Hollow microbead smoke and temperature suppression regenerated fireproof material and preparation method thereof
By compounding hollow microbeads with graphene and using glutaraldehyde-(3-aminopropyltriethoxysilane) modification technology, the carcinogenicity and insufficient graphene mechanical properties of traditional asbestos fiber fire-resistant plates are solved. A high compressive strength and low cost hollow microbead smoke suppression and temperature suppression regeneration fire-repellent materials are achieved.
Patent Information
- Application Number
- CN202411796141.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-09
- Publication Date
- 2025-02-14
AI Technical Summary
Traditional asbestos fiber fire-resistant plates have a risk of carcinogenicity, and graphene shows agglomeration in suppressing smoke and temperature, reducing the mechanical properties of the material.
The hollow microbeads and graphene composite materials are used to modify hollow microbeads @ graphene by glutaraldehyde-(3-aminopropyltriethoxysilane) to improve the compressive strength of the material and reduce the preparation cost.
The compressive strength of the material is significantly improved, and the preparation cost is reduced through the straw preparation of graphene, and the mechanical properties and safety of the material are improved.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] The invention belongs to the field of plates, and in particular relates to a hollow microsphere smoke and temperature suppression regenerative fireproof material and a preparation method thereof. Background Art
[0002] Traditional fireproof panels mostly use asbestos fibers as the main raw material in the production process. Although asbestos fibers can provide certain fireproof properties, scientific research shows that asbestos fibers are potentially carcinogenic and long-term exposure may pose a serious threat to human health. Therefore, fireproof panels using asbestos as raw materials have obvious deficiencies in safety.
[0003] Hollow microspheres, also called hollow glass microspheres, are often used to improve the mechanical properties of materials and flame retardant research due to their hollow and glassy structures. Hollow microspheres can significantly reduce the risk of fire from the perspective of smoke and temperature suppression. Graphene can effectively suppress smoke and temperature because of its honeycomb mesh structure, but graphene is easy to agglomerate and easily reduce the mechanical properties of the prepared material. Summary of the invention
[0004] In order to solve the problems existing in the prior art, the present invention provides a hollow microsphere smoke and temperature suppression regenerative fireproof material and a preparation method thereof The present invention is achieved through the following technical solutions: A hollow microsphere smoke and temperature suppression regenerative fireproof material, comprising, by mass, 80 to 120 parts of PVC resin, 20 to 30 parts of wood flour, 15 to 30 parts of calcium carbonate, 10 to 15 parts of epoxy soybean oil, 5 to 8 parts of coumarone resin, 5 to 8 parts of Ba / Cd composite stabilizer, 5 to 10 parts of DOP plasticizer, and 5 to 30 parts of hollow microsphere@graphene composite material; The hollow microbeads@graphene composite material is selected from one or more of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads@graphene, glutaraldehyde modified hollow microbeads@graphene, and 3-aminopropyltriethoxysilane modified hollow microbeads@graphene.
[0005] Preferably, the graphene composite material is selected from glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads@graphene.
[0006] Preferably, the preparation method of the glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads@graphene is: The hollow glass microspheres were soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution was 7:3; 6 g of hollow glass microspheres were added to 200 mL of ethanol, ultrasonicated for 10 minutes, and then 0.3 g of 3-aminopropyltriethoxysilane was added, and stirring was continued. The mixture was reacted at 40° C. for 4 hours, and then filtered, washed with deionized water, and vacuum dried at 100° C. to obtain 3-aminopropyltriethoxysilane-modified hollow microspheres; 3 g of 3-aminopropyltriethoxysilane-modified hollow microspheres were dissolved in 100 mL of neutral phosphate buffer solution, 0.6 g of glutaraldehyde was added, and then heated to 40 °C for 4 h, filtered, washed with deionized water, and vacuum dried at 100 °C to obtain glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, glutaraldehyde-modified hollow microbeads were added, wherein the mass ratio of graphene to glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microbeads was 1:1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microbeads@graphene.
