Impact-resistant ceramic polymer composite material and preparation method thereof

Abstract

The invention belongs to the technical field of polymer composite materials, and particularly relates to an impact-resistant ceramic polymer composite material and a preparation method thereof. The impact-resistant ceramic polymer composite material comprises the following components in parts by weight: 60-80 parts of epoxy resin, 20-30 parts of a ceramic material, 10-14 parts of glass fibers, 20-24 parts of a curing agent, 2-4 parts of an antistatic agent and 2-4 parts of an antioxidant, the preparation method of the ceramic material comprises the following steps: hybridizing commercially available ceramic powder to obtain hybridized ceramic powder; carrying out ion exchange treatment on the hybridized ceramic powder to obtain a ceramic powder-cobalt-nickel layered double-metal hydroxide; and finally, carrying out chelating treatment on the ceramic powder and the cobalt-nickel layered double-metal hydroxide to obtain the ceramic material.

Description

Technical Field

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

[0002] Ceramic polymer composite materials are a new type of composite materials that combine ceramic materials and polymer polymers, possessing the excellent properties of both, and are widely used in fields such as aerospace, electronic devices, biomedicine, and energy. Ceramic polymer composite materials have the following characteristics: (1) Wear resistance and corrosion resistance. The ceramic phase significantly improves the surface hardness of the material, while the polymer matrix enhances the impact resistance; (2) Lightweight. Compared with metal materials, ceramic composite materials have a lower density, making them suitable for weight-sensitive fields such as aerospace; (3) Chemical stability, with excellent resistance to acid-base and oxidation environments; (4) Processability. The addition of polymer materials makes the composite materials easy to form, and complex structures can be prepared through processes such as 3D printing and injection molding.

[0003] Chinese Patent (Publication No. CN114767940B) discloses a ceramic polymer composite material and a preparation method thereof. The invention uses a compression mold to perform low-pressure compression on the obtained green embryo, increasing the distance between the layered structures in the green embryo, improving the volume fraction of the green embryo, increasing the mechanical strength of the green embryo, while avoiding damage to the microstructure of the layered structure of the green embryo, ensuring the integrity of the layered structure, and further ensuring the continuity of the layered structure in the obtained ceramic skeleton, and further ensuring that the internal structure of the finally prepared ceramic polymer composite material has good continuity and fewer interfaces, improving the light transmittance of the ceramic polymer composite material.

[0004] However, in the prior art, the research on the flame retardancy and impact resistance of ceramic polymer composite materials is still insufficient. How to effectively improve the impact strength of the composite material while ensuring good flame retardancy has become a research direction. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an impact-resistant ceramic polymer composite material and a preparation method thereof; the present invention uses commercially available ceramic powder as a raw material, and prepares a ceramic material through hybridization treatment, ion exchange treatment, and chelation treatment in sequence, and is used in combination with epoxy resin, glass fiber, and a curing agent to prepare an impact-resistant ceramic polymer composite material, which significantly improves the impact resistance while ensuring that the material has excellent flame retardant properties.

[0006] The technical solutions adopted by the present invention to solve the above technical problems are as follows: In the first aspect of the present invention, there is provided an impact-resistant ceramic polymer composite material, which includes the following components in parts by weight: 60 - 80 parts of epoxy resin, 20 - 30 parts of ceramic material, 10 - 14 parts of glass fiber, 20 - 24 parts of curing agent, 2 - 4 parts of antistatic agent and 2 - 4 parts of antioxidant.

[0007] As a preferred embodiment, the weight parts of the epoxy resin in the present invention can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, etc.

[0008] As a preferred embodiment, the weight parts of the ceramic material in the present invention can be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, etc.

[0009] As a preferred embodiment, the weight parts of the glass fiber in the present invention can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, etc.

[0010] As a preferred embodiment, the weight parts of the curing agent in the present invention can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, etc.

[0011] As a preferred embodiment, the weight parts of the antistatic agent in the present invention can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, etc.

[0012] As a preferred embodiment, the weight parts of the antioxidant in the present invention can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, etc.

[0013] As a preferred embodiment, the preparation method of the ceramic material includes: first, hybridize the commercially available ceramic powder to obtain hybrid ceramic powder; then perform ion exchange treatment on the hybrid ceramic powder to obtain ceramic powder - cobalt nickel layered double hydroxide; finally, perform chelation treatment on the ceramic powder - cobalt nickel layered double hydroxide to obtain the ceramic material.

