Ablation-resistant composite material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of ablation-resistant materials, in particular to an ablation-resistant composite material and a preparation method and application thereof.The preparation method comprises the steps that silicon-modified polyphenyl ether resin, epoxy resin, a flame retardant, zirconium boride and an antioxidant are evenly stirred, and a mixture is obtained; and feeding the mixture into a twin-screw extruder, and carrying out side feeding, extrusion and granulation on the enhanced high-silica glass fiber to prepare the ablation-resistant composite material. According to the invention, the methoxyl group of the methoxyl-terminated organosilicon intermediate reacts with the hydroxyl group in the dihydroxyl-terminated polyphenyl ether, the organosilicon is grafted in the molecular chain of the dihydroxyl-terminated polyphenyl ether, the heat resistance of the silicon modified polyphenyl ether resin is enhanced, and the zirconium boride is matched, so that the ablation resistance of the composite material can be greatly improved.

Description

Technical Field

[0001] This invention relates to the field of ablation-resistant materials technology, specifically to an ablation-resistant composite material, its preparation method, and its application. Background Technology

[0002] Power batteries provide power for new energy vehicles and are one of the most important components. The battery pack casing provides protection for the battery, and its safety, lightweight design, and reliability have become the focus of industry attention. As national standards impose increasingly higher safety requirements on new energy batteries, the overall quality requirements for battery pack casings are also constantly increasing.

[0003] Currently, some battery pack casings use polyphenylene ether resin as the matrix, adding flame retardants and high-silica glass fibers to improve the material's ablation resistance, but the improvement is limited. Furthermore, while high-silica glass fibers can withstand high temperatures, their micropores lead to brittleness, which is detrimental to enhancing the material's strength. Based on this, an ablation-resistant composite material, its preparation method, and its applications are proposed. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an ablation-resistant composite material, its preparation method, and its application. By combining silicon-modified polyphenylene ether resin, zirconium boride, and reinforced high-silica glass fiber, the overall quality of the composite material is improved.

[0005] To achieve the above objectives, the present invention provides the following technical solution: an ablation-resistant composite material comprising the following raw materials in parts by weight: 50-60 parts of silicon-modified polyphenylene ether resin, 15-25 parts of epoxy resin, 8-12 parts of flame retardant, 5-10 parts of zirconium boride, 3-5 parts of reinforced high-silica glass fiber, and 0.5-1 parts of antioxidant.

[0006] Preferably, the preparation method of the silicon-modified polyphenylene ether resin is as follows: dissolve the bihydroxyl-terminated polyphenylene ether in acetone, then add the methoxyl-terminated organosilicon intermediate; after uniform stirring, add dibutyltin dilaurate and carry out the reaction at a higher temperature; after the reaction is completed, remove the solvent under reduced pressure to obtain the silicon-modified polyphenylene ether resin.

[0007] Preferably, based on the total mass of the silicon-modified polyphenylene ether resin, the terminal methoxy organosilicon intermediate accounts for 15-20%, dibutyltin dilaurate accounts for 0.1-0.15%, and the balance is dihydroxyl-terminated polyphenylene ether.

[0008] Preferably, the dissolution temperature of the double-hydroxyl-terminated polyphenylene ether in acetone is controlled at 80-85°C; the temperature of the heating reaction is 110-120°C, and the heating reaction time is 5-6 hours.

[0009] Preferably, the preparation method of the reinforced high-silica glass fiber is as follows: the high-silica glass fiber is ultrasonically dispersed in a silicate solution, and after separation, sulfuric acid solution is uniformly sprayed on its wet surface. After the reaction is completed, the above operation is repeated 2-3 times to obtain the reinforced high-silica glass fiber.

[0010] Preferably, the length of the high-silica glass fiber is 0.5-2 mm; the reaction temperature is 40-45℃; the reaction time is 30-35 min; and the mass fraction of the sulfuric acid solution is 5-8%.

[0011] Preferably, the silicate solution is prepared by mixing 5 wt% sodium silicate solution and 15 wt% sodium chloride solution in a volume ratio of 3:2.

[0012] Preferably, the flame retardant is selected from triphenyl phosphate and tetraphenylresorcinol diphosphate; the antioxidant is selected from antioxidant 1010, antioxidant DLTP and antioxidant 168.

[0013] This invention provides a method for preparing an ablation-resistant composite material, comprising the following steps: (1) The silicone-modified polyphenylene ether resin, epoxy resin, flame retardant, zirconium boride and antioxidant are stirred evenly to obtain a mixture; (2) The mixture is fed into a twin-screw extruder to side-feed the reinforced high-silica glass fiber, and then extruded and granulated to obtain an ablation-resistant composite material.

[0014] This invention also provides the application of ablation-resistant composite materials in the casing of power battery packs.

