripped montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone composite film before and after bending and folding. Image a is the unbent / unfolded image, images b and c are the bent images, and image d is the folded image. Figure 5 As can be seen from the present invention, the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone dielectric composite material can still be bent and folded into any shape without damage when the mass content of peeled montmorillonite filler is 9%, exhibiting good flexibility.
[0053] Experimental Example 6 This experiment uses a universal testing machine to investigate the tensile strength, tensile modulus, and elongation at break of the polyarylether ketone composite films prepared by the layer-by-layer scraping method in Example 1, and the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylether ketone composite films prepared in Examples 1-6 with filler mass fractions of 0%, 1%, 2%, 3%, 6%, and 9%, respectively. The results are shown in Table 1.
[0054] As shown in Table 1, the tensile strength, tensile modulus, and elongation at break of the peeled montmorillonite / hyperbranched zinc phthalocyanine / polyarylene ether ketone composite film prepared by the present invention tend to decrease with the increase of filler. When the content of peeled montmorillonite filler is 9 wt%, the tensile strength and tensile modulus are still higher than 90 MPa and 2500 MPa, respectively. This means that the composite material has excellent mechanical properties and can be used as a flexible dielectric material.
[0055] Table 1 The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A two-dimensional layered silicate / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material, characterized in that, Comprising: Using poly(aryl ether nitrile ketone) as the matrix, hyperbranched metal phthalocyanine and two-dimensional layered silicate as fillers, the mass ratio of hyperbranched metal phthalocyanine is less than or equal to 2%, and the mass ratio of two-dimensional layered silicate filler is less than or equal to 9%.
2. A method for preparing the two-dimensional layered silicate filler / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material according to claim 1, characterized in that, Comprising: (1) Preparation of poly(aryl ether nitrile ketone): Using 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile, 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone and a diphenol compound as comonomers, under the catalysis of potassium carbonate, a nucleophilic substitution polycondensation reaction is carried out using a composite solvent system composed of one of N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide and toluene. After the viscosity no longer increases, it is cooled. After cooling, the product is precipitated, washed and purified to obtain the poly(aryl ether nitrile ketone); (2) Preparation of hyperbranched metal phthalocyanine: First, phloroglucinol, 4-nitrophthalonitrile and potassium carbonate are dissolved in the organic solvent N,N-dimethylformamide, and a multi-functional phthalonitrile is prepared by a constant temperature water bath reaction. Then, the multi-functional phthalonitrile and a metal salt are heated under reflux with mechanical stirring to prepare hyperbranched metal phthalocyanine; (3) Exfoliation of two-dimensional layered silicate: The two-dimensional layered silicate is exfoliated by a heating / vaporization method; (4) Solution blending: First, the hyperbranched metal phthalocyanine and the exfoliated two-dimensional layered silicate are dispersed in a solvent to form a blend solution, and then the poly(aryl ether nitrile ketone) is added to the blend solution to obtain a mixed solution; (5) Preparation of dielectric composite material: Using a layer-by-layer scraping method, the mixed solution is made into a composite film; the solvent in the composite film is removed, and after removal, it is cooled and peeled off, and then hot pressing treatment is carried out to prepare the two-dimensional layered silicate / hyperbranched metal phthalocyanine / poly(aryl ether nitrile ketone) dielectric composite material.
3. The preparation method according to claim 2, characterized in that, In step (1), the molar ratio of the 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile, the diphenol compound and the 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone is n:(n + m):m, where 0 < n / (n + m) ≤ 50%, and the diphenol compound is one or more of phenolphthalein, biphenol, hydroquinone, resorcinol and bisphenol S; the volume ratio of N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide to toluene is 3:1; the molar ratio of potassium carbonate to 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile is 3:1; the solid content of the nucleophilic substitution polycondensation reaction system is 30% to 4. The preparation method according to claim 2, characterized in that, In step (2), the molar ratio of phloroglucinol, the 4-nitrophthalonitrile and the potassium carbonate is 1:3:4.5; the total mass concentration of the three components of phloroglucinol, the 5. The preparation method according to claim 2, characterized in that, In step (3), 2-5g of two-dimensional layered silicate material is placed in a beaker; heated at 100℃ for 10-20min, then 50-100mL of liquid nitrogen is poured in, and after it evaporates naturally, this step is repeated three times; then the obtained sample is dried in an oven at 60℃ for 8h to obtain the delaminated two-dimensional layered silicate, wherein the two-dimensional layered silicate filler includes at least one of montmorillonite, muscovite and talc.
6. The preparation method according to claim 2, characterized in that, In step (4), 0.02g-0.04g of hyperbranched metal phthalocyanine and 0.02g-0.18g of exfoliated two-dimensional layered silicate filler are first dissolved in 12-24mL of solvent. The mixture is ultrasonicated for 5min at a stirring speed of 200-300r / min and 160℃, and stirred for 1-2h. Then, 1-2g of polyarylether nitrile ketone is added and stirred until the matrix resin is completely dissolved and the filler is mixed evenly to prepare a mixed solution.
7. The preparation method according to claim 6, characterized in that, Hyperbranched metal phthalocyanine and exfoliated two-dimensional layered silicates are dispersed in N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.
8. The preparation method according to claim 2, characterized in that, In step (5), the dispersed mixed solution is poured evenly onto a horizontal glass plate in an oven in multiple batches, and the film is scraped layer by layer to a preset thickness to obtain a composite film; then the solvent in the composite film is removed by gradient heating; after removing the solvent, it is naturally cooled to room temperature, and the composite film is peeled off from the glass plate. After hot pressing at a temperature of 140-200℃ and a pressure of 15-25MPa, a two-dimensional layered silicate filler / hyperbranched metal phthalocyanine / polyarylene ether nitrile ketone composite film is obtained.
9. The preparation method according to claim 8, characterized in that, Solvent removal from the composite membrane by gradient heating involves heating the composite membrane at 80℃ for 1 hour, 100℃ for 1 hour, 120℃ for 1 hour, 160℃ for 2 hours, 200℃ for 2 hours, and 220℃ for 2 hours to remove the solvent.
10. The application of a two-dimensional layered silicate filler / hyperbranched metal phthalocyanine / polyarylether nitrile ketone dielectric composite material prepared by the preparation method according to any one of claims 17 in the preparation of thin film capacitors.