[0014] The ceramic material of the present invention uses ceramic powder as a raw material, prepares hybrid ceramic powder by adding cobalt nitrate hexahydrate and 2 - methylimidazole, then introduces nickel element through ion exchange treatment to form cobalt nickel layered double hydroxide on the surface of the ceramic powder, and finally realizes the deposition of phytic acid through the chelation of phytic acid and metal ions, thereby preparing the ceramic material.

[0015] As a preferred embodiment, the steps of the hybridization treatment include: in terms of weight parts, disperse 2 - 4 parts of commercially available ceramic powder in 360 - 400 parts of methanol, then add 2 - 4 parts of cobalt nitrate hexahydrate and 8 - 16 parts of 2 - methylimidazole, stir and react at a speed of 400 - 500 r / min for 4 - 6 h, centrifuge, wash with water, and dry to obtain hybrid ceramic powder.

[0016] As a preferred embodiment, the steps of the ion exchange treatment include: dispersing 2 to 4 parts of the hybrid ceramic powder in 280 to 300 parts of deionized water, adding 1.4 to 1.8 parts of nickel sulfate hexahydrate, and then stirring for 3 to 4 hours under the condition of 300 to 400 r / min, centrifuging, washing with water, and drying to obtain ceramic powder-cobalt nickel layered double metal hydroxide.

[0017] As a preferred embodiment, the steps of the chelation treatment include: dissolving 8 to 10 parts of phytic acid in 380 to 400 parts of absolute ethanol, then adding 2 to 4 parts of ceramic powder-layered double metal hydroxide and stirring for 160 to 180 minutes, centrifuging, washing with water, and drying to obtain the ceramic material.

[0018] As a preferred embodiment, the glass fiber is a surface-modified glass fiber; The preparation method of the surface-modified glass fiber includes: first purifying the commercially available glass fiber, then performing silane modification using 3-aminopropyltriethoxysilane to obtain silane-modified glass fiber; finally performing surface modification treatment on the silane-modified glass fiber to obtain the surface-modified glass fiber.

[0019] The surface-modified glass fiber of the present invention first removes the residual organic substances on the surface of the commercially available glass fiber through acetone purification, then grafts through 3-aminopropyltriethoxysilane to introduce amino groups on the surface of the glass fiber, and finally prepares the surface-modified glass fiber through the in-situ growth of polyphosphamide.

[0020] As a preferred embodiment, the steps of the purification treatment include: soaking the commercially available glass fiber in acetone for 120 to 140 minutes, filtering, and vacuum drying.

[0021] As a preferred embodiment, the steps of the silane modification include: taking 4 to 6 parts by weight of 3-aminopropyltriethoxysilane and dissolving it in 200 to 240 parts of absolute ethanol, then adding 10 to 14 parts of the purified glass fiber, condensing and refluxing for 100 to 120 minutes under the condition of 80 to 84 °C, filtering, washing, and drying at 110 to 120 °C for 12 to 16 hours to obtain the silane-modified glass fiber.

[0022] As a preferred embodiment, the steps of the surface modification include: mixing 4 to 6 parts of phosphorus oxychloride and 12 to 16 parts of acetonitrile to obtain solution A, adding 10 to 14 parts of the silane-modified glass fiber to 160 to 200 parts of acetonitrile and ultrasonically dispersing for 50 to 60 minutes, placing it in a nitrogen atmosphere, controlling the temperature at 2 to 4 °C, first adding 10 to 12 parts of triethylamine and 6 to 8 parts of 4,4-diaminodiphenylmethane, then adding 12 to 16 parts of solution A and reacting for 40 to 60 minutes, raising the temperature to 40 to 50 °C and refluxing for 20 to 24 hours, filtering with suction, washing, and drying to obtain the surface-modified glass fiber.

[0023] As a preferred solution, the curing agent is N-aminoethylpiperazine and methyltetrahydrophthalic anhydride.

[0024] As a preferred solution, the mass ratio of N-aminoethylpiperazine to methyltetrahydrophthalic anhydride in the curing agent is (1-2):1.

