Preparation method of ablation-resistant poly (arylene ether) -zirconium diboride modified boron phenolic-nitrile resin composite material
By combining boron phenolic-nitrile resin copolymerization with polyarylene ether@zirconia diboride filler, an ablation-resistant polyarylene ether@zirconia diboride modified boron phenolic-nitrile resin composite material is formed, which solves the problems of brittleness and insufficient ablation efficiency of traditional phenolic resin in high heat flux environment and realizes a high-performance thermal protection material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SICHUAN GOLDEN ELEPHANT SINCERITY CHEM CO LTD
- Filing Date
- 2026-05-06
- Publication Date
- 2026-07-10
AI Technical Summary
Traditional phenolic resins suffer from brittleness and insufficient ablation efficiency under high heat flux environments. Although existing boron phenolic-nitrile resin copolymer systems have shown some improvement, they still fail to meet the ablation resistance requirements of aerospace and other fields.
Boron phenolic resin was copolymerized with phthalonitrile containing a benzoxazine ring, and polyarylene ether@zirconia diboride filler was added to form an ablation-resistant polyarylene ether@zirconia diboride modified boron phenolic resin-nitrile resin composite material. A new copolymer was formed through chemical reaction. Combined with the synergistic effect of high silica fiber cloth and zirconium diboride, the ablation resistance of the material was improved.
It significantly improves the ablation resistance and char residue of composite materials, reduces linear ablation rate and mass ablation rate, and forms a dense ablation barrier, making it suitable for thermal protection materials for hypersonic vehicles.
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Figure CN122356536A_ABST
Abstract
Description
[0001] Technical Field This invention belongs to the field of polymer materials technology, specifically a method for preparing an ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material.
[0002] Background Technology With the rapid development of aerospace and hypersonic vehicle technologies, increasingly stringent requirements are being placed on the ablation resistance and abrasion resistance of thermal protection materials in extreme environments. Traditional phenolic resins are widely used as matrix resins for ablation-resistant composite materials due to their high char yield and good thermal stability. However, their inherent brittleness and structural defects generated during ablation limit their application in higher heat flux environments.
[0003] Boron-phenolic resins, by introducing boron into phenolic resins, form BO bonds with higher bond energy, significantly improving the resin's heat resistance, char residue, and mechanical properties at high temperatures; however, its ablation efficiency still needs further improvement. To overcome the shortcomings of single boron-phenolic resins, the copolymerization system of boron-phenolic resins and nitrile resins exhibits unique advantages. The active hydrogen of boron-phenolic resins can catalyze the curing of nitrile resins and reduce the cost of traditional nitrile resin systems, while also improving the overall processability of the system; the introduction of nitrile resins greatly improves the system's heat resistance. The copolymerization of the two is not a simple physical mixing; after copolymerization, both the curing reaction peak of boron-phenolic resins and the ring-opening polymerization peak of benzoxazine disappear, indicating that boron-phenolic resins and nitrile resins have formed a new copolymer, and the synthesized prepolymer has a wide processing window and a low initial processing temperature.
[0004] Although the heat resistance of the system has been improved, it is still insufficient to meet the ablation resistance requirements of practical applications such as aerospace. Therefore, we need to conduct further research and development to obtain composite materials with improved overall performance. Summary of the Invention
[0005] The purpose of this invention is to address the problems mentioned in the prior art by providing a method for preparing an ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material. In this method, on the one hand, boron phenolic resin is copolymerized with phthalonitrile containing a benzoxazine ring for modification, which greatly improves the processing performance of the nitrile resin while reducing material costs; on the other hand, polyarylene ether@zirconium diboride filler is added to further improve the ablation resistance of the composite material, thereby increasing the strength of the composite material while also improving the resin's ablation resistance and char residue, resulting in a significant performance improvement.