[0015] This invention provides an ablation-resistant composite material, its preparation method, and its application, which have the following advantages compared with the prior art: This invention utilizes the reaction between the methoxy group of a methoxy-terminated organosilicon intermediate and the hydroxyl group of a hydroxyl-terminated polyphenylene ether (PPE) to graft organosilicon into the molecular chain of PPE, enhancing the heat resistance of the silicon-modified PPE resin. Combined with zirconium boride, this significantly improves the ablation resistance of the composite material. Specifically, the methoxy-terminated organosilicon intermediate generates silicon-containing free radicals during pyrolysis, which are more readily combined with oxygen than carbon atoms, thus facilitating their combination with free radicals generated during matrix degradation. Furthermore, the pyrolysis of organosilicon forms a protective layer of silica compounds, collectively inhibiting matrix degradation. Simultaneously, the matrix reacts with zirconium boride during high-temperature pyrolysis to generate boron oxide, which melts above 450°C and fills pores and cracks, further improving the ablation resistance of the composite material.

[0016] This invention incorporates reinforced high-silica glass fibers into a resin matrix. By coating the surface of the high-silica glass fibers with nano-silica particles, some of the nanoparticles fill the micropores of the high-silica glass fibers, thereby enhancing the strength of the high-silica glass fibers and improving the mechanical properties of the composite material. Attached Figure Description

[0017] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings: Figure 1 Electron micrographs of the ablation-resistant composite materials in Example 7 and Comparative Example 3 of the present invention; Figure 2 The images show the ablation patterns of the ablation-resistant composite materials in Embodiment 7 and Comparative Examples 1-3 of the present invention. Detailed Implementation

[0018] The following embodiments are provided to illustrate the implementation of this application in detail, so that the process of how this application uses technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.

[0019] Example 1 The preparation method of silicone-modified polyphenylene ether resin is as follows: hydroxyl-terminated polyphenylene ether is dissolved in acetone at 85°C, followed by the addition of a methoxyl-terminated organosilicon intermediate; after uniform stirring, dibutyltin dilaurate is added, and the reaction is carried out at 110°C for 6 hours; after the reaction is completed, the solvent is removed under reduced pressure to obtain silicone-modified polyphenylene ether resin.

[0020] Based on the total mass of silicon-modified polyphenylene ether resin, the methoxy-terminated organosilicon intermediate accounts for 15%, dibutyltin dilaurate accounts for 0.15%, and the balance is dihydroxyl-terminated polyphenylene ether.

[0021] Example 2 The preparation method of silicone-modified polyphenylene ether resin is as follows: hydroxyl-terminated polyphenylene ether is dissolved in acetone at 80°C, followed by the addition of a methoxyl-terminated organosilicon intermediate; after uniform stirring, dibutyltin dilaurate is added, and the reaction is carried out at 120°C for 5 hours; after the reaction is completed, the solvent is removed under reduced pressure to obtain silicone-modified polyphenylene ether resin.

[0022] Based on the total mass of silicon-modified polyphenylene ether resin, the methoxylated organosilicon intermediate accounts for 20%, dibutyltin dilaurate accounts for 0.1%, and the remainder is dihydroxylated polyphenylene ether.

[0023] Example 3 The preparation method of reinforced high-silica glass fiber is as follows: Prepare a silicate solution by mixing 5wt% sodium silicate solution and 15wt% sodium chloride solution at a volume ratio of 3:2. Disperse high-silica glass fibers with a length of 0.5-2mm in the silicate solution by ultrasonication. After separation, spray 8wt% sulfuric acid solution evenly on the wet surface of the fiber. React at 40℃ for 35min. After the reaction is completed, repeat the above operation twice to obtain reinforced high-silica glass fiber.

[0024] Example 4 The preparation method of reinforced high silica glass fiber is as follows: Prepare a silicate solution by mixing 5wt% sodium silicate solution and 15wt% sodium chloride solution at a volume ratio of 3:2. Disperse high silica glass fibers with a length of 0.5-2mm in the silicate solution by ultrasonication. After separation, spray 5wt% sulfuric acid solution evenly on the wet surface of the fiber. React at 45℃ for 30min. After the reaction is completed, repeat the above operation 3 times to obtain reinforced high silica glass fiber.

[0025] Example 5 A refractory composite material comprises the following raw materials in parts by weight: 60 parts of silicone-modified polyphenylene ether resin, 15 parts of epoxy resin, 12 parts of triphenyl phosphate, 5 parts of zirconium boride, 5 parts of reinforced high-silica glass fiber, and 0.5 parts of antioxidant 168.

