Anti-puncture composite material and preparation method thereof

Abstract

The invention discloses an anti-puncture composite material and a preparation method thereof, and belongs to the technical field of anti-puncture composites.The two sides of a pre-coated carbon fiber cloth are coated with a composite adhesive, composite aerogel films are pasted on the two sides of the pre-coated carbon fiber cloth respectively, a layer of fabric is pasted through the coated composite adhesive after rolling compounding is conducted, rolling compounding is conducted again, and the anti-puncture composite material is obtained. And curing to obtain the anti-puncture composite material. The pre-coated carbon fiber cloth is impregnated with tetrapod-like nano zinc oxide whiskers and can play a role of barbing, the composite adhesive is added with flaky nano carbon nitride powder, compared with spherical filler, the composite adhesive is more easily limited by the tetrapod-like nano zinc oxide whiskers, slippage between the pre-coated carbon fiber cloth and the composite aerogel film is reduced, and the composite aerogel film is more durable. The puncture force can be better dispersed into the whole composite material, so that the anti-puncture performance is improved; the composite aerogel film mixed with the calcium phosphate particles can effectively disperse stress and prevent crack propagation, and the compression resistance and puncture resistance of the puncture-proof composite material can be improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of puncture-resistant composite materials, and particularly relates to a puncture-resistant composite material and a preparation method thereof. Background Art

[0002] In today's society, the demand for safety protection is increasing day by day, especially for materials that can effectively prevent puncture injuries, and their importance has become even more prominent. Traditional anti-stab materials can be classified into three categories according to hardness: hard, semi-hard, and soft (flexible), but each type of material has certain limitations.

[0003] Hard anti-stab materials, such as metals and ceramics, although they have excellent anti-stab performance, their weight is relatively large, resulting in poor comfort when worn, which limits their application in scenarios that require long-term wearing or flexible movement. Semi-hard anti-stab materials usually improve the anti-stab effect by adding metal or ceramic inserts to the fabric, but there are still problems such as being bulky and having poor integrity. When worn, not only is the comfort poor, but it may also cause additional burden on the body due to excessive weight, and even cause injuries.

[0004] Soft (flexible) anti-stab materials mainly rely on high-performance fibers such as aramid fibers or ultra-high molecular weight polyethylene fibers. Although they have good comfort, their high raw material and production costs make the manufacturing cost remain high, making it difficult to achieve large-scale popularization. If ordinary fibers are used as substitutes, it is difficult to achieve the ideal anti-stab effect and cannot meet people's needs for high-efficiency protection.

[0005] In addition, some new anti-stab materials and technologies are also being continuously explored. For example, shear thickening materials have shown potential application value in the field of personal protection due to their unique stimulus-responsive properties. However, currently, the preparation process of anti-stab products based on shear thickening materials is relatively complex and the cost is high, which limits their actual application range. At the same time, some anti-stab materials reported in patents, such as semi-hard anti-stab materials based on the turtle shell structure, although they have improved the anti-stab performance and breathability to a certain extent, still have not completely solved the problems of being bulky, having poor integrity, and insufficient comfort.

[0006] In summary, developing a lightweight, flexible, low-cost, and effectively puncture-resistant wearable anti-stab material for the human body is of great practical significance for meeting the needs of modern society for personal protection. There is still a large room for optimization in the balance between the performance and cost of existing anti-stab materials, in order to achieve wider application and better protection effects. Summary of the Invention

[0007] The purpose of the present invention is to provide a puncture-resistant composite material and a preparation method thereof.

[0008] The purpose of the present invention can be achieved by the following technical solutions:

[0009] A preparation method of a puncture-proof composite material, comprising the following steps:

[0010] Step 1: Mix polyurethane, polypropylene, polyimide, polyether ether ketone, flaky nano-carbon nitride powder, nano-aluminum nitride powder, zinc naphthenate and flame retardant BTA5 evenly according to a mass ratio of 60-70:40-45:20-25:20-25:40-50:30-40:2-5:2-5 to obtain a composite adhesive;

[0011] Step 2: Coat the composite adhesive on both sides of the pre-coated carbon fiber cloth, paste the composite aerogel film respectively, roll and compound, and then paste a fabric on the coated composite adhesive, roll and compound again, and cure to obtain a puncture-proof composite material.