[0006] To achieve the objectives of this invention, the specific technical solution adopted is as follows: A method for preparing an ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material includes the following steps: (1) Preparation of boron phenolic-acrylic resin copolymer: Boron phenolic resin and PN1 type nitrile resin were solution prepolymerized to prepare boron phenolic resin-nitrile resin copolymer. (2) Preparation of polyarylene ether@zirconium diboride: First, polyarylene ether is dissolved in a solvent, then zirconium diboride is added and ultrasonically stirred. The resulting product is then centrifuged, dried, and ground to finally obtain polyarylene ether@zirconium diboride (filler). (3) Preparation of boron phenolic-nitrile resin solution containing polyarylene ether@zirconium diboride: The polyarylene ether@zirconia diboride filler obtained in step (2) is subjected to ultrasonic (heating and stirring) treatment with the boron phenolic-acrylic resin copolymer obtained in step (1) to obtain a polyarylene ether@zirconia diboride modified boron phenolic-acrylic resin solution. (4) Preparation of polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material: The polyarylene ether@zirconia diboride modified boron phenolic-nitrile resin solution obtained in step (3) is uniformly coated on the prepreg reinforcement, and after drying and pressing, a composite material of polyarylene ether@zirconia diboride modified boron phenolic-nitrile resin is prepared.
[0007] Further, in step (1), the PN1 type nitrile resin is provided by Meishan Jinxiang Chemical Co., Ltd.; the mass ratio of boron phenolic resin to PN1 type nitrile resin is 10~90:90~10 (more preferably 50:50); the temperature during prepolymerization is 60℃~150℃ (more preferably 80℃), and the prepolymerization time is 1~6 h (more preferably 1 h).
[0008] Further, in step (2), the solvent is N,N-dimethylformamide, xylene, N,N-dimethylacetamide, ethanol, N-methylpyrrolidone, etc. The polyarylene ether is an active polyarylene ether, and more specifically, a polyarylene ether nitrile (polyarylene ether) containing reactive functional groups of amine oxime and carboxyl groups; zirconium diboride is a high-temperature resistant ceramic material; The mass ratio of polyarylene ether to zirconium diboride is 20~1:80~99 parts (more preferably 10:90); the ultrasonic treatment time is 1~48h (more preferably 24h).
[0009] Further, in step (3), the mass ratio of polyarylene ether@zirconium diboride filler to boron phenolic-nitrile resin copolymer is 0~5:100~95 (specifically, it can be 1:99, 2:98, 3:97, 4:96, 5:95, etc.); the ultrasonic treatment temperature is 60℃~100℃, and the time is 0.5h~3h.
[0010] Furthermore, the structural formula of the boron phenolic resin described in the above method is shown below: .
[0011] Furthermore, the structural formula of the PN1 type nitrile resin described in the above method is as follows: .
[0012] Furthermore, the structural formula of the active polyarylene ether described in the above method is shown below: .
[0013] Furthermore, the average particle size of zirconium diboride described in the above method is 1-3 micrometers.
[0014] Furthermore, the prepreg reinforcement described in the above method is a high-silica fiber cloth, and the resulting composite material is a composite laminate.
[0015] This invention also protects the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material prepared by the above combinable method steps.
[0016] In this invention, the addition of inorganic fillers as reinforcing phases to the system can further improve the system's ablation resistance. The ablation mechanism of resin-based materials involves the sacrificial loss of surface materials to carry away and consume a large amount of heat energy, thereby confining the extreme high-temperature environment to the material surface and protecting the internal structure. Among many modified fillers, inorganic ceramic particles have become a research hotspot due to their excellent thermal stability. Among them, the ultra-high temperature ceramic material zirconium diboride (ZrB2) has attracted much attention due to its extremely high melting point exceeding 3000℃, excellent thermal conductivity, and outstanding antioxidant ablation resistance. Blending zirconium diboride as a functional filler with high-temperature resistant resins not only simplifies the process and significantly reduces costs, but also qualitatively improves the overall performance of fiber-reinforced composite materials.
[0017] Compared with the prior art, the main advantages of the present invention are as follows: (1) Although boron phenolic resin significantly improves heat resistance, char residue, and high-temperature mechanical properties by introducing boron to form high-energy BO bonds, its inherent brittleness and ablation efficiency remain bottlenecks that urgently need to be overcome. To overcome this limitation, this invention turns to a copolymerization system of boron phenolic resin and nitrile resin. The advantage of this system does not stem from simple physical blending, but rather from molecular-level synergy achieved through chemical reaction—differential scanning calorimetry (DSC) analysis shows that the curing reaction peak of boron phenolic resin and the ring-opening polymerization peak of benzoxazine both disappear after copolymerization, which strongly confirms that a new copolymer is formed. The prepolymer synthesized by this copolymerization reaction also has excellent processability, characterized by a wider processing window and a lower processing initiation temperature, which facilitates the preparation of subsequent composite materials.