[0007] Preferably, the hollow microbeads@graphene composite material is selected from glutaraldehyde modified hollow microbeads@graphene.
[0008] Preferably, the preparation method of the glutaraldehyde modified hollow microspheres @ graphene is: soaking the hollow glass microspheres in a mixed solution of concentrated sulfuric acid and hydrogen peroxide for 30 minutes, washing with distilled water and then drying, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution of concentrated sulfuric acid and hydrogen peroxide is 7:3; taking 6g of hollow glass microspheres and adding them to 200mL of neutral phosphate buffer solution, ultrasonicating for 10min, then adding 0.3g of glutaraldehyde, continuing to stir, reacting at 40°C for 4h, then filtering and washing with deionized water, and vacuum drying at 100°C to obtain glutaraldehyde modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, glutaraldehyde-modified hollow microbeads were added, wherein the mass ratio of graphene to glutaraldehyde-modified hollow microbeads was 1:1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain glutaraldehyde-modified hollow microbeads@graphene.
[0009] Preferably, the hollow microbeads@graphene composite material is selected from penta-3-aminopropyltriethoxysilane modified hollow microbeads@graphene.
[0010] Preferably, the preparation method of the 3-aminopropyltriethoxysilane modified hollow microbeads@graphene is: The hollow glass microspheres were soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution was 7:3; 6 g of hollow glass microspheres were added to 200 mL of ethanol, ultrasonicated for 10 minutes, and then 0.3 g of 3-aminopropyltriethoxysilane was added, and stirring was continued. The mixture was reacted at 40° C. for 4 hours, and then filtered, washed with deionized water, and vacuum dried at 100° C. to obtain 3-aminopropyltriethoxysilane-modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, 3-aminopropyltriethoxysilane-modified hollow microbeads were added, wherein the mass ratio of graphene to 3-aminopropyltriethoxysilane-modified hollow microbeads was 1:1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain 3-aminopropyltriethoxysilane-modified hollow microbeads@graphene.
[0011] Preferably, the preparation method of graphene in the hollow microsphere@graphene composite material is: The corn stalks were crushed and then passed through a 100-mesh sieve. The sieved powder was then washed three times with 0.1M HCl to remove impurities. The powder was then washed with distilled water and dried for later use. 5 g of dry powder was weighed and put into a reactor. 50 mL of deionized water was added and reacted in an oven at 170°C for 12 h. After natural cooling, the mixture was centrifuged and the supernatant was filtered through a 0.22 μm microporous membrane to purify the graphene, which was then vacuum dried for later use.
[0012] Furthermore, the present invention also provides a method for preparing a hollow microbead smoke and temperature suppressant regenerated fireproof material, wherein the raw materials are stirred at 1000 r / min at room temperature for 0.5 h, extruded into granules, and the extrusion granulation temperature is 140°C. The granules are cast into sheets and then calendered with calendering rollers to obtain sheets with a thickness of 2 mm. The calendering is carried out using two groups of calendering rollers, and the calendering temperature is 130°C. The hollow microbead smoke and temperature suppressant regenerated fireproof material is cut into pieces.
[0013] Compared with the prior art, the present invention has the following advantages and beneficial effects: The present invention obtains a composite material by surface-modifying hollow microspheres and compounding them with renewable graphene, which significantly improves the compressive strength of the material. At the same time, the graphene is prepared through straw to reduce the preparation cost. DETAILED DESCRIPTION
[0014] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The illustrative embodiments of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.
