Polyarylene ether nitrile wear-resistant dielectric composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of material preparation, and relates to a polyarylene ether nitrile wear-resistant dielectric composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: firstly, synthesizing poly (arylene ether nitrile) matrix resin with a phthalonitrile-terminated biphenyl structure by adopting a nucleophilic substitution reaction, and secondly, introducing a copper phthalocyanine modification layer on the surface of a molybdenum disulfide nanosheet by utilizing a chemical grafting method, so as to prepare the novel functional nanofiller. The cyano group of copper phthalocyanine in the functionalized nanofiller not only can improve the compatibility between the molybdenum disulfide nanosheet and the polyarylene ether nitrile matrix, but also can be chemically crosslinked with the cyano group of the matrix resin, and then the cyano group and the cyano group are combined through a film casting method and then subjected to a solid-phase chemical reaction to prepare the composite material. The molybdenum disulfide nanosheets have the effects of improving the wear resistance and the dielectric constant, and the finally prepared composite material has the advantages of high glass transition temperature, high dielectric constant, excellent wear resistance, low friction coefficient, good processability, simple and efficient preparation process, and suitableness for large-scale production and application.

Description

Technical Field

[0001] This invention belongs to the field of materials preparation technology, and relates to the synthesis of polymer materials and the preparation process of nanocomposite materials. Specifically, it relates to a method for preparing a wear-resistant dielectric composite material of polyarylene ether nitrile, and more particularly to a method for preparing a high-dielectric polyarylene ether nitrile composite material for high wear-resistant and high-temperature energy storage film capacitors. Background Technology

[0002] As electronic devices evolve towards integration, lightweight design, and long lifespan, film capacitors not only need excellent dielectric properties and thermal stability but also face the challenge of wear resistance under complex operating conditions. Traditional dielectric materials, such as polyvinylidene fluoride (PVDF), while possessing high dielectric constants and breakdown strength at room temperature, have operating temperatures below 120°C and poor wear resistance. In environments with frequent friction or vibration, they are prone to surface wear and dielectric degradation, severely impacting device lifespan. Therefore, developing dielectric composite materials that combine high glass transition temperature, high dielectric constant, and excellent wear resistance has become crucial for expanding the application scenarios of dielectric materials.

[0003] To improve the dielectric properties of polymer materials, researchers often construct composite systems by filling them with functional fillers. However, traditional fillers suffer from the problem of simultaneously achieving high dielectric strength and high wear resistance. Molybdenum disulfide (MoS2), as a typical layered sulfide, possesses a unique graphene-like sheet structure with weak van der Waals forces between the sheets, facilitating slippage. It is a recognized high-efficiency solid lubricant widely used in wear-resistant materials, significantly reducing the coefficient of friction of composite materials. Simultaneously, the conjugated electronic structure and high specific surface area of ​​MoS2 enable it to form charge transport pathways within the polymer matrix, contributing to an increase in the dielectric constant of the composite material and achieving synergistic optimization of wear resistance and dielectric properties. Polyarylene ether nitrile (PEN), as a thermoplastic specialty polymer, possesses excellent thermal stability, mechanical strength, and processability. Its strongly polar -CN side chain groups endow it with basic dielectric properties, and the cyano groups can further enhance the material's temperature resistance and structural stability through cyclization crosslinking reactions, making it an ideal matrix for preparing high-performance dielectric composite materials. However, there are interfacial compatibility issues between molybdenum disulfide nanosheets and the polymer matrix. Direct filling easily leads to agglomeration, which not only fails to fully utilize its wear resistance and dielectric enhancement effects but may also reduce the material's breakdown strength.

[0004] In existing technologies, although there are studies on using molybdenum disulfide for polymer wear-resistant modification, most of them focus on improving the wear resistance of a single property, neglecting the synergistic optimization of dielectric properties. At the same time, the interfacial bonding problem between the filler and the matrix has not been effectively solved, making it difficult for the composite material to meet the integrated requirements of high wear resistance, high dielectric and high temperature resistance. Summary of the Invention

[0005] Therefore, the purpose of this invention is to provide a wear-resistant dielectric composite material of polyarylether nitrile, its preparation method, and its application. By improving the compatibility between molybdenum disulfide and the polyarylether nitrile matrix through surface modification, the wear resistance, dielectric properties, and heat resistance are simultaneously enhanced, which has significant research value and application prospects.