[0018] (2) The present invention selects high-silica fiber cloth as the reinforcement of the prepreg, which significantly improves the ablation resistance of the composite material. High-silica fiber cloth (SiO2 content > 96%) has an extremely high melting point and excellent thermal stability. Under extreme ablation environment, the resin matrix consumes a large amount of heat energy through carbonization and ceramization, while the high-silica fiber acts as a strong, non-melting three-dimensional skeleton network embedded in the carbon / ceramic layer. This synergistic effect of "resin sacrificial protection" and "fiber skeleton support" can effectively prevent the ablation layer from peeling off and maintain the structural integrity of the protective layer, thereby significantly reducing the linear ablation rate and mass ablation rate of the composite material.
[0019] (3) In this invention, zirconium diboride filler with excellent ablation resistance is added to boron phenolic-nitrile resin. Zirconium diboride is a recognized ultra-high temperature ceramic with a melting point exceeding 3000℃ and excellent thermal stability. Under high-temperature ablation conditions, ZrB2 can serve as a robust skeleton, effectively resisting the erosion and corrosion of high-temperature heat flow. At the same time, it will oxidize at high temperatures to generate ZrO2 and B2O3; among them, ZrO2 itself has a high melting point and can form a stable structural skeleton, while B2O3, as a viscous glass, can effectively cover and seal cracks and pores on the material surface, preventing oxygen from diffusing inward. This "skeleton-sealing" dual protection mechanism, together with the carbon layer formed after resin carbonization, can construct an extremely dense, stable, and self-healing ablation barrier, thereby significantly reducing the mass ablation rate and linear ablation rate of the material. Attached Figure Description
[0020] 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.
[0021] Figure 1 The image shows the DSC curve of the boron phenolic-nitrile resin copolymer system.
[0022] Figure 2 The TGA curves are for the boron phenolic-nitrile resin copolymer system.
[0023] Figure 3 Temperature scanning rheological curves of the boron phenolic-nitrile resin copolymer system (Example 1).
[0024] Figure 4 The gelation time of the polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin mixture at 150°C.
[0025] Figure 5Bar chart showing the flexural strength / modulus of polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin fiber composite.
[0026] Figure 6 The mass ablation rate and linear ablation rate of the polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin fiber composite are given. Detailed Implementation
[0027] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0028] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.
[0029] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application. As used herein, the singular form includes the plural form unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this description, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.
[0030] In this invention, some conventional operating equipment, devices and components have been omitted or only briefly described.
[0031] Unless otherwise specified in the examples, the conditions shall be performed according to the standard conditions or the conditions recommended by the manufacturer.
[0032] In this application, unless otherwise specified, "parts" refers to parts by weight, and each part is considered as 1g or 1kg, etc.
[0033] The structural formula of the boron phenolic resin in the following examples is shown below: The boron phenolic resin is the F-2124 model product (commercially available) provided by Hangmo Technology New Materials (Fuyang) Co., Ltd.
[0034] The structural formula of the PN1 type nitrile resin described in the following examples is shown below: The PN1 type nitrile resin was provided by Sichuan Jinxiang Sairui Chemical Co., Ltd. (Meishan, Sichuan) (commercially available).
[0035] The structural formulas of the active polyarylene ethers described in the following examples are shown below: .
[0036] In the following examples, all portions are by weight, and each portion may be 1 kilogram or 1 gram.
[0037] In the following examples, the solvents are all mixed solvents of N,N-dimethylformamide and xylene in a mass ratio of 2:1.
[0038] Example 1: A method for preparing a boron phenolic-nitrile resin copolymer system specifically includes the following steps: Step (1): Add 50 parts of boron phenolic resin and 50 parts of PN1 type nitrile resin to 150 parts of solvent (DMF: xylene = 2:1), stir at 80°C for 1 hour to obtain boron phenolic-nitrile resin copolymer solution.
[0039] Step (2) The boron phenol-nitrile resin copolymer solution obtained in step (1) is placed in a vacuum oven and cured according to the heating program of (140℃ / 2h, 160℃ / 2h, 180℃ / 2h, 200℃ / 2h, 220℃ / 2h, 240℃ / 2h, 280℃ / 2h, 300℃ / 2h) to obtain the cured boron phenol-nitrile resin copolymer.