[0025] The curing agent is selected as N-aminoethylpiperazine and methyltetrahydrophthalic anhydride for compounding, and by controlling the mass ratio of the two, N-aminoethylpiperazine can achieve efficient curing of epoxy resin, while methyltetrahydrophthalic anhydride can improve the flexibility and impact resistance of the cured product; with the reaction of N-aminoethylpiperazine and phytic acid, bio-based polymer ammonium phytate is obtained, which can be used as a reactive flame retardant, and by forming a phosphorus-rich expanded carbon layer, it plays a role in blocking the transfer of heat and oxygen in the condensed phase, improving the flame retardancy and smoke suppression performance of the composite material.

[0026] As a preferred solution, the antistatic agent is selected from octadecylamine polyoxyethylene ether or castor oil polyoxyethylene ether.

[0027] As a preferred solution, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, and antioxidant 168.

[0028] In the second aspect of the present invention, a method for preparing the impact-resistant ceramic polymer composite material as described in the first aspect is provided, including the following steps: By weight, 60-80 parts of epoxy resin are heated to a molten state, 20-30 parts of ceramic material, 10-14 parts of glass fiber, 2-4 parts of antistatic agent, and 2-4 parts of antioxidant are added and stirred evenly to obtain a mixture, and then 20-24 parts of curing agent are added and mixed evenly, followed by vacuum defoaming, and after curing, the impact-resistant ceramic polymer composite material is obtained.

[0029] As a preferred solution, the curing conditions include: pre-curing at 40-50°C for 80-100 min first, then curing at 80-100°C for 2-4 h, and cooling to room temperature.

[0030] Compared with the prior art, the present invention has the following beneficial effects: (1) The phytic acid deposited on the outer layer of the ceramic material in the present invention can not only react with N-aminoethylpiperazine, but also combine with the amino groups in the surface-modified glass fiber, and has good compatibility in the epoxy matrix. By improving the interfacial bonding situation, stress is effectively dispersed and the impact strength is increased; at the same time, through the synergistic effect of silicon element, cobalt-nickel bimetal and phytic acid in the ceramic material, combined with the interfacial flame retardancy of the surface-modified glass fiber, the flame retardancy of the composite material can be effectively improved.

[0031] (2) The specific surface area of silicon dioxide in the ceramic material of the present invention is large, making it easier to form a continuous carbon layer. Cobalt-nickel layered double metal hydroxide has good catalytic effects, significantly improving the density of the carbon layer, reducing the release of heat and toxic gases. The dehydration and carbonization of phytic acid effectively increase the residual weight ratio. Through the synergistic effects of silicon element, cobalt-nickel bimetal and phytic acid, the oxygen index of the material is effectively improved. In addition, the phytic acid deposited on the outermost layer of the ceramic material has good compatibility with the epoxy resin matrix, improving the interfacial bonding between the ceramic component and the polymer component, reducing stress concentration and thus increasing the impact strength.

[0032] (3) The surface-modified glass fiber of the present invention can achieve interfacial flame retardancy through the polyphosphamide flame retardant layer. By forming a surface topography with extremely large roughness, the wettability and diffusion rate of the resin melt on the surface of the glass fiber are reduced. At the same time, as combustion progresses, the flame retardant layer begins to crack, forming high-temperature polyphosphoric acid and pyrophosphoric acid intermediates, and simultaneously generating a large amount of incombustible gases that diffuse into the combustion zone, diluting the concentration of combustible gases and oxygen, and reducing the combustion rate in the flame zone. In addition, due to the introduction of amino groups, the surface-modified glass fiber can improve the dispersibility and interfacial compatibility of the glass fiber in the polymer resin matrix, reduce the stress concentration effect, and thus improve the impact strength of the composite material. Specific embodiments