[0012] Further, the thickness of the adhesive coated each time is 0.3-0.8 mm.

[0013] Further, the pre-coated carbon fiber cloth is prepared by the following steps:

[0014] Step 1: Add modified tetrapod-like zinc oxide whiskers, dopamine hydrochloride and deionized water into a stirring kettle according to a mass ratio of 1:0.5-1:100, stir for 5-10 min under nitrogen protection and at 200-300 r / min, ultrasonically disperse for 2-5 min, and adjust the pH value to 8.5 with ammonia water to obtain a dispersion slurry.

[0015] Step 2: Immerse the carbon fiber cloth in an acetone solution for 48-72 h to remove the sizing agent on the surface, wash it with absolute ethanol 2-3 times, and dry it to obtain a pretreated carbon fiber cloth; coat the dispersion slurry on both sides of the pretreated carbon fiber cloth according to a dosage of 5-10 mL / cm 2 and dip-roll it 3-5 times, transfer it to a sodium periodate solution with a mass fraction of 0.5%, stir and react for 2-3 h, take it out, wash it with deionized water 2-3 times, and dry it to obtain a pre-coated carbon fiber cloth.

[0016] Further, the modified tetrapod-like zinc oxide whiskers are prepared by the following steps:

[0017] Add tetrapod-like zinc oxide whiskers and silane coupling agent KH570 into a reaction kettle according to a mass ratio of 100:1, adjust the pH value to 3 with hydrochloric acid with a concentration of 1 mol / L, stir at 500-800 r / min for 30-50 min, filter by suction, wash the filter cake with deionized water until the last washing liquid is neutral to obtain modified tetrapod-like zinc oxide whiskers.

[0018] Further, the composite aerogel film is prepared by the following steps:

[0019] Transfer DMSO, succinic anhydride and triethylamine into a reaction kettle and stir to mix. Then add the silica aerogel film into the reaction kettle and react at 55 - 60 °C for 20 - 24 h. After taking out the aerogel film, wash it with absolute ethanol 2 - 3 times and dry it under vacuum to obtain a carboxylated silica aerogel film;

[0020] The dosage ratio of DMSO, succinic anhydride, triethylamine and silica aerogel film is 10 mL : 15 mg : 8.5 - 9 mg : 15 - 20 mg.

[0021] Transfer the carboxylated silica aerogel film into an aqueous calcium chloride solution with a concentration of 1 mol / L and soak it for 40 - 50 h. Then take it out, wash it with deionized water 2 - 3 times, and transfer it into SBF simulated body fluid and mineralize it at 37 °C for 72 h. Wash it with deionized water 2 - 3 times again and dry it by supercritical drying to obtain a composite aerogel film.

[0022] Furthermore, the silica aerogel film is prepared by the following steps:

[0023] Mix tetraethyl orthosilicate, absolute ethanol and deionized water evenly according to a molar ratio of 1 : 8 : 3.5 - 4 to obtain a precursor solution. Adjust the pH value of the precursor solution to 3 - 3.5 with hydrochloric acid, stir at 20 - 25 °C and 200 - 300 r / min for 14 - 16 h, adjust the pH value to 9 - 10 with ammonia water with a concentration of 0.5 mol / L, and continue to stir for 10 - 12 h. Transfer the product into a mold to spread the film, then transfer it into absolute ethanol and age it at 50 - 60 °C for 20 - 24 h. Soak the obtained gel film in n - hexane for 12 - 16 h and dry it by supercritical drying to obtain a silica aerogel film with a thickness of 1 - 2 mm.