[0015] The preparation method of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads@graphene in the present invention: The hollow glass microspheres were soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution was 7:3; 6 g of hollow glass microspheres were added to 200 mL of ethanol, ultrasonicated for 10 minutes, and then 0.3 g of 3-aminopropyltriethoxysilane was added, and stirring was continued. The mixture was reacted at 40° C. for 4 hours, and then filtered, washed with deionized water, and vacuum dried at 100° C. to obtain 3-aminopropyltriethoxysilane-modified hollow microspheres; 3 g of 3-aminopropyltriethoxysilane-modified hollow microspheres were dissolved in 100 mL of neutral phosphate buffer solution, 0.6 g of glutaraldehyde was added, and then heated to 40 °C for 4 h, filtered, washed with deionized water, and vacuum dried at 100 °C to obtain glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, glutaraldehyde-modified hollow microbeads were added, wherein the mass ratio of graphene to glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microbeads was 1:1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microbeads@graphene.
[0016] The preparation method of glutaraldehyde modified hollow microbeads@graphene in the present invention: The hollow glass microspheres were soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution was 7:3; 6 g of hollow glass microspheres were added to 200 mL of neutral phosphate buffer solution, ultrasonicated for 10 minutes, and then 0.3 g of glutaraldehyde was added, and stirring was continued. The mixture was reacted at 40°C for 4 hours, and then filtered, washed with deionized water, and vacuum dried at 100°C to obtain glutaraldehyde-modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, glutaraldehyde-modified hollow microbeads were added, wherein the mass ratio of graphene to glutaraldehyde-modified hollow microbeads was 1:1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain glutaraldehyde-modified hollow microbeads@graphene.
[0017] The preparation method of 3-aminopropyltriethoxysilane modified hollow microbeads@graphene in the present invention: The hollow glass microspheres were soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution was 7:3; 6 g of hollow glass microspheres were added to 200 mL of ethanol, ultrasonicated for 10 minutes, and then 0.3 g of 3-aminopropyltriethoxysilane was added, and stirring was continued. The mixture was reacted at 40° C. for 4 hours, and then filtered, washed with deionized water, and vacuum dried at 100° C. to obtain 3-aminopropyltriethoxysilane-modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, 3-aminopropyltriethoxysilane-modified hollow microbeads were added, wherein the mass ratio of graphene to 3-aminopropyltriethoxysilane-modified hollow microbeads was 1:1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain 3-aminopropyltriethoxysilane-modified hollow microbeads@graphene.
[0018] The preparation method of hollow microspheres@graphene in the present invention: Graphene was added to 100 mL of deionized water, the pH was adjusted to 5-6 using a Na2CO3 solution, and then hollow microbeads were added, wherein the mass ratio of graphene to hollow microbeads was 1:1, and then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate, which was washed with distilled water and dried at 60°C for 48 hours to obtain hollow microbeads@graphene.
[0019] The preparation method of graphene in the present invention: The corn stalks were crushed and then passed through a 100-mesh sieve. The sieved powder was then washed three times with 0.1M HCl to remove impurities. The powder was then washed with distilled water and dried for later use. 5 g of dry powder was weighed and put into a reactor. 50 mL of deionized water was added and reacted in an oven at 170°C for 12 h. After natural cooling, the mixture was centrifuged and the supernatant was filtered through a 0.22 μm microporous membrane to purify the graphene, which was then vacuum dried for later use.
[0020] Example 1, a hollow microsphere smoke and temperature suppression regenerative fireproof material, which includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 5 parts of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microspheres @ graphene.
[0021] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0022] Example 2, a hollow microsphere smoke and temperature suppression regenerative fireproof material, includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 7 parts of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microspheres @ graphene.
[0023] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0024] Example 3, a hollow microsphere smoke and temperature suppression regenerative fireproof material, which includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 10 parts of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microspheres @ graphene.
[0025] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0026] Example 4, a hollow microsphere smoke and temperature suppression regenerative fireproof material, includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 15 parts of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microspheres @ graphene.
[0027] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0028] Example 5, a hollow microsphere smoke and temperature suppression regenerative fireproof material, which includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 20 parts of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microspheres @ graphene.
[0029] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0030] Example 6, a hollow microsphere smoke and temperature suppression regenerative fireproof material, which includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 25 parts of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microspheres @ graphene.