[0006] Specifically, this invention employs a synergistic technical route involving nucleophilic substitution reaction, chemical grafting modification, solution blending, and solid-phase crosslinking reaction. A copper phthalocyanine modification layer is introduced onto the surface of molybdenum disulfide nanosheets via chemical grafting. The conjugated structure of copper phthalocyanine enhances dielectric properties. Simultaneously, the cyano groups in the modification layer undergo a crosslinking reaction with the cyano groups of the matrix resin, improving interfacial compatibility and enhancing wear resistance in conjunction with the layered sliding properties of molybdenum disulfide. Ultimately, a polyarylene ether nitrile composite film exhibiting high glass transition temperature, high dielectric constant, low coefficient of friction, and excellent mechanical stability is obtained, providing theoretical support and technical assurance for the large-scale production of high-wear-resistant, high-dielectric energy storage materials.

[0007] It should be noted that the molybdenum disulfide nanofiller with copper phthalocyanine modified layer designed in this invention, on the one hand, enhances the interfacial bonding between copper phthalocyanine and the polyarylene ether nitrile matrix through structural compatibility enhancement, thus avoiding filler agglomeration; on the other hand, the 18π electron conjugated structure of copper phthalocyanine can improve the dielectric constant, the molybdenum disulfide sheet structure reduces the friction coefficient, and the cyano crosslinking reaction restricts molecular chain movement, thereby improving the heat resistance level, achieving a three-in-one performance optimization of "wear resistance-dielectricity-heat resistance".

[0008] To achieve the above objectives, the present invention provides the following technical solution: The first technical objective of this invention is to provide a method for preparing a wear-resistant dielectric composite material of polyarylether nitrile, specifically including the following steps: Step 1: Synthesis of phthalonitrile-terminated biphenyl polyarylether nitrile; 1.1 A three-necked flask reaction system equipped with a thermometer, a water separator, a reflux condenser, and a mechanical stirrer was constructed. 4,4-dihydroxybiphenyl and 2,6-dichlorobenzonitrile were added to the flask as reactants, and potassium carbonate was added as a catalyst. The molar ratio of the three was strictly controlled at 1.01:1.00:1.20. A mixture of 15 mL toluene and 15 mL water was pre-injected into the water separator for water separation during the reaction.

[0009] 1.2 The mixed powder obtained in step 1.1 is added to a mixed solvent composed of N-methylpyrrolidone (NMP) and toluene to prepare a mixed solution A; wherein the amount of mixed solvent added is 1~1.5mL per 1g of mixed powder, and the volume ratio of NMP to toluene in the mixed solvent is 3:1.

[0010] 1.3 The mixture A was subjected to a programmed temperature increase reaction: the temperature was increased to 145~160℃ using an electric heating mantle and kept at a constant temperature for 2~4 hours; the temperature was further increased to 170~175℃ and kept at a constant temperature for 1~2 hours; the water separator valve was quickly opened to release 5 mL of toluene and then closed; the temperature was then increased to 180~190℃ and kept at a constant temperature for 2~4 hours; the temperature was then decreased to 80~90℃ in the later stage of the reaction, and 4-nitrophthalonitrile, potassium carbonate and NMP were added to the system, wherein each 1 g of potassium carbonate and 0.5~1 g of 4-nitrophthalonitrile powder corresponded to 5~10 mL of NMP, and the mixture was kept at a constant temperature of 80~90℃ for 4~8 hours to obtain a viscous hot solution.

[0011] 1.4 The above hot solution is slowly injected into a 0.1~0.2 mol / L hydrochloric acid solution and stirred rapidly to form a thin strip solid A; after soaking solid A in hydrochloric acid solution for 12 h, it is crushed and washed repeatedly with deionized water 3~5 times until the washing solution is neutral; the washed powder is placed in a vacuum oven and dried for 12 h to obtain a polyarylene ether nitrile with a phthalonitrile-terminated biphenyl structure.

