High-performance inorganic silicon-aluminum material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of buildings, in particular to a high-performance inorganic silicon-aluminum material and a preparation method and application thereof. The high-performance inorganic silicon-aluminum material comprises the following components: a carbon framework material formed by carbonizing a polymer material, quartz sand, cement, gypsum, aluminum powder, fly ash and a flame-retardant additive, the polymer material is selected from polyurethane, and the flame-retardant additive comprises an antimony oxide-heteroatom doped graphene composite material and a metal oxide material formed after hydrotalcite is subjected to heat treatment; the high-performance inorganic silicon-aluminum material disclosed by the invention has good thermal insulation property, flame retardant property and mechanical property.

Description

Technical Field

[0001] The present disclosure relates to the field of building technologies, and particularly to a high-performance inorganic silicon-aluminum material, a preparation method thereof, and an application thereof. Background Art

[0002] Thermal insulation materials generally refer to materials with a thermal conductivity less than or equal to 0.2. They play a role in saving energy, reducing energy consumption, reducing harmful substance emissions, improving people's living environment, and extending the service life of buildings, and gradually become an important part of building materials.

[0003] At present, the commonly used building thermal insulation materials in China can be divided into organic thermal insulation materials and inorganic thermal insulation materials. Among them, the organic thermal insulation materials include polystyrene foam materials, foamed rubber materials, polyurethane foam materials, etc. Although such thermal insulation materials have a small density, a small thermal conductivity, good insulation performance, and good heat preservation performance, they have low strength, poor heat resistance, poor aging resistance, a short service life, and are easy to burn, which is likely to cause fires; the inorganic thermal insulation materials include rock wool, slag wool, glass wool, cement foaming materials, etc. Although such thermal insulation materials have good heat resistance, flame retardancy effects, high stability, and convenient construction, they have a large bulk density, lack toughness in materials, and have poor heat preservation effects. Therefore, in order to solve these technical problems, people have started to explore and research new thermal insulation materials - nano thermal insulation materials. Therefore, there is an urgent need for a new type of inorganic silicon-aluminum thermal insulation material. Summary of the Invention

[0004] The present disclosure provides a high-performance inorganic silicon-aluminum material, a preparation method thereof, and an application thereof to solve the deficiencies in the related technologies.

[0005] According to a first aspect of an embodiment of the present disclosure, there is provided a high-performance inorganic silicon-aluminum material, which comprises the following components: a carbon skeleton material formed by carbonizing a polymer material, quartz sand, cement, gypsum, aluminum powder, fly ash, and a flame retardant additive.

[0006] In an aspect of an embodiment of the present disclosure, the mass ratio of the quartz sand, cement, gypsum, aluminum powder, fly ash, and flame retardant additive is selected from (25 - 40):(15 - 35):(15 - 25):(10 - 15):(5 - 10):(0.5 - 1); preferably, the mass ratio of the quartz sand, cement, gypsum, aluminum powder, fly ash, and flame retardant additive is selected from (30 - 35):(20 - 25):(18 - 22):(12 - 14):(5 - 8):(0.5 - 1).

[0007] In an aspect of an embodiment of the present disclosure, the polymer material is selected from polyurethane.

[0008] In one aspect of the embodiments of the present disclosure, the flame retardant additive includes both of the following: a) an antimony oxide - heteroatom - doped graphene composite material; b) a metal oxide material formed by heat - treating hydrotalcite.

[0009] In one aspect of the embodiments of the present disclosure, in the flame retardant additive, the mass ratio of the antimony oxide - heteroatom - doped graphene composite material to the metal oxide material formed by heat - treating hydrotalcite is selected from 1:(0.75 - 1.5).

[0010] According to the second aspect of the embodiments of the present disclosure, a method for preparing a high - performance inorganic silicon - aluminum material is provided. The method includes the following steps: Step 1: Prepare an antimony hydroxide - heteroatom - doped graphene oxide composite material; Step 2: Prepare a zinc - aluminum - cerium hydrotalcite material; Step 3: Prepare a polyurethane prepolymer; and add the polyurethane prepolymer to an organic solvent to form a polyurethane hydrogel; Step 4: Add quartz sand, cement, gypsum, aluminum powder, fly ash, and the antimony hydroxide - heteroatom - doped graphene oxide composite material prepared in Step 1 and the zinc - aluminum - cerium hydrotalcite material prepared in Step 2 to the polyurethane hydrogel respectively. Add a chain extender and a catalyst under stirring, continue stirring for 1 - 2 h and then stop stirring, then react for 3 - 5 h and add a terminator, and then remove the organic solvent in the reaction system by heating; Step 5: Heat - treat the product obtained in Step 4 under the protection of an inert gas at 450°C - 650°C to obtain the high - performance inorganic silicon - aluminum material; wherein, the polyurethane forms a carbon skeleton after heat - treatment, the antimony hydroxide - heteroatom - doped graphene oxide composite material forms an antimony oxide - heteroatom - doped graphene composite material after heat - treatment, and the zinc - aluminum - cerium hydrotalcite material forms a metal oxide material after heat - treatment.