[0033] For the convenience of understanding the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0034] The sources of some components in the examples and comparative examples are as follows: Epoxy resin, product number HYSZ01, purchased from Jinan Shanhaichem Technology Co., Ltd.; Commercially available ceramic powder, purchased from Jiangsu Jingshengyuan New Material Technology Co., Ltd.; Cobalt nitrate hexahydrate, CAS No. 10026-22-9, purchased from Shanghai Macklin Biochemical Co., Ltd.; 2-Methylimidazole, CAS No. 693-98-1, purchased from Sinopharm Chemical Reagent Co., Ltd.; Nickel sulfate hexahydrate, CAS No. 10101-97-0, purchased from Shanghai Macklin Biochemical Co., Ltd.; Phytic acid, CAS No. 83-86-3, purchased from Sinopharm Chemical Reagent Co., Ltd.; Commercially available glass fiber, product number S30527, purchased from Shanghai Yuanye Bio-Technology Co., Ltd.; 3-Aminopropyltriethoxysilane, CAS No. 919-30-2, purchased from Shanghai Macklin Biochemical Co., Ltd.; Phosphorus oxychloride, CAS No. 10025-87-3, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Triethylamine, CAS No. 121-44-8, was purchased from Sinopharm Chemical Reagent Co., Ltd.; 4,4-Diaminodiphenylmethane, CAS No. 101-77-9, was purchased from Sinopharm Chemical Reagent Co., Ltd.; N-aminoethylpiperazine, CAS No. 140-31-8, was purchased from Hubei Chengfeng Chemical Co., Ltd.; Methyltetrahydrophthalic anhydride, CAS No. 19438-64-3, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; Octadecaneamine polyoxyethylene ether, CAS No. 26635-92-7, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; Castor oil polyoxyethylene ether, CAS No. 61791-12-6, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Antioxidant 1010, CAS No. 6683-19-8, was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.; Antioxidant 1076, CAS No. 2082-79-3, was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.; Antioxidant 168, CAS No. 31570-04-4, was purchased from Nantong Runfeng Petrochemical Co., Ltd.

[0035] Example 1 This embodiment provides a method for preparing an impact-resistant ceramic polymer composite material, comprising the following steps: In parts by weight, 80 parts of epoxy resin are heated to a molten state, 30 parts of ceramic material, 14 parts of surface-modified glass fiber, 4 parts of antistatic agent octadecylamine polyoxyethylene ether and 4 parts of antioxidant 1010 are added and stirred evenly to obtain a mixture, and then 24 parts of curing agent (16 parts of N-aminoethylpiperazine and 8 parts of methyltetrahydrophthalic anhydride) are added and mixed evenly, and then vacuum degassing is performed, and the mixture is pre-cured at 50°C for 80 minutes, then cured at 100°C for 2 hours, and cooled to room temperature to obtain an impact-resistant ceramic polymer composite material.

[0036] Preparation of the ceramic material: By weight, disperse 4 parts of commercially available ceramic powder in 400 parts of methanol, then add 4 parts of cobalt nitrate hexahydrate and 16 parts of 2-methylimidazole, stir and react at a speed of 500 r / min for 4 h, centrifuge, wash with water, and dry to obtain hybrid ceramic powder; Disperse 4 parts of the hybrid ceramic powder in 300 parts of deionized water, add 1.8 parts of nickel sulfate hexahydrate, and stir at 400 r / min for 3 h, centrifuge, wash with water, and dry to obtain ceramic powder-cobalt nickel layered double metal hydroxide; Dissolve 10 parts of phytic acid in 400 parts of absolute ethanol, then add 4 parts of the ceramic powder-layered double metal hydroxide and stir for 180 min, centrifuge, wash with water, and dry to obtain the ceramic material.

[0037] Preparation of the surface-modified glass fiber: First, soak the commercially available glass fiber in acetone for 140 min, filter, and dry in vacuum. Dissolve 6 parts of 3-aminopropyltriethoxysilane in 240 parts of absolute ethanol, then add 14 parts of the purified glass fiber, and carry out condensation reflux at 84 °C for 100 min, filter, wash, and dry at 120 °C for 12 h to obtain the silane-modified glass fiber; Mix 6 parts of phosphorus oxychloride and 16 parts of acetonitrile to obtain solution A. Add 14 parts of the silane-modified glass fiber to 200 parts of acetonitrile, ultrasonically disperse for 60 min, place in a nitrogen atmosphere, control the temperature at 4 °C, first add 12 parts of triethylamine and 8 parts of 4,4-diaminodiphenylmethane, then add 16 parts of solution A and react for 60 min, raise the temperature to 50 °C and reflux for 20 h, filter with suction, wash, and dry to obtain the surface-modified glass fiber.