[0024] The beneficial effects of the present invention:

[0025] The anti - puncture composite material of the present invention structurally includes a pre - coated carbon fiber cloth in the middle, and a composite aerogel film and a fabric are adhesively bonded to both sides in sequence. The composite aerogel film can provide good flexibility and heat insulation performance. While providing good anti - puncture performance, this composite material can bring a good user experience.

[0026] The pre - coated carbon fiber cloth is impregnated with tetrapod - shaped zinc oxide whiskers. Then, through the adhesion of polydopamine, the adhesion force of the tetrapod - shaped zinc oxide whiskers and the roughness of the pre - coated carbon fiber cloth are improved. The tetrapod - shaped zinc oxide whiskers can play a role of barbs. Flaky nano - carbon nitride powder is added to the composite adhesive. Compared with spherical fillers, it is easier to be limited by the tetrapod - shaped zinc oxide whiskers, reducing the slippage between the pre - coated carbon fiber cloth and the composite aerogel film, and can better disperse the puncture force to the whole composite material, thereby improving the anti - puncture performance.

[0027] The composite aerogel membrane is based on silica aerogel membrane. The porous structure of the aerogel has a larger specific surface area. After treatment with succinic anhydride and the like, a carboxylated silica aerogel membrane with carboxyl groups is obtained. After adsorbing calcium ions and mineralizing through SBF simulated body fluids, a composite aerogel membrane mixed with calcium phosphate particles is prepared, which can effectively disperse stress and prevent crack propagation, help to improve the compressive resistance of the puncture-resistant composite material and further improve the puncture-resistant performance. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0029] Embodiment 1: A method for preparing a puncture-resistant composite material, comprising the following steps:

[0030] S1: Add tetrapod-shaped nano zinc oxide whiskers and silane coupling agent KH570 into a reactor at a mass ratio of 100:1, adjust the pH value to 3 with 1 mol / L hydrochloric acid, stir for 30 min at 500 r / min, filter, and wash the filter cake with deionized water until the last washing liquid is neutral to obtain modified tetrapod-shaped nano zinc oxide whiskers.

[0031] S2: Add modified tetrapod-shaped nano zinc oxide whiskers, dopamine hydrochloride and deionized water in a mass ratio of 1:0.5:100 into a stirring tank, stir for 5 min under nitrogen protection and 200 r / min, ultrasonically disperse for 2 min, adjust the pH value to 8.5 with aqueous ammonia to obtain a dispersed slurry.

[0032] S3: The carbon fiber cloth was immersed in an acetone solution for 48 hours to remove the sizing agent on the surface, washed twice with anhydrous ethanol, and dried to obtain a pretreated carbon fiber cloth; the dispersed slurry was stirred at 5 mL / cm 2 The pre-treated carbon fiber cloth was coated with an amount of , dipped and rolled three times, transferred to a sodium periodate solution with a mass fraction of 0.5%, stirred and reacted for 2 hours, taken out, washed twice with deionized water, and dried to obtain a pre-coated carbon fiber cloth.

[0033] S4: Mix tetraethyl orthosilicate, absolute ethanol, and deionized water evenly according to a molar ratio of 1:8:3.5 to obtain a precursor solution. Adjust the pH value of the precursor solution to 3 with hydrochloric acid, stir for 14 h at 20 °C and 200 r / min, adjust the pH value to 9 with 0.5 mol / L ammonia water, continue stirring for 10 h, transfer the product to a mold for film laying, then transfer it to absolute ethanol, age at 50 °C for 20 h, soak the obtained gel film in n - hexane for 12 h, and perform supercritical drying to obtain a silica aerogel film with a thickness of 1 mm.

[0034] S5: Transfer 100 L of DMSO, 150 g of succinic anhydride, and 85 g of triethylamine to a reaction kettle for stirring and mixing, then add 150 g of the silica aerogel film to the reaction kettle, react at 55 °C for 20 h, take out the aerogel film and wash it 2 times with absolute ethanol, and perform vacuum drying to obtain a carboxylated silica aerogel film.