[0011] In one aspect of the embodiments of the present disclosure, Step 1 includes: Step 1 - 1: Provide graphene oxide; add the graphene oxide and phosphorus oxychloride to tetrahydrofuran, then ultrasonicate at room temperature for 45 - 120 min. At the same time, dissolve triethanolamine in tetrahydrofuran to form a triethanolamine solution, and slowly drop the triethanolamine solution into the tetrahydrofuran containing graphene oxide and phosphorus oxychloride while ultrasonicating; Step 1 - 2: After the ultrasonication process ends, add 4,4'-diaminodiphenylmethane to the solution obtained in Step 1 - 1, and then react at room temperature for 20 - 30 h; then carry out centrifugation, washing, and drying to obtain a nitrogen / phosphorus co - doped graphene oxide material; Step 1-3: Add the nitrogen / phosphorus co-doped graphene oxide material prepared in Step 1-2 and an antimony salt into an acidic solution. While stirring, add a complexing agent and a co-precipitating agent, then heat to 45°C - 55°C, continue stirring for 3 - 5 h, and then obtain an antimony hydroxide-heteroatom-doped graphene oxide composite material through centrifugation, washing, and drying.

[0012] In one aspect of the embodiments of the present disclosure, the graphene oxide is prepared through the following steps: Step 6-1: Add sodium nitrate into concentrated sulfuric acid. After the sodium nitrate is completely dissolved, obtain the solution of Step 6-1. Step 6-2: Place the solution of Step 6-1 in an ice-water bath and perform magnetic stirring. While maintaining magnetic stirring, add flake graphite, and then continue stirring for 30 - 70 min. Step 6-3: While maintaining the temperature of the reaction system below 4°C, add potassium permanganate in multiple portions. After the addition of potassium permanganate is completed, continue stirring for 120 - 200 min. Then transfer the reaction vessel to an oil bath at 30°C - 40°C and continue stirring for 120 - 200 min. Then slowly add water. After adding water, transfer the reaction vessel to a water bath at 85°C - 95°C and continue stirring for 30 - 60 min. Step 6-4: Pour out the liquid in the reaction vessel and let it stand to cool down. When the temperature of the liquid drops to 50°C - 60°C, then slowly add water. After adding water, add hydrogen peroxide solution until no gas is generated, and then obtain the product after filtration in Step 6-4 through filtration. Step 6-5: Wash the product after filtration in Step 6-4 multiple times with an acidic solution and water, and then obtain the graphene oxide after drying.

[0013] In one aspect of the embodiments of the present disclosure, specifically, Step 1 includes: Step 1-1: Weigh 100 g of graphene oxide. Add 100 g of graphene oxide and 25 mL of phosphorus oxychloride into 250 mL of tetrahydrofuran, and then ultrasonicate at room temperature for 60 min. At the same time, dissolve 35 mL of triethanolamine in 100 mL of tetrahydrofuran to form a triethanolamine solution, and slowly add the triethanolamine solution dropwise into the tetrahydrofuran containing graphene oxide and phosphorus oxychloride within 25 min while ultrasonicating. Step 1-2: After the ultrasonication process ends, add 5 g of 4,4'-diaminodiphenylmethane to the solution obtained in Step 1-1, and then react at room temperature for 24 h. Then obtain the nitrogen / phosphorus co-doped graphene oxide material through centrifugation, washing, and drying. Step 1-3: Add the nitrogen / phosphorus co-doped graphene oxide material prepared in Step 1-2 and 8 g of SbCl3 into 200 mL of 2 mol / L hydrochloric acid solution. While stirring, add the complexing agent sodium dodecylbenzenesulfonate and the co-precipitant oxalic acid, then heat to 50 °C, continue stirring for 4.5 h, and then obtain the antimony hydroxide-heteroatom-doped graphene oxide composite material through centrifugation, washing, and drying.