[0038] Example 2

[0039] This example provides a preparation method of an impact-resistant ceramic polymer composite material, including the following steps: By weight, heat 60 parts of epoxy resin to a molten state, add 20 parts of the ceramic material, 10 parts of the surface-modified glass fiber, 2 parts of the antistatic agent castor oil polyoxyethylene ether, and 2 parts of the antioxidant 1076, stir evenly to obtain a mixture, then add 20 parts of the curing agent (10 parts of N-aminoethylpiperazine and 10 parts of methyltetrahydrophthalic anhydride), mix evenly, and then carry out vacuum degassing. First, pre-cure at 40 °C for 100 min, then cure at 100 °C for 2 h, and cool to room temperature to obtain the impact-resistant ceramic polymer composite material.

[0040] Preparation of the ceramic material: By weight, disperse 2 parts of commercially available ceramic powder in 360 parts of methanol, then add 2 parts of cobalt nitrate hexahydrate and 8 parts of 2-methylimidazole, stir and react at a speed of 400 r / min for 6 h, centrifuge, wash with water, and dry to obtain hybrid ceramic powder; Disperse 2 parts of the hybrid ceramic powder in 280 parts of deionized water, add 1.4 parts of nickel sulfate hexahydrate, and stir at 300 r / min for 4 h, centrifuge, wash with water, and dry to obtain ceramic powder-cobalt nickel layered double metal hydroxide; Dissolve 8 parts of phytic acid in 380 parts of absolute ethanol, then add 2 parts of the ceramic powder-layered double metal hydroxide and stir for 160 min, centrifuge, wash with water, and dry to obtain the ceramic material.

[0041] Preparation of the surface-modified glass fiber: First, soak commercially available glass fiber in acetone for 120 min, filter, and dry in vacuum. Dissolve 4 parts of 3-aminopropyltriethoxysilane in 200 parts of absolute ethanol, then add 10 parts of the purified glass fiber, and condense and reflux at 80 °C for 120 min, filter, wash, and dry at 110 °C for 16 h to obtain silane-modified glass fiber; Mix 4 parts of phosphorus oxychloride and 12 parts of acetonitrile to obtain solution A. Add 10 parts of the silane-modified glass fiber to 160 parts of acetonitrile, ultrasonically disperse for 50 min, place in a nitrogen atmosphere, control the temperature at 2 °C, first add 10 parts of triethylamine and 6 parts of 4,4-diaminodiphenylmethane, then add 12 parts of solution A and react for 40 min, raise the temperature to 40 °C and reflux for 24 h, filter with suction, wash, and dry to obtain the surface-modified glass fiber.

[0042] Example 3

[0043] This example provides a preparation method of an impact-resistant ceramic polymer composite material, including the following steps: By weight, heat 70 parts of epoxy resin to a molten state, add 25 parts of the ceramic material, 12 parts of the surface-modified glass fiber, 3 parts of the antistatic agent octadecylamine polyoxyethylene ether, and 3 parts of the antioxidant 168, stir evenly to obtain a mixture, then add 22 parts of the curing agent (14 parts of N-aminoethylpiperazine and 8 parts of methyltetrahydrophthalic anhydride), mix evenly, and then perform vacuum degassing. First, pre-cure at 45 °C for 90 min, then cure at 90 °C for 3 h, and cool to room temperature to obtain the impact-resistant ceramic polymer composite material.

[0044] Preparation of the ceramic material: By weight, disperse 3 parts of commercially available ceramic powder in 380 parts of methanol, then add 3 parts of cobalt nitrate hexahydrate and 12 parts of 2-methylimidazole, stir and react at a speed of 450 r / min for 5 h, centrifuge, wash with water, and dry to obtain hybrid ceramic powder; Disperse 3 parts of the hybrid ceramic powder in 290 parts of deionized water, add 1.6 parts of nickel sulfate hexahydrate, and stir at 350 r / min for 3.5 h, centrifuge, wash with water, and dry to obtain ceramic powder-cobalt nickel layered double metal hydroxide; Dissolve 9 parts of phytic acid in 390 parts of absolute ethanol, then add 3 parts of the ceramic powder-layered double metal hydroxide and stir for 170 min, centrifuge, wash with water, and dry to obtain the ceramic material.