[0040] Example 2 A method for preparing a boron phenolic-nitrile resin copolymer system specifically includes the following steps: Step (1) Add 50 parts of boron phenolic resin and 50 parts of PN1 type nitrile resin to 150 parts of solvent (DMF: xylene = 2:1) and stir at 108℃ for 1 h to obtain boron phenolic-nitrile resin copolymer solution.
[0041] Step (2) The boron phenol-nitrile resin copolymer solution obtained in step (1) is placed in a vacuum oven and cured according to the heating program of (140℃ / 2h, 160℃ / 2h, 180℃ / 2h, 200℃ / 2h, 220℃ / 2h, 240℃ / 2h, 280℃ / 2h, 300℃ / 2h) to obtain the cured boron phenol-nitrile resin copolymer.
[0042] Example 3 A method for preparing a boron phenolic-nitrile resin copolymer system specifically includes the following steps: Step (1) Add 50 parts of boron phenolic resin and 50 parts of PN1 type nitrile resin to 150 parts of solvent (DMF: xylene = 2:1) and stir at 108℃ for 2 hours to obtain boron phenolic-nitrile resin copolymer solution.
[0043] Step (2) The boron phenol-nitrile resin copolymer solution obtained in step (1) is placed in a vacuum oven and cured according to the heating program of (140℃ / 2h, 160℃ / 2h, 180℃ / 2h, 200℃ / 2h, 220℃ / 2h, 240℃ / 2h, 280℃ / 2h, 300℃ / 2h) to obtain the cured boron phenol-nitrile resin copolymer.
[0044] Performance testing experiments were conducted on Examples 1-3 to verify the superior performance of this technology compared to existing technologies. The specific experimental content and analysis are as follows: like Figure 1 , Figure 2 As shown, after copolymerization of boron phenolic resin and nitrile resin, both the curing reaction peak (160-170℃) and the ring-opening polymerization peak (243℃) of the boron phenolic resin disappeared. When the reaction condition was (80℃ / 1h), the boron phenolic resin and nitrile resin had formed a copolymer, and the synthesized prepolymer had a long processing window and a low processing initiation temperature. When boron phenolic resin-nitrile copolymers under different reaction conditions underwent the same curing treatment, the sample with the copolymerization reaction condition (80℃ / 1h) had a high thermal decomposition temperature of 469℃ and a high char rate of 76%, which were significantly improved compared to pure boron phenolic resin and pure nitrile resin, and were close to the test results of the reaction condition (108℃ / 2h). Under comprehensive evaluation, (80℃ / 1h) is the optimal reaction time and temperature.
[0045] like Figure 3 As shown, after copolymerization of boron phenolic resin and nitrile resin, a single viscosity plateau appears, proving that the crosslinking reaction of boron phenolic resin under the catalysis of nitrile resin and the benzoxazine ring-opening reaction of nitrile resin are a one-step reaction, further verifying that boron phenolic resin and nitrile resin have formed a copolymer. The viscosity initiation temperature is 150℃, indicating that the initial processing temperature of the boron phenolic resin-nitrile resin copolymer system is 150℃.
[0046] Example 4 A method for preparing an ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material, specifically including the following steps: Step (1): Add 50 parts of boron phenolic resin and 50 parts of PN1 type nitrile resin to 150 parts of solvent (DMF: xylene = 2:1), stir at 80°C for 1 hour to obtain boron phenolic-nitrile resin copolymer.
[0047] Step (2): Dissolve 8 parts of polyarylene ether in sufficient N,N-dimethylformamide solvent, then add 92 parts of zirconium diboride, continuously stir and sonicate the solution for 24 hours, then centrifuge at high speed, filter the supernatant to obtain polyarylene ether@zirconium diboride; then dry and grind to obtain polyarylene ether@zirconium diboride filler powder.
[0048] Step (3): 1 part of polyarylene ether@zirconia diboride filler and 99 parts of boron phenolic-acrylic resin copolymer are ultrasonically stirred at 80°C for 30 minutes to obtain a mixture containing polyarylene ether@zirconia diboride modified boron phenolic-acrylic resin; the mixture is then uniformly coated onto high silica fiber cloth and then placed in a vacuum oven to dry at 60°C for 40 minutes to obtain prepreg cloth.