[0026] The preparation method of the above-mentioned ablation-resistant composite material includes the following steps: (1) The silicone-modified polyphenylene ether resin, epoxy resin, flame retardant, zirconium boride and antioxidant are stirred evenly to obtain a mixture; (2) The mixture is fed into a twin-screw extruder to side-feed the reinforced high-silica glass fiber, and then extruded and granulated to obtain an ablation-resistant composite material with a vertical burning rating of V-0.

[0027] In this embodiment, the silicon-modified polyphenylene ether resin prepared in Example 1 is used; and the reinforced high-silica glass fiber prepared in Example 3 is used.

[0028] Example 6 An ablation-resistant composite material comprises the following raw materials in parts by weight: 50 parts of silicone-modified polyphenylene ether resin, 25 parts of epoxy resin, 8 parts of tetraphenylresorcinol diphosphate, 10 parts of zirconium boride, 3 parts of reinforced high-silica glass fiber, and 1 part of antioxidant DLTP.

[0029] The preparation method of the above-mentioned ablation-resistant composite material includes the following steps: (1) The silicone-modified polyphenylene ether resin, epoxy resin, flame retardant, zirconium boride and antioxidant are stirred evenly to obtain a mixture; (2) The mixture is fed into a twin-screw extruder to side-feed the reinforced high-silica glass fiber, and then extruded and granulated to obtain an ablation-resistant composite material with a vertical burning rating of V-0.

[0030] In this embodiment, the silicon-modified polyphenylene ether resin prepared in Example 2 is used; and the reinforced high-silica glass fiber prepared in Example 4 is used.

[0031] Example 7 A refractory composite material comprises the following raw materials in parts by weight: 55 parts of silicone-modified polyphenylene ether resin, 20 parts of epoxy resin, 10 parts of triphenyl phosphate, 8 parts of zirconium boride, 4 parts of reinforced high-silica glass fiber, and 0.8 parts of antioxidant 1010.

[0032] The preparation method of the above-mentioned ablation-resistant composite material includes the following steps: (1) The silicone-modified polyphenylene ether resin, epoxy resin, flame retardant, zirconium boride and antioxidant are stirred evenly to obtain a mixture; (2) The mixture is fed into a twin-screw extruder to side-feed the reinforced high-silica glass fiber, and then extruded and granulated to obtain an ablation-resistant composite material with a vertical burning rating of V-0.

[0033] In this embodiment, the silicon-modified polyphenylene ether resin prepared in Example 1 is used; and the reinforced high-silica glass fiber prepared in Example 4 is used.

[0034] Comparative Example 1 A refractory composite material comprises the following raw materials in parts by weight: 55 parts of silicone-modified polyphenylene ether resin, 20 parts of epoxy resin, 10 parts of triphenyl phosphate, 4 parts of reinforced high-silica glass fiber, and 0.8 parts of antioxidant 1010.

[0035] The preparation method of the above-mentioned ablation-resistant composite material is as described in Example 7.

[0036] In this comparative example, the silicone-modified polyphenylene ether resin prepared in Example 1 and the reinforced high-silica glass fiber prepared in Example 4 were used.

[0037] Comparative Example 2 A refractory composite material comprises the following raw materials in parts by weight: 55 parts of hydroxyl-terminated polyphenylene ether, 20 parts of epoxy resin, 10 parts of triphenyl phosphate, 8 parts of zirconium boride, 4 parts of reinforced high-silica glass fiber, and 0.8 parts of antioxidant 1010.

[0038] The preparation method of the above-mentioned ablation-resistant composite material is as described in Example 7.

[0039] In this comparative example, the reinforced high-silica glass fiber prepared in Example 4 was used.

[0040] Comparative Example 3 A refractory composite material comprises the following raw materials in parts by weight: 55 parts of silicone-modified polyphenylene ether resin, 20 parts of epoxy resin, 10 parts of triphenyl phosphate, 8 parts of zirconium boride, 4 parts of high-silica glass fiber, and 0.8 parts of antioxidant 1010.

[0041] The preparation method of the above-mentioned ablation-resistant composite material is as described in Example 7.

[0042] In this comparative example, the silicone-modified polyphenylene ether resin prepared in Example 1 was used.

[0043] Performance testing Samples were prepared using the ablation-resistant composite materials from Examples 5-7 and Comparative Examples 1-3, and then tested.

[0044] 1. Mechanical property testing: The specimen size was controlled at 80×10×3mm, and the bending performance of the specimen was tested using a universal testing machine; the impact strength of the specimen was tested according to the standard GB / T 1843-2008. The specific test results are shown in Table 1.

[0045] Table 1 Mechanical Properties As shown in Table 1, compared with Example 7, the mechanical properties of the sample in Comparative Example 1, which did not contain zirconium boride, did not change significantly; the sample in Comparative Example 2, which used unmodified double-terminated hydroxyl polyphenylene ether, and the sample in Comparative Example 3, which used unmodified high-silica glass fiber, showed a significant decrease in flexural strength and impact strength.