[0012] Step 2: Preparation of molybdenum disulfide nanosheets with copper phthalocyanine modification layer 2.1 Add molybdenum disulfide nanosheets and 2-3 mol / L sodium hydroxide solution to a three-necked flask, wherein each 1 g of molybdenum disulfide nanosheets corresponds to 30-50 mL of sodium hydroxide solution; after ultrasonic dispersion and mechanical stirring, transfer to a water bath and stir at room temperature for 24 h to obtain liquid mixture B; filter mixture B, wash with deionized water and ethanol alternately until neutral, and dry in a vacuum oven at 60 °C for 12 h to obtain hydroxylated molybdenum disulfide nanosheets (MoS2-OH).

[0013] 2.2 Hydroxylated molybdenum disulfide nanosheets were added to N,N-dimethylformamide (DMF) and ultrasonically dispersed to obtain a mixed solution C. At a ratio of 100-120 mL DMF, 10-15 mL isophorone diisocyanate, 1-3 g 3-aminophenoxyphthalonitrile, and 100-150 μL stannous isooctanoate per 1 g of hydroxylated molybdenum disulfide nanosheets, isophorone diisocyanate was first added to mixed solution C, and the reaction was carried out at 50 °C for 6-8 h under nitrogen protection. Then, 3-aminophenoxyphthalonitrile and stannous isooctanoate were added, and the temperature was raised to 85 °C for another 4-6 h. After the reaction was completed, the product was washed repeatedly with methanol, ethanol, and deionized water, and dried at 50 °C for 12 h to obtain cyano-modified molybdenum disulfide nanosheets (MoS2-CN).

[0014] 2.3 Cyano-modified molybdenum disulfide nanosheets were added to N,N-dimethylacetamide (DMAc) and ultrasonically dispersed to obtain a mixture D; biphenyl-type phthalonitrile resin and cuprous chloride were added to mixture D, and the mixture was heated under reflux for 2-6 hours to obtain a mixed solution F; the mixed solution F was filtered, and the resulting black powder was washed and purified with DMAc and deionized water, and then dried in a vacuum oven at 60℃ for 12 hours to finally obtain molybdenum disulfide nanosheets (MoS2-CuPc) with a copper phthalocyanine modified layer.

[0015] Step 3: Preparation of PEN / MoS2-CuPc composite thin film 3.1 The phthalonitrile-terminated biphenyl polyarylene nitrile obtained in step 1 and the MoS2-CuPc nanofiller obtained in step 2 were added to NMP respectively: the polyarylene nitrile was heated and stirred at 200℃ for 1~3h to form a uniform polyarylene nitrile hot solution I; the MoS2-CuPc nanofiller was ultrasonically dispersed and mechanically stirred at room temperature for 1h to form a stable filler dispersion II.

[0016] 3.2 The filler dispersion II was slowly added to the polyarylene ether nitrile hot solution I. After stirring at 200℃ for 2 hours, a film was formed by casting. The heating program for casting was as follows: 80℃, 100℃, 120℃, and 160℃ for 1 hour each, and finally held at 200℃ for 2-4 hours to obtain the PEN / MoS2-CuPc precursor film. The amount of MoS2-CuPc nanofiller added was 5wt% to 40wt% of the mass of polyarylene ether nitrile.

[0017] Step 4: Preparation of polyarylethernitrile wear-resistant dielectric composite material The PEN / MoS2-CuPc precursor film obtained in step 3 was placed in a muffle furnace and kept at 320~350℃ for 4~8h. During this period, cross-linking reactions occurred between polyarylene ether nitrile molecules and with the cyano groups on the surface of the MoS2-CuPc filler. After the reaction was completed, the mixture was naturally cooled to room temperature to obtain the polyarylene ether nitrile wear-resistant dielectric composite material.

[0018] Specifically, the preparation of the above-mentioned polyarylene ether nitrile wear-resistant dielectric composite material is achieved through a multi-step reaction synergistically constructing a high-performance composite material, and its core mechanism is as follows: A polyarylene ether nitrile with a phthalonitrile-terminated biphenyl structure was synthesized using a nucleophilic substitution reaction, providing a matrix resin with both thermal stability and dielectric properties for the composite material. Hydroxyl groups, cyano groups, and copper phthalocyanine modification layers were sequentially introduced onto the surface of molybdenum disulfide nanosheets via chemical grafting to form a functionalized filler, MoS2-CuPc. The cyano groups in the modification layer can crosslink with the cyano groups of the matrix resin, simultaneously improving the interfacial compatibility between molybdenum disulfide and the polyarylene ether nitrile and preventing filler agglomeration. The layered structure of the molybdenum disulfide nanosheets allows for lamellar sliding during friction, significantly reducing the coefficient of friction of the composite material and imparting excellent wear resistance. Its conjugated electronic structure synergistically enhances the dielectric constant of the composite material with the 18π electron system of copper phthalocyanine. Through casting and subsequent solid-phase crosslinking, the composite material forms a dense and stable crosslinked structure, further optimizing its heat resistance and structural stability. Ultimately, a polyarylene ether nitrile composite film with high glass transition temperature, high dielectric constant, low coefficient of friction, and good processability is obtained. The preparation process is simple and controllable, suitable for large-scale production applications.