[0045] Preparation of the surface-modified glass fiber: First, soak the commercially available glass fiber in acetone for 130 min, filter, and dry in vacuum. Dissolve 5 parts of 3-aminopropyltriethoxysilane in 220 parts of absolute ethanol, then add 12 parts of the purified glass fiber, and carry out condensation reflux at 82 °C for 110 min, filter, wash, and dry at 115 °C for 14 h to obtain silane-modified glass fiber; Mix 5 parts of phosphorus oxychloride and 14 parts of acetonitrile to obtain solution A. Add 12 parts of the silane-modified glass fiber to 180 parts of acetonitrile, ultrasonically disperse for 55 min, place in a nitrogen atmosphere, control the temperature at 3 °C, first add 11 parts of triethylamine and 7 parts of 4,4-diaminodiphenylmethane, then add 14 parts of solution A and react for 50 min, raise the temperature to 45 °C and reflux for 22 h, filter with suction, wash, and dry to obtain the surface-modified glass fiber.

[0046] Comparative Example 1 The difference between this comparative example and Example 1 is that commercially available ceramic powder is used to replace the ceramic material prepared in the present invention.

[0047] Comparative Example 2 The difference between this comparative example and Example 1 is that commercially available glass fiber (product number S30527) is used to replace the surface-modified glass fiber.

[0048] Comparative Example 3 The difference between this comparative example and Example 1 is that the dosage of N-aminoethylpiperazine in the curing agent is changed to 20 parts and the dosage of methyltetrahydrophthalic anhydride is changed to 4 parts.

[0049] Comparative Example 4 The difference between this comparative example and Example 1 is that the dosage of N-aminoethylpiperazine in the curing agent is changed to 8 parts and the dosage of methyltetrahydrophthalic anhydride is changed to 16 parts.

[0050] Test the performance of the composite materials provided in the above examples and comparative examples. The test method is as follows: Oxygen index test: The test was carried out according to the requirements of "GB / T 8924-2005 Test method for combustion properties of fiber reinforced plastics - Oxygen index method".

[0051] Impact strength test: The test was carried out according to the requirements of "GB / T 1043.1-2008 Plastics - Determination of Charpy impact properties - Part 1: Non-instrumented impact test".

[0052] The above performance test data are shown in Table 1.

[0053] Table 1 Performance test results

[0054] As can be seen from the above, in the present invention, commercially available ceramic powder is used as a raw material, and ceramic materials are prepared through hybridization treatment, ion exchange treatment and chelation treatment in sequence. In combination with epoxy resin, glass fiber and curing agent, an impact-resistant ceramic polymer composite material (Examples 1 to 3) is prepared, and its comprehensive performance is the best, with an oxygen index of 34.2 to 34.7% and an impact strength of 12.43 to 12.68 kJ / m 2 。

[0055] Compared with Example 1, when using commercially available ceramic powder to replace the ceramic material prepared in the present invention, the flame retardancy performance becomes worse and the impact strength decreases (Comparative Example 1); compared with Example 1, when using commercially available glass fiber (product number S30527) to replace the surface-modified glass fiber, the flame retardancy performance becomes worse and the impact strength decreases (Comparative Example 2); compared with Example 1, when the dosage of N-aminoethylpiperazine in the curing agent is changed to 20 parts and the dosage of methyltetrahydrophthalic anhydride is changed to 4 parts, due to the too small dosage of methyltetrahydrophthalic anhydride, the flexibility of the cured product decreases, and the impact strength decreases (Comparative Example 3); compared with Example 1, when the dosage of N-aminoethylpiperazine in the curing agent is changed to 8 parts and the dosage of methyltetrahydrophthalic anhydride is changed to 16 parts, due to the too small dosage of N-aminoethylpiperazine, the formation of ammonium phytate with phytic acid decreases, and the flame retardancy performance becomes worse (Comparative Example 4).

Claims

1. An impact-resistant ceramic polymer composite material, characterized in that by weight, it comprises the following components: 60 - 80 parts of epoxy resin, 20 - 30 parts of ceramic material, 10 - 14 parts of glass fiber, 20 - 24 parts of curing agent, 2 - 4 parts of antistatic agent and 2 - 4 parts of antioxidant; The preparation method of the ceramic material includes: first, hybridize the commercially available ceramic powder to obtain hybrid ceramic powder; then perform ion exchange treatment on the hybrid ceramic powder to obtain ceramic powder - cobalt nickel layered double metal hydroxide; finally, perform chelation treatment on the ceramic powder - cobalt nickel layered double metal hydroxide to obtain the ceramic material.