[0049] Step (4): The 8 layers of prepreg fabric obtained in step (3) are placed into a hot press and hot pressed to obtain laminates according to the hot pressing process of (150℃ / 1h, 200℃ / 2h, 240℃ / 2h, 300℃ / 2h).
[0050] Example 5 A method for preparing an ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material, specifically including the following steps: Step (1): Add 50 parts of boron phenolic resin and 50 parts of nitrile resin to 150 parts of solvent (DMF: xylene = 2:1) of (N,N-dimethylformamide: xylene = 2:1), stir at 80°C for 1 hour to obtain boron phenolic-nitrile resin copolymer. That is, the copolymer system in Example 1 (uncured).
[0051] Step (2): Dissolve 8 parts of polyarylene ether in sufficient N,N-dimethylformamide solvent, then add 92 parts of zirconium diboride, continuously stir and sonicate the solution for 24 hours, then centrifuge at high speed, filter the supernatant to obtain polyarylene ether@zirconium diboride; then dry and grind to obtain polyarylene ether@zirconium diboride filler powder.
[0052] Step (3): Mix 2 parts of polyarylene ether@zirconia diboride filler with 98 parts of boron phenolic-acrylic resin copolymer and ultrasonically stir at 80°C for 30 minutes to obtain a mixture containing polyarylene ether@zirconia diboride modified boron phenolic-acrylic resin; then uniformly coat the mixture onto a high-silica fiber cloth and dry it in a vacuum oven at 60°C for 40 minutes to obtain a prepreg cloth.
[0053] Step (4): The 8 layers of prepreg fabric obtained in step (3) are placed into a hot press and hot pressed to obtain laminates according to the hot pressing process of (150℃ / 1h, 200℃ / 2h, 240℃ / 2h, 300℃ / 2h).
[0054] Example 6 A method for preparing an ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material, specifically including the following steps: Step (1): Add 50 parts of boron phenolic resin and 50 parts of nitrile resin to 150 parts of solvent (DMF: xylene = 2:1) of (N,N-dimethylformamide: xylene = 2:1), stir at 80°C for 1 h to obtain boron phenolic-nitrile resin copolymer.
[0055] Step (2): Dissolve 8 parts of polyarylene ether in sufficient N,N-dimethylformamide solvent, then add 92 parts of zirconium diboride, continuously stir and sonicate the solution for 24 hours, then centrifuge at high speed, filter the supernatant to obtain polyarylene ether@zirconium diboride; then dry and grind to obtain polyarylene ether@zirconium diboride filler powder.
[0056] Step (3): Mix 5 parts of polyarylene ether@zirconia diboride filler with 95 parts of boron phenolic-acrylic resin copolymer and ultrasonically stir at 80°C for 30 minutes to obtain a mixture containing polyarylene ether@zirconia diboride modified boron phenolic-acrylic resin; then uniformly coat the mixture onto a high-silica fiber cloth and dry it in a vacuum oven at 60°C for 40 minutes to obtain a prepreg cloth.
[0057] Step (4): The 8 layers of prepreg fabric obtained in step (3) are placed into a hot press and hot pressed to obtain laminates according to the hot pressing process of (150℃ / 1h, 200℃ / 2h, 240℃ / 2h, 300℃ / 2h).
[0058] Performance testing experiments were conducted on Examples 4-6 above (results are shown in...). Figures 4-6 This was used to verify and demonstrate the superior performance of this technology compared to existing technologies. The specific experimental content and analysis are as follows: like Figure 4 As shown, the gelation time of the copolymer at 150°C continuously decreases with the increase of polyarylene ether@zirconia diboride content. Specifically, when the amount of polyarylene ether@zirconia diboride filler added is 5wt%, the gelation time of the blend is reduced to 330s, which significantly improves the curing activity of the blend system.
[0059] like Figure 5 As shown, the flexural strength of the composite material initially increases and then decreases with increasing polyarylene ether@zirconium diboride content. Specifically, when the polyarylene ether@zirconium diboride content is 1 wt%, the flexural strength reaches 435 MPa. This is mainly because the carboxyl groups on the side chains of the thermoplastic resin polyarylene ether form a strong chemical interface with the matrix resin, greatly improving stress transfer efficiency and energy dissipation capacity, preventing the interface from becoming a weak point, and thus achieving a toughening effect. Simultaneously, the introduction of the inorganic filler zirconium diboride further improves the rigidity of the resin. However, excessive filler leads to a decrease in the mechanical properties of the composite material. Too much filler can cause some polymerization inhibition, reduce covalent bonds, and thus lower the cohesive energy of the polymer, resulting in a decrease in the mechanical properties of the composite material.