[0019] The second technical objective of this invention is to provide a wear-resistant dielectric composite material of polyarylether nitrile prepared by the method described above.

[0020] The third technical objective of this invention is to provide an application of the polyarylene ether nitrile wear-resistant dielectric composite material in a high-temperature energy storage film capacitor prepared by the method described above.

[0021] As can be seen from the above technical solutions, compared with the prior art, the polyarylene ether nitrile wear-resistant dielectric composite material, its preparation method, and its application provided by the present invention have the following superior effects: 1) Synergistic optimization of wear resistance and dielectric properties: The layered sliding characteristics of molybdenum disulfide nanosheets combined with the electronic conjugation effect of copper phthalocyanine solve the technical bottleneck of traditional materials that are difficult to balance wear resistance and dielectric properties, and achieve the dual goals of significantly reducing the coefficient of friction and effectively improving the dielectric constant. 2) Strong interfacial bonding: Through the cross-linking reaction between the cyano groups of the copper phthalocyanine modified layer and the matrix resin, a strong interfacial bond is constructed, which avoids filler agglomeration and ensures the stability of the mechanical and dielectric properties of the composite material. 3) Excellent heat resistance: The aromatic heterocyclic structure formed by the cross-linking reaction restricts the movement of molecular chains, which greatly increases the glass transition temperature and thermal decomposition temperature of the composite material and broadens the working temperature range of the material. 4) Highly efficient preparation process: The process route adopts a synergistic approach of nucleophilic substitution, chemical grafting, solution casting and post-solid crosslinking. It is simple to operate, the parameters are controllable, no complex equipment is required, and it is suitable for large-scale industrial production.

[0022] In summary, this invention successfully prepared a polyaryletheronitrile composite material that integrates high wear resistance, high dielectric strength, and high heat resistance, providing new material support and technical solutions for the development of devices such as high wear-resistant and high-temperature-resistant energy storage thin-film capacitors. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0024] Figure 1 This is a comparison chart of glass transition temperatures for Examples 1-3 and Comparative Examples 1-2.

[0025] Figure 2 The thermal expansion coefficients of Examples 1-3 and Comparative Examples 1-2 are shown in the range of 35-350℃.

[0026] Figure 3 The graph shows the dielectric constant comparison data of Examples 1-3 and Comparative Examples 1-2 at a frequency of 1kHz.

[0027] Figure 4 This is a comparison chart of friction coefficients between Examples 1-3 and Comparative Examples 1-2. Detailed Implementation

[0028] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.

[0029] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0030] Example 1 Synthesis of phthalonitrile-terminated biphenyl polyarylether nitrile: 1.1 Add 9.4g of 4,4-dihydroxybiphenyl, 8.6g of 2,6-dichlorobenzonitrile and 8.3g of potassium carbonate to a three-necked flask, and add 15mL of toluene and 15mL of water to a water separator; 1.2 Add 30 mL of a mixed solvent of NMP and 10 mL of toluene to form mixture A; 1.3 The reaction was carried out at a programmed temperature: 150 ℃ for 2 h → 170 ℃ for 1 h → 5 mL toluene was released → 180 ℃ for 3 h → the temperature was lowered to 90 ℃, 1.5 g potassium carbonate, 1 g 4-nitrophthalonitrile and 9 mL NMP were added, and the temperature was maintained at 80 ℃ for 5 h. 1.4 The hot solution was injected into a 0.2 mol / L hydrochloric acid solution, and after soaking in the hydrochloric acid solution for 12 hours, it was crushed and washed repeatedly with deionized water 3 to 5 times until the washing solution was neutral. The washed powder was placed in a vacuum oven and dried for 12 hours to obtain polyarylene ether nitrile.