[0046] 2. Ablation Performance Test: The ablation performance of the samples was tested using an oxygen-acetylene ablation test, according to the standard GJB 323A-2019. The test conditions were adjusted to 500 L / h oxygen and 560 L / h acetylene, with a heat flux density of approximately 1800 kW / m³. 2 The sample was adjusted to a cylinder with a diameter of 30 mm and a thickness of 10 mm, and placed in a graphite mold for ablation testing. The distance between the sample and the flame nozzle was 50 mm, and the ablation time was 40 s. The linear ablation rate and mass ablation rate were calculated using the following formulas: In the formula: Linear ablation rate, mm / s; The mass ablation rate is expressed in g / s. The thickness of the sample before ablation is in mm; The thickness of the sample before ablation is in mm; The mass of the sample before ablation is in grams. The mass of the sample after ablation is in grams. The ablation time is in seconds (s).

[0047] The specific test results are shown in Table 2.

[0048] Table 2 Ablation Resistance As shown in Table 2, compared with Example 7, the sample in Comparative Example 1 did not add zirconium boride, and its ablation resistance was reduced; the sample in Comparative Example 2 used unmodified double-terminated hydroxyl polyphenylene ether, and its ablation resistance was significantly reduced; the sample in Comparative Example 3 used unmodified high silica glass fiber, and its ablation resistance did not change significantly.

[0049] Combination Figure 1 It can be seen that the packing material in Example 7 is severely agglomerated, while the packing material in Comparative Example 3 is more evenly dispersed.

[0050] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. An ablation-resistant composite material, characterized in that, The raw materials include the following parts by weight: 50-60 parts of silicone-modified polyphenylene ether resin, 15-25 parts of epoxy resin, 8-12 parts of flame retardant, 5-10 parts of zirconium boride, 3-5 parts of reinforced high-silica glass fiber, and 0.5-1 part of antioxidant.

2. The ablation-resistant composite material according to claim 1, characterized in that, The preparation method of the silicon-modified polyphenylene ether resin is as follows: dissolve the bihydroxyl-terminated polyphenylene ether in acetone, then add the methoxyl-terminated organosilicon intermediate; after uniform stirring, add dibutyltin dilaurate and heat the reaction; after the reaction is completed, remove the solvent under reduced pressure to obtain the silicon-modified polyphenylene ether resin.

3. The ablation-resistant composite material according to claim 2, characterized in that, Based on the total mass of the silicon-modified polyphenylene ether resin, the terminal methoxy organosilicon intermediate accounts for 15-20%, dibutyltin dilaurate accounts for 0.1-0.15%, and the balance is dihydroxyl-terminated polyphenylene ether.

4. The ablation-resistant composite material according to claim 2, characterized in that, The dissolution temperature of the double-hydroxyl-terminated polyphenylene ether in acetone is controlled at 80-85℃; the temperature of the heating reaction is 110-120℃, and the heating reaction time is 5-6h.

5. The ablation-resistant composite material according to claim 1, characterized in that, The preparation method of the reinforced high-silica glass fiber is as follows: the high-silica glass fiber is ultrasonically dispersed in a silicate solution, and after separation, sulfuric acid solution is uniformly sprayed on its wet surface. After the reaction is completed, the above operation is repeated 2-3 times to obtain the reinforced high-silica glass fiber.

6. The ablation-resistant composite material according to claim 5, characterized in that, The length of the high-silica glass fiber is 0.5-2 mm; the reaction temperature is 40-45℃, the reaction time is 30-35 min; and the mass fraction of the sulfuric acid solution is 5-8%.

7. The ablation-resistant composite material according to claim 5, characterized in that, The silicate solution is prepared by mixing 5 wt% sodium silicate solution and 15 wt% sodium chloride solution in a volume ratio of 3:

2.

8. The ablation-resistant composite material according to claim 1, characterized in that, The flame retardant is selected from triphenyl phosphate and tetraphenylresorcinol diphosphate; the antioxidant is selected from antioxidant 1010, antioxidant DLTP and antioxidant 168.

9. The method for preparing the ablation-resistant composite material according to any one of claims 1-8, characterized in that, Includes the following steps: (1) The silicone-modified polyphenylene ether resin, epoxy resin, flame retardant, zirconium boride and antioxidant are stirred evenly to obtain a mixture; (2) The mixture is fed into a twin-screw extruder to side-feed the reinforced high-silica glass fiber, and then extruded and granulated to obtain an ablation-resistant composite material.

10. The application of the ablation-resistant composite material according to any one of claims 1-8, characterized in that, It is applied to the casing of power battery packs.

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