[0060] like Figure 6 As shown, the polyarylene ether@zirconia diboride modified boron phenolic-nitrile resin high-silica fiber composite material prepared by prepreg molding process, with an addition amount of 1wt% polyarylene ether@zirconia diboride filler, exhibits good oxidation corrosion resistance and ablation resistance. The mass ablation rate and linear ablation rate after 20 s at 3000℃ are 0.0173 g / s. -1 The ablation rate of -0.0108 mm / s indicates that the material exhibits near-zero ablation characteristics. Furthermore, the ablation mechanism was revealed through analysis of ablation behavior and microstructure. The results show that during ablation, by sacrificing ZrB2, the material functions as an oxygen-consuming, oxygen-suppressing, self-healing, carbon-fixing, and reaction-endothermic agent, thus constructing an in-situ thermal barrier composed of carbon- and boron-containing multiphase ceramics. This ceramic composite material is of significant importance and holds promise as a large-area thermal protection material for hypersonic vehicles.
[0061] 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 an ablation-resistant polyaryl ether@zirconium diboride modified boron phenolic-nitrile resin composite material, characterized in that, The method includes the following steps: (1) Boron phenolic resin and PN1 type nitrile resin were prepolymerized in solution to prepare boron phenolic resin-nitrile resin copolymer; (2) Dissolve the active polyarylene ether in a solvent, add zirconium diboride and then sonicate. The resulting product is then centrifuged, dried and ground to obtain polyarylene ether@zirconium diboride filler. (3) The polyarylene ether@zirconia diboride filler obtained in step (2) is ultrasonically treated with the boron phenolic-acrylic resin copolymer obtained in step (1) to obtain a polyarylene ether@zirconia diboride modified boron phenolic-acrylic resin solution. (4) The polyarylene ether@zirconia diboride modified boron phenolic-nitrile resin liquid obtained in step (3) is uniformly coated on the prepreg reinforcement, and after drying and pressing, a composite material of polyarylene ether@zirconia diboride modified boron phenolic-nitrile resin is prepared.
2. The preparation method of the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to claim 1, characterized in that, In step (1), the mass ratio of boron phenolic resin to PN1 type nitrile resin is 1-90:90-10; the temperature during solution prepolymerization is 60-150℃ and the time is 1-6h.
3. The preparation method of the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to claim 1, characterized in that, In step (2), the solvent is N,N-dimethylformamide, xylene, N,N-dimethylacetamide, ethanol, or N-methylpyrrolidone; the active polyarylene ether is a polyarylene ether nitrile containing reactive functional groups of amine oxime and carboxyl groups; the mass ratio of the active polyarylene ether to zirconium diboride is 20-1:80-99; and the ultrasonic treatment time is 1-48h.
4. The preparation method of the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to claim 1, characterized in that, In step (3), the mass ratio of polyarylene ether@zirconium diboride filler to boron phenolic-nitrile resin copolymer is 0~5:100~95; the ultrasonic treatment temperature is 60℃~100℃ and the time is 0.5h~3h.
5. The method for preparing the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to any one of claims 1-4, characterized in that, The structural formula of the boron phenolic resin is shown below: 。 6. The method for preparing the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to any one of claims 1-4, characterized in that, The structural formula of the PN1 type nitrile resin is shown below: 。 7. The method for preparing the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to any one of claims 1-4, characterized in that, The structural formula of the active polyarylene ether is shown below: 。 8. The method for preparing the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to any one of claims 1-4, characterized in that, The average particle size of the zirconium diboride is 1-3 micrometers.
9. The method for preparing the ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material according to any one of claims 1-4, characterized in that, The prepreg reinforcement is a high-silica fiber cloth, and the resulting composite material is a composite laminate.
10. The ablation-resistant polyarylene ether@zirconium diboride modified boron phenolic-nitrile resin composite material prepared by any of the methods described in claims 1-4.