[0031] Preparation of MoS2-CuPc functionalized nanofillers: 2.1 Add 2g of molybdenum disulfide nanosheets and 80mL of 2mol / L sodium hydroxide solution to a three-necked flask, stir at room temperature for 24h, and then wash and dry to obtain MoS2-OH; 2.2 Add 100 mL of DMF and sonicate, then add 10 mL of isophorone diisocyanate and react at 50 °C for 7 h; then add 2 g of 3-aminophenoxyphthalonitrile and 150 μL of stannous isooctanoate and react at 85 °C for 5 h. After washing three times with methanol, ethanol and deionized water in sequence, and drying at 50 °C for 12 h, MoS2-CN is obtained. 2.3 Add 50 mL of DMAc and sonicate. Add 1 g of biphenyl phthalonitrile resin and 0.1 g of cuprous chloride. Heat under reflux for 4 h. After purification by washing with DMAc and deionized water three times, dry in a vacuum oven at 60 °C for 12 h to obtain MoS2-CuPc.

[0032] Preparation of PEN / MoS2-CuPc composite material: 3.1 Add NMP to polyarylene ether nitrile and stir at 200℃ for 2h to obtain hot solution I; add 10wt% MoS2-CuPc to NMP and sonicate for 1h to obtain dispersion II; 3.2 Mixture I and dispersion II were stirred at 200℃ for 2 hours and then cast into a film (1 hour each at 80℃, 100℃, 120℃, and 160℃, followed by 2 hours of heat treatment at 200℃) to obtain the precursor film.

[0033] Preparation of wear-resistant dielectric composite materials of polyarylether nitrile: The precursor film was kept in a muffle furnace at 340℃ for 5 hours and then cooled to room temperature to obtain a wear-resistant dielectric composite material of polyarylether nitrile.

[0034] Performance test results: glass transition temperature 252℃, coefficient of thermal expansion (35-350℃) 78 ppm / ℃, dielectric constant at 1kHz 6.2, coefficient of friction 0.22.

[0035] Example 2 The difference between this embodiment and Example 1 is that the amount of MoS2-CuPc added in step 3.1 is 20 wt% of the mass of polyarylether nitrile, while the rest of the preparation steps are exactly the same.

[0036] Performance test results: glass transition temperature 266℃, coefficient of thermal expansion (35-350℃) 35 ppm / ℃, dielectric constant at 1kHz 9.7, coefficient of friction 0.18.

[0037] Example 3 The difference between this embodiment and Example 1 is that the amount of MoS2-CuPc added in step 3.1 is 40 wt% of the mass of polyarylene ether nitrile, while the rest of the preparation steps are exactly the same.

[0038] Performance test results: glass transition temperature 278℃, coefficient of thermal expansion (35-350℃) 21 ppm / ℃, dielectric constant at 1kHz 14.1, coefficient of friction 0.15.

[0039] Comparative Example 1 The difference between this comparative example and Example 1 is that: in step 2, the molybdenum disulfide nanosheets were not modified with copper phthalocyanine, and 20wt% pure molybdenum disulfide nanosheets were directly added to the polyarylene ether nitrile matrix; the rest of the preparation steps were exactly the same.

[0040] Performance test results: glass transition temperature 242℃, coefficient of thermal expansion (35-350℃) 84 ppm / ℃, dielectric constant at 1kHz 9.2, coefficient of friction 0.23.

[0041] Comparative Example 2 This comparative example is a pure polyarylene ether nitrile film, and the preparation steps are as follows: Phthalate-terminated biphenyl polyarylene nitrile was synthesized according to step 1 of Example 1; Take 1g of polyarylene ether nitrile powder and add it to 15mL of NMP. Stir at 200℃ for 2h to obtain a hot solution. Cast film (80℃, 100℃, 120℃, 160℃ for 1 hour each, and 200℃ for 2 hours), the film is kept in a muffle furnace at 340℃ for 5 hours, and then cooled to room temperature to obtain cross-linked PEN film.

[0042] Performance test results: glass transition temperature 240℃, coefficient of thermal expansion (35-350℃) 112 ppm / ℃, dielectric constant at 1kHz 3.8, coefficient of friction 0.31.