[0031] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0032] Example 7, a hollow microsphere smoke and temperature suppression regenerative fireproof material, which includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 30 parts of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microspheres @ graphene.
[0033] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0034] Example 8, a hollow microsphere smoke and temperature suppression regenerative fireproof material, includes, by mass, 100 parts of PVC resin, 25 parts of wood powder, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 30 parts of glutaraldehyde-modified hollow microspheres @ graphene.
[0035] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0036] Comparative Example 1, a hollow microsphere smoke and temperature suppression regenerative fireproof material, includes, by mass, 100 parts of PVC resin, 25 parts of wood flour, 20 parts of calcium carbonate, 10 parts of epoxy soybean oil, 5 parts of coumarone resin, 5 parts of Ba / Cd composite stabilizer, 5 parts of DOP plasticizer, and 30 parts of hollow microspheres @ graphene.
[0037] Preparation method: Stir the raw materials at 1000r / min at room temperature for 0.5h, extrude and granulate at a temperature of 140°C, cast the granules into sheets and calender them with calendering rollers to obtain sheets with a thickness of 2mm. Calendering is carried out using two sets of calendering rollers at a temperature of 130°C; cut them to obtain a hollow microbead smoke and temperature suppression regenerated fireproof material.
[0038] Test case 1, Tensile properties: Tested in accordance with GB / T 1040.1-2018, the narrowest dimension of the dumbbell-shaped standard specimen is 15mm×4mm, and the tensile speed is 50mm / min. Impact strength is tested in accordance with GB / T 1843-2008.
[0039] Table 1 Performance test
[0040] It can be seen from the data in Table 1 that compared with Comparative Example 1, the hollow microbead smoke and temperature suppression regenerated fireproof materials using glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads @ graphene and glutaraldehyde modified hollow microbeads @ graphene in Examples 1 to 7 have better tensile strength and impact strength, and exhibit excellent mechanical properties.
Claims
1. A hollow microsphere smoke and temperature suppression regenerative fireproof material, characterized in that: The composition includes 80-120 parts of PVC resin, 20-30 parts of wood flour, 15-30 parts of calcium carbonate, 10-15 parts of epoxidized soybean oil, 5-8 parts of coumarone resin, 5-8 parts of Ba / Cd composite stabilizer, 5-10 parts of DOP plasticizer, and 5-30 parts of hollow microsphere@graphene composite material by weight; The hollow microbeads@graphene composite material is selected from one or more of glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads@graphene, glutaraldehyde modified hollow microbeads@graphene, and 3-aminopropyltriethoxysilane modified hollow microbeads@graphene.
2. The hollow microsphere smoke and temperature suppression regenerative fireproof material according to claim 1, characterized in that: The graphene composite material is selected from glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads@graphene.
3. The hollow microsphere smoke and temperature suppression regenerative fireproof material according to claim 2, characterized in that: The preparation method of the glutaraldehyde-(3-aminopropyltriethoxysilane) modified hollow microbeads@graphene is: The hollow glass microspheres were soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution was 7:3; 6 g of hollow glass microspheres were added to 200 mL of ethanol, ultrasonicated for 10 minutes, and then 0.3 g of 3-aminopropyltriethoxysilane was added, and stirring was continued. The mixture was reacted at 40° C. for 4 hours, and then filtered, washed with deionized water, and vacuum dried at 100° C. to obtain 3-aminopropyltriethoxysilane-modified hollow microspheres; 3 g of 3-aminopropyltriethoxysilane-modified hollow microspheres were dissolved in 100 mL of neutral phosphate buffer solution, 0.6 g of glutaraldehyde was added, and then heated to 40 °C for 4 h, filtered, washed with deionized water, and vacuum dried at 100 °C to obtain glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, glutaraldehyde-modified hollow microbeads were added, wherein the mass ratio of graphene to glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microbeads was 1:
1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain glutaraldehyde-(3-aminopropyltriethoxysilane)-modified hollow microbeads@graphene.