[0014] In one aspect of the embodiments of the present disclosure, Step 2 includes: Step 2-1: Slowly stir and pour concentrated nitric acid into water to form a nitric acid solution; successively weigh ZnO, Al(NO3)3·9H2O, and Ce(NO3)3·6H2O and dissolve them in the nitric acid solution: ultrasonicate at room temperature for 10 - 30 min to obtain the mixed solution of Step 2-1; Step 2-2: Prepare an alkali solution by mixing NaOH and NaNO3; place the mixed solution of Step 2-1 under nitrogen protection, and while stirring at a rate of 300 - 500 r / min, slowly add part of the alkali solution to the mixed solution within 5 - 15 min; then quickly add another part of the alkali solution to the mixed solution, and increase the stirring rate to 700 - 1000 r / min and stir for 3 - 10 min, and then slowly add the remaining part of the alkali solution to the mixed solution within 5 - 15 min, controlling the pH value of the reaction system to be 9 - 10; Step 2-3: Stir the solution obtained in Step 2-2 at 40 °C - 50 °C for 1 - 3 h, then crystallize at 85 °C - 95 °C for 6 - 10 h, and then obtain the zinc-aluminum-cerium hydrotalcite material through filtration, washing, and drying.

[0015] In one aspect of the embodiments of the present disclosure, specifically, Step 2 includes: Step 2-1: Slowly stir and pour 23.82 mL of concentrated nitric acid into 800 mL of deionized water to form a nitric acid solution; successively weigh 24.4 g of ZnO, 37.5 g of Al(NO3)3·9H2O, and 43.4 g of Ce(NO3)3·6H2O and dissolve them in the nitric acid solution, where n(Zn 2 + ): n(Al 3+ ): n(Ce 3+ ) = 3:1:1; ultrasonicate at room temperature for 20 min to obtain the mixed solution of Step 2-1; Step 2-2: Dissolve 32 g of NaOH and 5 mL of 68% concentrated nitric acid in 400 mL of water to obtain an alkaline solution mixed with NaOH and NaNO3; place the mixed solution from Step 2-1 under nitrogen protection, and at a stirring rate of 500 r / min, slowly add 60 mL of the alkaline solution to the mixed solution within 12 min; then quickly add 200 mL of the alkaline solution to the mixed solution, increase the stirring rate to 1000 r / min, stir for 8 min, and then slowly add the remaining 140 mL of the alkaline solution to the mixed solution within 15 min, controlling the pH value of the reaction system to be 9.5; Step 2-3: Stir the solution obtained in Step 2-2 at 45 °C for 2 h, then crystallize at 90 °C for 8 h, and then obtain the zinc-aluminum-cerium hydrotalcite material through filtration, washing, and drying.

[0016] In one aspect of the embodiments of the present disclosure, Step 3 includes: Step 3-1: Heat the hydrophilic polyester polyol or hydrophilic polyether polyol to 90 °C - 110 °C, then add a chain extender, maintain the vacuum degree at 0.05 - 0.1 MPa for dehydration, and then naturally cool to room temperature; Step 3-2: Add the dehydrated hydrophilic polyester polyol or hydrophilic polyether polyol to the polyisocyanate in 3 - 5 portions, with the addition intervals selected from 5 - 15 min, and then react at 70 °C - 85 °C for 2 - 4 h; obtain a polyurethane prepolymer through vacuum degassing; Step 3-3: Dissolve the polyurethane prepolymer in an organic solvent to obtain a polyurethane hydrogel.

[0017] In one aspect of the embodiments of the present disclosure, in Step 3-1, the hydrophilic polyester polyol or hydrophilic polyether polyol is selected from at least one of polytetrahydrofuran diol, polyethylene adipate diol, polyethylene adipate-1,4-butanediol ester diol, polyethylene glycol, and castor oil polyadipate polyol; and the average molecular weight of the hydrophilic polyester polyol or hydrophilic polyether polyol is selected from 1000 to 4000 g / mol; In one aspect of the embodiments of the present disclosure, in Step 3-1 and Step 4, the chain extender is selected from at least one of 1,4-butanediol, diethylene glycol, trimethylolpropane, ethylene glycol, glycerol, 1,4-cyclohexanediol, and resorcinol hydroxy ether.

[0018] In one aspect of the embodiments of the present disclosure, in step 3-2, the polyisocyanate is selected from at least one of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, benzylidene diisocyanate, methylcyclohexyl diisocyanate, tetramethylbenzylidene diisocyanate, IPDI trimer, HDI trimer, TDI trimer, and MDI trimer.

[0019] In one aspect of the embodiments of the present disclosure, in step 1-3, the antimony salt is selected from antimony trichloride; the complexing agent is selected from sodium dodecylbenzenesulfonate, and the coprecipitating agent is selected from oxalic acid.

[0020] In one aspect of the embodiments of the present disclosure, in step 5, the catalyst is selected from tin catalysts, titanium catalysts, germanium catalysts, or metallocene catalysts; preferably a tin catalyst; specifically, it can be selected from dibutyltin dilaurate catalyst.