[0043] Depend on Figures 1-4The performance data in Examples 1, 2, and 3 show that the performance changes are due to different filler contents. Since the cyano groups in the CuPc filler-modified layer can undergo chemical cross-linking reactions with the cyano groups in the PEN matrix, the number of chemical cross-linking sites increases with the increase of filler content, and the cross-linking density of the composite film also increases. Therefore, with the increase of filler content, the glass transition temperature gradually increases. Figure 1 The coefficient of thermal expansion decreases ( Figure 2 The coefficient of friction also decreases. Figure 4 Furthermore, the increased amount of high-dielectric MoS2-CuPc filler also increases the dielectric constant of the composite film. Figure 3 ).

[0044] In Comparative Example 1, pure MoS2 nanofiller without CuPc surface modification was directly added. Therefore, the compatibility between this inorganic filler and the polymer PEN is poor. Furthermore, because its surface lacks cyano groups that can chemically crosslink with the PEN matrix, its degree of crosslinking is low, resulting in lower performance. In Comparative Example 2, as a pure PEN film without the addition of inorganic nanofiller, its performance is even worse.

[0045] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a wear-resistant dielectric composite material of polyarylether nitrile, characterized in that, A process route combining nucleophilic substitution reaction, chemical grafting, solution casting, and post-solid-phase chemical reaction was adopted to prepare polyarylene ether nitrile composite films exhibiting high glass transition temperature, high dielectric constant, and excellent wear resistance. The specific steps are as follows: 1) Synthesis of phthalonitrile-terminated biphenyl polyarylether nitrile; 2) Preparation of molybdenum disulfide nanofillers with copper phthalocyanine modified layers; 3) Preparation of polyarylene ether nitrile-based composite films; The phthalonitrile-terminated biphenyl-structured polyarylene ether nitrile obtained in step 1) and the molybdenum disulfide nanofiller with copper phthalocyanine modification layer prepared in step 2) were respectively added to N-methylpyrrolidone. Among them, the phthalonitrile-terminated biphenyl-structured polyarylene ether nitrile was heated and stirred to form a uniform polyarylene ether nitrile hot solution I, and the molybdenum disulfide nanofiller with copper phthalocyanine modification layer was ultrasonically dispersed and mechanically stirred to form a stable filler dispersion II. The filler dispersion II was added to the polyarylene ether nitrile hot solution I, and after heating and stirring, a film was formed by casting to obtain a PEN / MoS2-CuPc composite film. 4) Preparation of wear-resistant dielectric composite materials of polyarylethernitrile; The PEN / MoS2-CuPc composite film obtained in step 3) was subjected to high-temperature treatment and then naturally cooled to room temperature to finally obtain the polyarylether nitrile wear-resistant dielectric composite material.

2. The preparation method of the polyarylene ether nitrile wear-resistant dielectric composite material according to claim 1, characterized in that, For every 1g of phthalonitrile-terminated biphenyl-structured polyarylene ether nitrile powder, 10-15mL of N-methylpyrrolidone is added; for every 1g of molybdenum disulfide nanofiller with a copper phthalocyanine modification layer, 10-15mL of N-methylpyrrolidone is added; the mass ratio of the polyarylene ether nitrile to the molybdenum disulfide nanofiller with a copper phthalocyanine modification layer is 1:(0.01-0.5).

3. The method for preparing the polyarylene ether nitrile wear-resistant dielectric composite material according to claim 1 or 2, characterized in that, The heating process for film formation by casting is as follows: holding at 80℃, 100℃, 120℃ and 160℃ for 0.5~2h each, followed by holding at 200℃ for 2~4h.

4. The preparation method of the polyarylene ether nitrile wear-resistant dielectric composite material according to claim 1, characterized in that, In step 4), the PEN / MoS2-CuPc composite film is placed in a muffle furnace and kept at 320~350℃ for 4~8h.