[0035] S6: Transfer the carboxylated silica aerogel film to a 1 mol / L aqueous calcium chloride solution for soaking for 40 h, then take it out and wash it 2 times with deionized water, then transfer it to SBF simulated body fluid, mineralize at 37 °C for 72 h, wash it 2 times with deionized water again, and perform supercritical drying to obtain a composite aerogel film.

[0036] S7: Mix polyurethane, polypropylene, polyimide, polyether ether ketone, flaky nano - carbon nitride powder, nano - aluminum nitride powder, zinc naphthenate, and flame retardant BTA5 evenly according to a mass ratio of 60:40:20:20:40:30:2:2 to obtain a composite adhesive.

[0037] S8: Coat the composite adhesive on both sides of the pre - coated carbon fiber cloth, paste the composite aerogel film respectively, roll and compound, then paste a fabric lining through the coated composite adhesive, the thickness of the adhesive coated each time is 0.3 mm, roll and compound again, and cure to obtain a puncture - resistant composite material.

[0038] Example 2: A preparation method of a puncture - resistant composite material, comprising the following steps:

[0039] S1: Add tetrapod - shaped zinc oxide whiskers and silane coupling agent KH570 to a reaction kettle according to a mass ratio of 100:1, adjust the pH value to 3 with 1 mol / L hydrochloric acid, stir at 650 r / min for 40 min, perform suction filtration, wash the filter cake with deionized water until the last washing liquid is neutral to obtain modified tetrapod - shaped zinc oxide whiskers.

[0040] S2: Add modified tetrapod-like zinc oxide whiskers, dopamine hydrochloride, and deionized water into a stirring kettle according to a mass ratio of 1:0.75:100, stir for 7.5 min under nitrogen protection and at 250 r / min, perform ultrasonic dispersion for 3.5 min, and adjust the pH value to 8.5 with ammonia water to obtain a dispersion slurry.

[0041] S3: Immerse the carbon fiber cloth in an acetone solution for 60 h to remove the sizing agent on the surface, wash it 2.5 times with absolute ethanol, and dry it to obtain a pretreated carbon fiber cloth; coat the dispersion slurry on both sides of the pretreated carbon fiber cloth according to a dosage of 7.5 mL / cm 2 , roll it 4 times, transfer it to a sodium periodate solution with a mass fraction of 0.5%, stir and react for 2.5 h, take it out, wash it 2.5 times with deionized water, and dry it to obtain a pre-coated carbon fiber cloth.

[0042] S4: Mix tetraethyl orthosilicate, absolute ethanol, and deionized water evenly according to a molar ratio of 1:8:4 to obtain a precursor solution. Adjust the pH value of the precursor solution to 3.25 with hydrochloric acid, stir for 15 h under the conditions of 22.5 °C and 250 r / min, adjust the pH value to 9.5 with ammonia water with a concentration of 0.5 mol / L, continue to stir for 11 h, transfer the product to a mold for film laying, then transfer it to absolute ethanol, age it at 55 °C for 22 h, soak the obtained gel film in n-hexane for 14 h, and perform supercritical drying to obtain a silica aerogel film with a thickness of 1.5 mm.

[0043] S5: Transfer 100 L of DMSO, 150 g of succinic anhydride, and 87.5 g of triethylamine to a reaction kettle for stirring and mixing, then add 175 g of the silica aerogel film to the reaction kettle, react at 57.5 °C for 22 h, take out the aerogel film, wash it 2.5 times with absolute ethanol, and perform vacuum drying to obtain a carboxylated silica aerogel film.

[0044] S6: Transfer the carboxylated silica aerogel film to a calcium chloride aqueous solution with a concentration of 1 mol / L and soak it for 45 h, then take it out, wash it 2.5 times with deionized water, transfer it to SBF simulated body fluid again, mineralize it at 37 °C for 72 h, wash it 2.5 times with deionized water again, and perform supercritical drying to obtain a composite aerogel film.