2. The impact-resistant ceramic polymer composite material according to claim 1, characterized in that The steps of the hybridization treatment include: by weight, disperse 2 - 4 parts of commercially available ceramic powder in 360 - 400 parts of methanol, then add 2 - 4 parts of cobalt nitrate hexahydrate and 8 - 16 parts of 2 - methylimidazole, stir and react at a speed of 400 - 500 r / min for 4 - 6 h, centrifuge, wash with water, and dry to obtain hybrid ceramic powder.

3. The impact-resistant ceramic polymer composite material according to claim 1, characterized in that The steps of the ion exchange treatment include: disperse 2 - 4 parts of hybrid ceramic powder in 280 - 300 parts of deionized water, add 1.4 - 1.8 parts of nickel sulfate hexahydrate, and stir at 300 - 400 r / min for 3 - 4 h, centrifuge, wash with water, and dry to obtain ceramic powder - cobalt nickel layered double metal hydroxide.

4. The impact-resistant ceramic polymer composite material according to claim 1, characterized in that The steps of the chelation treatment include: dissolve 8 - 10 parts of phytic acid in 380 - 400 parts of absolute ethanol, then add 2 - 4 parts of ceramic powder - layered double metal hydroxide and stir for 160 - 180 min, centrifuge, wash with water, and dry to obtain the ceramic material.

5. The impact-resistant ceramic polymer composite material according to claim 1, characterized in that The glass fiber is surface-modified glass fiber; The preparation method of the surface-modified glass fiber includes: first, purify the commercially available glass fiber, and then perform silane modification with 3 - aminopropyltriethoxysilane to obtain silane-modified glass fiber; Finally, perform surface modification treatment on the silane-modified glass fiber to obtain surface-modified glass fiber.

6. The impact-resistant ceramic polymer composite material according to claim 5, characterized in that The steps of the silane modification include: by weight, dissolve 4 - 6 parts of 3 - aminopropyltriethoxysilane in 200 - 240 parts of absolute ethanol, then add 10 - 14 parts of purified glass fiber, condense and reflux at 80 - 84 °C for 100 - 120 min, filter, wash, and dry at 110 - 120 °C for 12 - 16 h to obtain silane-modified glass fiber.

7. The impact-resistant ceramic polymer composite material according to claim 5, characterized in that The steps of the surface modification include: mixing 4 to 6 parts of phosphorus oxychloride and 12 to 16 parts of acetonitrile to obtain solution A; adding 10 to 14 parts of silane-modified glass fiber into 160 to 200 parts of acetonitrile, ultrasonically dispersing for 50 to 60 min, placing in a nitrogen atmosphere, controlling the temperature at 2 to 4 °C, first adding 10 to 12 parts of triethylamine and 6 to 8 parts of 4,4-diaminodiphenylmethane, then adding 12 to 16 parts of solution A and reacting for 40 to 60 min, heating to 40 to 50 °C and refluxing for 20 to 24 h, filtering, washing, and drying to obtain surface-modified glass fiber.

8. The impact-resistant ceramic polymer composite material according to claim 1, wherein the curing agent is N-aminoethylpiperazine and methyltetrahydrophthalic anhydride; the mass ratio of N-aminoethylpiperazine to methyltetrahydrophthalic anhydride in the curing agent is (1 to 2):

1.

9. The impact-resistant ceramic polymer composite material according to claim 1, wherein the antistatic agent is selected from octadecylamine polyoxyethylene ether or castor oil polyoxyethylene ether.

10. A method for preparing an impact-resistant ceramic polymer composite material, characterized in that it includes the following steps: first, hybridize the commercially available ceramic powder to obtain hybrid ceramic powder; then perform ion exchange treatment on the hybrid ceramic powder to obtain ceramic powder-cobalt nickel layered double metal hydroxide; finally, perform chelation treatment on the ceramic powder-cobalt nickel layered double metal hydroxide to obtain a ceramic material; by weight, heat 60 to 80 parts of epoxy resin to a molten state, add 20 to 30 parts of the ceramic material, 10 to 14 parts of glass fiber, 2 to 4 parts of antistatic agent, and 2 to 4 parts of antioxidant, stir evenly to obtain a mixture, then add 20 to 24 parts of curing agent, mix evenly, and then perform vacuum degassing, and cure to obtain the impact-resistant ceramic polymer composite material.

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