5. The method for preparing the polyarylene ether nitrile wear-resistant dielectric composite material according to claim 1, characterized in that, Step 1) The specific steps for synthesizing the phthalonitrile-terminated biphenyl polyarylether nitrile are as follows: 4,4-Dihydroxybiphenyl and 2,6-dichlorobenzonitrile were added as reactants to a three-necked flask, and potassium carbonate was added as a catalyst. The mixture was stirred until homogeneous to obtain a powdered mixture. The powdered mixture was then added to a mixed solvent of N-methylpyrrolidone and toluene to prepare a mixed solution A. Mixed solution A was reacted at 145-160℃ for 2-4 hours, then heated to 170-175℃ and reacted at the same temperature for 1-2 hours, then heated to 180-190℃ and reacted at the same temperature for 2-4 hours. After cooling to 80-90℃, 4-nitrophthalonitrile, potassium carbonate, and N-methylpyrrolidone were added to the reaction system and stirred until homogeneous. The mixture was then reacted at 80-90℃ for 4-8 hours to obtain a hot solution. The hot solution was slowly poured into a 0.1-0.2 mol / L hydrochloric acid solution and stirred rapidly to form a thin strip-shaped solid A. Solid A was soaked in hydrochloric acid solution for 12 hours and then pulverized. It was washed with deionized water 3 to 5 times until the washing solution was neutral. The washed powder was then dried in a vacuum oven for 12 hours to obtain polyarylene ether nitrile with phthalonitrile-terminated biphenyl structure.

6. The method for preparing the polyarylene ether nitrile wear-resistant dielectric composite material according to claim 5, characterized in that, The molar ratio of 4,4-dihydroxybiphenyl, 2,6-dichlorobenzonitrile, and potassium carbonate is 1.01:1.00:1.20; 1~1.5 mL of mixed solvent is added for every 1 g of the mixture powder, and the volume ratio of N-methylpyrrolidone to toluene in the mixed solvent is 3:1; 5~10 mL of N-methylpyrrolidone is added for every 1 g of potassium carbonate and 0.5~1 g of 4-nitrophthalonitrile mixed powder.

7. The method for preparing the polyarylene ether nitrile wear-resistant dielectric composite material according to claim 1, characterized in that, Step 2) The specific steps for preparing molybdenum disulfide nanofillers with copper phthalocyanine modification layers are as follows: (1) Add molybdenum disulfide nanosheets and 2-3 mol / L sodium hydroxide solution to a three-necked flask, wherein each 1 g of molybdenum disulfide nanosheets corresponds to 30-50 mL of sodium hydroxide solution; after ultrasonic dispersion combined with mechanical stirring, transfer to a water bath and stir at room temperature for 24 h to obtain liquid mixture B; filter liquid mixture B, wash the filter residue alternately with deionized water and ethanol until neutral, and dry it in a vacuum oven to obtain hydroxylated molybdenum disulfide nanosheets MoS2-OH; (2) Hydroxylated molybdenum disulfide nanosheets were added to N,N-dimethylformamide (DMF) and ultrasonically dispersed to obtain a mixture C. According to the ratio of 100~120mL DMF, 10~15mL isophorone diisocyanate, 1~3g 3-aminophenoxyphthalonitrile and 100~150μL stannous isooctanoate for every 1g of hydroxylated molybdenum disulfide nanosheets, isophorone diisocyanate was first added to the mixture C and reacted at 50℃ for 6~8h under nitrogen protection. Then 3-aminophenoxyphthalonitrile and stannous isooctanoate were added and the temperature was raised to 85℃ to continue the reaction for 4~6h. After the reaction was completed, the product was washed with methanol, ethanol and deionized water in sequence, and dried at 50℃ for 12h to obtain cyano-modified molybdenum disulfide nanosheets MoS2-CN. (3) Add cyano-modified molybdenum disulfide nanosheets to N,N-dimethylacetamide and disperse them by ultrasonication to obtain a mixture D; add biphenyl-type phthalonitrile resin and cuprous chloride to the mixture D and heat under reflux for 2-6 h to obtain a mixed solution F; filter the mixed solution F to obtain a black powder; wash and purify the black powder with N,N-dimethylacetamide and deionized water, and dry it in a vacuum oven at 60°C for 12 h to obtain molybdenum disulfide nanosheets MoS2-CuPc with copper phthalocyanine modification layer.

8. A wear-resistant dielectric composite material of polyarylether nitrile prepared by the method described in claim 1.

9. The application of a polyarylene ether nitrile wear-resistant dielectric composite material prepared by the method described in claim 1 in a high-temperature energy storage thin-film capacitor.

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