[0045] S7: Mix polyurethane, polypropylene, polyimide, polyether ether ketone, flaky nano-carbon nitride powder, nano-aluminum nitride powder, zinc naphthenate, and flame retardant BTA5 evenly according to a mass ratio of 65:42.5:22.5:22.5:45:35:3.5:3.5 to obtain a composite adhesive.

[0046] S8: Coat the composite adhesive on both sides of the pre-coated carbon fiber cloth, paste the composite aerogel film respectively, roll and compound them, and then paste a fabric layer through the coated composite adhesive. The thickness of the adhesive coated each time is 0.55 mm. Roll and compound again, and cure to obtain the puncture-proof composite material.

[0047] Example 3: A preparation method of a puncture-proof composite material, comprising the following steps:

[0048] S1: Add tetrapod-shaped zinc oxide whiskers and silane coupling agent KH570 into the reaction kettle according to a mass ratio of 100:1, adjust the pH value to 3 with hydrochloric acid with a concentration of 1 mol / L, stir at 800 r / min for 50 min, filter by suction, wash the filter cake with deionized water until the last washing liquid is neutral to obtain modified tetrapod-shaped zinc oxide whiskers.

[0049] S2: Add the modified tetrapod-shaped zinc oxide whiskers, dopamine hydrochloride and deionized water into the stirring kettle according to a mass ratio of 1:1:100, stir at 300 r / min under nitrogen protection for 10 min, ultrasonically disperse for 5 min, and adjust the pH value to 8.5 with ammonia water to obtain a dispersion slurry.

[0050] S3: Immerse the carbon fiber cloth in acetone solution for 72 h to remove the sizing agent on the surface, wash it 3 times with absolute ethanol, and dry it to obtain the pretreated carbon fiber cloth; coat the dispersion slurry on both sides of the pretreated carbon fiber cloth according to the dosage of 10 mL / cm 2 Roll it 5 times, transfer it to a sodium periodate solution with a mass fraction of 0.5%, stir and react for 3 h, take it out, wash it 3 times with deionized water, and dry it to obtain the pre-coated carbon fiber cloth.

[0051] S4: Mix tetraethyl orthosilicate, absolute ethanol and deionized water evenly according to a molar ratio of 1:8:4 to obtain a precursor solution. Adjust the pH value of the precursor solution to 3.5 with hydrochloric acid, stir at 25 °C and 300 r / min for 16 h, adjust the pH value to 10 with ammonia water with a concentration of 0.5 mol / L, continue to stir for 12 h, transfer the product to a mold for film laying, then transfer it to absolute ethanol, age at 60 °C for 24 h, soak the obtained gel film in n-hexane for 16 h, and perform supercritical drying to obtain a silica aerogel film with a thickness of 2 mm.

[0052] S5: Transfer 100 L of DMSO, 150 g of succinic anhydride and 90 g of triethylamine to the reaction kettle and stir and mix them, then add 200 g of silica aerogel film to the reaction kettle, react at 60 °C for 24 h, take out the aerogel film, wash it 3 times with absolute ethanol, and dry it under vacuum to obtain a carboxylated silica aerogel film.

[0053] S6: Transfer the carboxylated silica aerogel film to an aqueous calcium chloride solution with a concentration of 1 mol / L and soak it for 50 h. Then take it out, wash it three times with deionized water, transfer it to SBF simulated body fluid, mineralize it at 37 °C for 72 h, wash it three times with deionized water again, and perform supercritical drying to obtain the composite aerogel film.

[0054] S7: Mix polyurethane, polypropylene, polyimide, polyether ether ketone, flaky nano-carbon nitride powder, nano-aluminum nitride powder, zinc naphthenate, and flame retardant BTA5 evenly according to a mass ratio of 70:45:25:25:50:40:5:5 to obtain the composite adhesive.