4. The hollow microsphere smoke and temperature suppression regenerative fireproof material according to claim 1, characterized in that: The hollow microbead@graphene composite material is selected from glutaraldehyde modified hollow microbead@graphene.
5. The hollow microsphere smoke and temperature suppression regenerative fireproof material according to claim 4, characterized in that: The preparation method of the glutaraldehyde modified hollow microspheres@graphene is as follows: the hollow glass microspheres are soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and then dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution is 7:3; 6g of the hollow glass microspheres are added to 200mL of a neutral phosphate buffer solution, ultrasonicated for 10 minutes, and then 0.3g of glutaraldehyde is added, and stirring is continued, reacting at 40°C for 4h, and then filtering and washing with deionized water, and vacuum drying at 100°C to obtain glutaraldehyde modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, glutaraldehyde-modified hollow microbeads were added, wherein the mass ratio of graphene to glutaraldehyde-modified hollow microbeads was 1:
1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain glutaraldehyde-modified hollow microbeads@graphene.
6. The hollow microsphere smoke and temperature suppression regenerative fireproof material according to claim 1, characterized in that: The hollow microbead@graphene composite material is selected from penta-3-aminopropyltriethoxysilane modified hollow microbead@graphene.
7. The hollow microsphere smoke and temperature suppression regenerative fireproof material according to claim 6, characterized in that: The preparation method of the 3-aminopropyltriethoxysilane modified hollow microbeads@graphene is: The hollow glass microspheres were soaked in a concentrated sulfuric acid and hydrogen peroxide mixed solution for 30 minutes, washed with distilled water and dried, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the concentrated sulfuric acid and hydrogen peroxide mixed solution was 7:3; 6 g of hollow glass microspheres were added to 200 mL of ethanol, ultrasonicated for 10 minutes, and then 0.3 g of 3-aminopropyltriethoxysilane was added, and stirring was continued. The mixture was reacted at 40° C. for 4 hours, and then filtered, washed with deionized water, and vacuum dried at 100° C. to obtain 3-aminopropyltriethoxysilane-modified hollow microspheres; Graphene was added to 100 mL of deionized water, and the pH was adjusted to 5-6 using a Na2CO3 solution. Then, 3-aminopropyltriethoxysilane-modified hollow microbeads were added, wherein the mass ratio of graphene to 3-aminopropyltriethoxysilane-modified hollow microbeads was 1:
1. The mixture was then heated to 80°C for reaction for 2 hours, and then filtered to obtain a precipitate. The precipitate was washed with distilled water and dried at 60°C for 48 hours to obtain 3-aminopropyltriethoxysilane-modified hollow microbeads@graphene.
8. The hollow microsphere smoke and temperature suppression regenerative fireproof material according to claim 1, characterized in that: The preparation method of graphene in the hollow microsphere@graphene composite material is: The corn stalks were crushed and then passed through a 100-mesh sieve. The sieved powder was then washed three times with 0.1M HCl to remove impurities. The powder was then washed with distilled water and dried for later use. 5 g of dry powder was weighed and put into a reactor. 50 mL of deionized water was added and reacted in an oven at 170°C for 12 h. After natural cooling, the mixture was centrifuged and the supernatant was filtered through a 0.22 μm microporous membrane to purify the graphene, which was then vacuum dried for later use.
9. The method for preparing the hollow microsphere smoke and temperature suppression regenerative fireproof material according to claims 1 to 8, characterized in that: The raw materials were stirred at 1000 r / min at room temperature for 0.5 h, extruded into granules at a temperature of 140°C, and the granules were cast into sheets and calendered with calendering rollers to obtain sheets with a thickness of 2 mm. The calendering was carried out using two sets of calendering rollers at a temperature of 130°C. The sheets were cut into a hollow microbead smoke and temperature suppression regenerated fireproof material.