[0055] S8: Coat the composite adhesive on both sides of the pre-coated carbon fiber cloth, paste the composite aerogel film respectively, roll and compound them, and then paste a fabric material through the coated composite adhesive. The thickness of the adhesive coated each time is 0.8 mm, roll and compound them again, and cure to obtain the puncture-proof composite material.

[0056] The fabric material used in the examples is polyester fiber fabric. The fabric material in this solution includes but is not limited to polyester fiber fabric. The rest of the raw materials in the examples are all commercially available products.

[0057] Comparative example 1: On the basis of Example 3, in step S8, replace the pre-coated carbon fiber cloth with a conventional carbon fiber cloth, and keep the rest of the steps unchanged to prepare the puncture-proof composite material.

[0058] Comparative example 2: On the basis of Example 3, in step S8, replace the composite aerogel film with the carboxylated silica aerogel film in step S5, and keep the rest of the steps unchanged to prepare the puncture-proof composite material.

[0059] Comparative example 3: On the basis of Example 3, in step S7, replace the flaky nano-carbon nitride powder with the same mass of nano-aluminum nitride powder, and keep the rest of the steps unchanged to prepare the puncture-proof composite material.

[0060] Perform performance tests on Examples 1 - 3 and Comparative examples 1 - 3. Referring to the method in GB / T12017 - 1989, cut the fabric material into circular specimens with a diameter of 5 cm required by the specimen holder, and perform a quasi-static anti-stabbing performance test on the three-dimensional fabric composite material with a quasi-static anti-stabbing test device loaded on Instron 5565:

[0061] (1) Install the long nail on the upper part of the frame, clamp the cut specimen to be tested between the upper and lower spiral plates of the specimen holder, tighten the nut to ensure that the specimen to be tested will not be distorted, and evenly spread it flat in the specimen holder, with the front side of the fabric material facing the long nail. Then adjust both ends of the base to fix the specimen holder at the bottom.

[0062] (2) Raise the frame with spikes to 70 cm, click to zero the load displacement, and then operate the universal testing machine to move downward at a speed of 25 mm / min, so that the puncture nail pierces the specimen to be tested until it penetrates the specimen.

[0063] Record the changes in the puncture force and puncture depth of the spikes during the puncture of different circular specimens in the test. The results are shown in Table 1:

[0064] Table 1

[0065] Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Maximum puncture force (N) 757 774 788 745 736 760 Puncture depth (mm) 12.26 12.47 12.71 15.46 15.24 14.78

[0066] It can be seen from Table 1 that the maximum puncture force in Comparative Example 1 decreases and the puncture depth increases. This may be because the pre-coated carbon fiber cloth has a better bonding force with other layers, which can improve the dispersion effect of the puncture force; the anti-puncture performance in Comparative Example 3 decreases. This may be because the flaky nano-cubic boron nitride powder is more easily restricted compared to the spherical filler, reducing the slippage between the pre-coated carbon fiber cloth and the composite aerogel film; the anti-puncture performance in Comparative Example 2 decreases because the mechanical properties of the aerogel without calcium phosphate filling are lacking.

[0067] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device.

[0068] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a puncture-resistant composite material, characterized in that: The steps include: Step 1: uniformly mix polyurethane, polypropylene, polyimide, polyetheretherketone, flaky nano carbon nitride powder, nano aluminum nitride powder, zinc cyclohexaneate and flame retardant BTA5 in a mass ratio of 60-70:40-45:20-25:20-25:40-50:30-40:2-5:2-5 to obtain a composite adhesive; Step 2: Coat the composite adhesive on both sides of the pre-coated carbon fiber cloth, paste the composite aerogel film respectively, roll-press and compound, and then paste a layer of fabric through the coated composite adhesive. The thickness of the adhesive coated each time is 0.3-0.8mm, roll-press and compound again, and obtain the puncture-proof composite material after curing.

2. The method for preparing a puncture-resistant composite material according to claim 1, characterized in that: The pre-coated carbon fiber cloth is prepared by the following steps: The carbon fiber cloth is immersed in an acetone solution for 48-72 hours to remove the sizing agent on the surface, washed with anhydrous ethanol 2-3 times, and dried to obtain a pretreated carbon fiber cloth; the dispersed slurry is dispersed at 5-10mL / cm 2 The pre-treated carbon fiber cloth is coated with an amount of and dipped 3-5 times, transferred to a sodium periodate solution with a mass fraction of 0.5%, stirred for reaction for 2-3 hours, taken out, washed with deionized water for 2-3 times, and dried to obtain a pre-coated carbon fiber cloth.

3. The method for preparing a puncture-resistant composite material according to claim 2, characterized in that: The dispersed slurry is prepared by the following steps: The modified tetrapod-shaped nano zinc oxide whiskers, dopamine hydrochloride and deionized water were added into a stirring kettle at a mass ratio of 1:0.5-1:100, stirred for 5-10 minutes under nitrogen protection and 200-300 r / min, ultrasonically dispersed for 2-5 minutes, and the pH value was adjusted to 8.5 with ammonia water to obtain a dispersed slurry.

4. The method for preparing a puncture-resistant composite material according to claim 3, characterized in that: The modified four-needle nano zinc oxide whisker is prepared by the following steps: The tetrapod-shaped nano zinc oxide whiskers and the silane coupling agent KH570 were added into the reactor in a mass ratio of 100:1, the pH value was adjusted to 3 with 1 mol / L hydrochloric acid, stirred for 30-50 min at 500-800 r / min, filtered, and the filter cake was washed with deionized water until the last washing liquid was neutral to obtain modified tetrapod-shaped nano zinc oxide whiskers.

5. The method for preparing a puncture-resistant composite material according to claim 1, characterized in that: The composite aerogel film is prepared by the following steps: The carboxylated silica aerogel membrane was transferred to a 1 mol / L calcium chloride aqueous solution and soaked for 40-50 hours, then taken out and washed 2-3 times with deionized water, and then transferred to SBF simulated body fluid, mineralized at 37°C for 72 hours, washed again with deionized water 2-3 times, and supercritically dried to obtain a composite aerogel membrane.

6. The method for preparing a puncture-resistant composite material according to claim 5, characterized in that: The carboxylated silica aerogel film is prepared by the following steps: DMSO, succinic anhydride and triethylamine were transferred to a reactor and stirred and mixed, and then the silica aerogel membrane was added to the reactor and reacted at 55-60° C. for 20-24 hours. After the aerogel membrane was taken out, it was washed with anhydrous ethanol for 2-3 times and vacuum dried to obtain a carboxylated silica aerogel membrane.

7. The method for preparing a puncture-resistant composite material according to claim 6, characterized in that: The usage ratio of the DMSO, succinic anhydride, triethylamine and silica aerogel film is 10 mL: 15 mg: 8.5-9 mg: 15-20 mg.

8. The method for preparing a puncture-resistant composite material according to claim 6, characterized in that: The silica aerogel film is prepared by the following steps: Ethyl orthosilicate, anhydrous ethanol and deionized water are mixed uniformly in a molar ratio of 1:8:3.5-4 to obtain a precursor solution, the pH value of the precursor solution is adjusted to 3-3.5 with hydrochloric acid, and stirred for 14-16 hours at 20-25°C and 200-300r / min, and the pH value is adjusted to 9-10 with 0.5mol / L ammonia water, and stirring is continued for 10-12 hours. The product is transferred to a mold for film laying, and then transferred to anhydrous ethanol, aged at 50-60°C for 20-24 hours, and the obtained gel film is soaked in n-hexane for 12-16 hours, and supercritically dried to obtain a silica aerogel film with a thickness of 1-2 mm.

9. A puncture-resistant composite material, characterized in that: It is prepared by the preparation method described in any one of claims 1 to 8.