[0021] In one aspect of the embodiments of the present disclosure, in step 5, the terminator is selected from at least one of n-butanol, cyclohexanol, ethanolamine, diethanolamine, N,N-diethylamine, and N,N-dibutylamine.

[0022] In one aspect of the embodiments of the present disclosure, in the preparation method, the mass ratio of the polyurethane prepolymer to the quartz sand is selected from (20-30):(25-40).

[0023] According to the third aspect of the embodiments of the present disclosure, there is provided an application of the foregoing high-performance inorganic silicon-aluminum material, or the high-performance inorganic silicon-aluminum material prepared by the foregoing method, in the preparation of a thermal insulation and flame retardant material.

[0024] The technical solutions provided by the embodiments of the present disclosure may include the following beneficial effects: As can be seen from the above embodiments, the present disclosure has prepared a high-performance inorganic silicon-aluminum material with good thermal insulation performance, flame retardant performance, and mechanical properties.

[0025] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present disclosure. Detailed Description of the Invention

[0026] To make the objectives, technical solutions, and advantages of the present application clearer, the technical solutions of the present application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present application. The described embodiments herein are illustrative in nature and are intended to provide a basic understanding of the present application. The embodiments of the present application should not be construed as limiting the present application.

[0027] For the sake of brevity, only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, each individually disclosed point or single numerical value by itself can serve as a lower limit or an upper limit and be combined with any other point or single numerical value or with other lower limits or upper limits to form a range not explicitly recited.

[0028] In this document, the terms "comprising", "including" or any other variant thereof are intended to cover non-exclusive inclusion, such that a process, method, article or apparatus comprising a series of elements includes not only those elements but also other elements not expressly listed or elements inherent to such process, method, article or apparatus. Without further limitation, an element defined by the phrase "comprising an..." does not exclude the presence of additional identical elements in the process, method, article or apparatus comprising said element.

[0029] In the description herein, unless otherwise specified, "above" and "below" include the number itself.

[0030] Unless otherwise specified, the terms used in this disclosure have the well-known meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values of the various parameters mentioned in this disclosure can be measured by various commonly used measurement methods in the art (for example, they can be tested according to the methods given in the embodiments of this disclosure).

[0031] The term "about" is used to describe and account for small variations. When used in conjunction with an event or circumstance, the term can refer to instances where the event or circumstance occurs precisely and instances where the event or circumstance occurs very nearly. For example, when used in conjunction with a numerical value, the term can refer to a variation range of ±10% or less than or equal to the numerical value, such as ±5% or less than or equal to, ±4% or less than or equal to, ±3% or less than or equal to, ±2% or less than or equal to, ±1% or less than or equal to, ±0.5% or less than or equal to, ±0.1% or less than or equal to, or ±0.05% or less than or equal to. Additionally, sometimes quantities, ratios and other numerical values are presented in range format in this document. It should be understood that such range format is for convenience and brevity and should be understood flexibly to include not only the numerical values explicitly specified as range limits but also all individual numerical values or sub-ranges subsumed within said range as if each numerical value and sub-range were explicitly specified.

[0032] A list of items joined by the term "at least one of", "at least a", "at least a kind of" or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may include a single component or multiple components. Item B may include a single component or multiple components. Item C may include a single component or multiple components.

[0033] The present disclosure will be further elaborated below in conjunction with embodiments. It should be understood that these embodiments are only used to illustrate the present disclosure and not to limit the scope of the present disclosure.

[0034] Examples and comparative examples: Examples

[0035] Example 1 includes the following steps: 1. Prepare graphene oxide: Add 20 g of sodium nitrate to 500 mL of concentrated sulfuric acid. After the sodium nitrate is completely dissolved, place the solution in an ice-water bath and carry out mechanical stirring; while maintaining mechanical stirring, add 40 g of flake graphite, and then continue stirring for 60 min; while maintaining the temperature of the reaction system below 4 °C, slowly add 120 g of potassium permanganate in 3 portions. After the addition of potassium permanganate is completed, continue stirring for 150 min; then transfer the reaction vessel to an oil bath at 35 °C and continue stirring for 150 min; then slowly add 1200 mL of water. After adding water, transfer the reaction vessel to a water bath at 90 °C and continue stirring for 45 min; pour out the liquid in the reaction vessel and let it stand and cool. After the temperature of the liquid drops to 55 °C, slowly add 1000 mL of water. After adding water, slowly add 30% hydrogen peroxide solution until no gas is generated, and then obtain the filtered product through filtration; wash the filtered product 6 times with 5% dilute hydrochloric acid and water, and then obtain graphene oxide after drying.

[0036] Repeat the above steps multiple times to obtain a sufficient amount of graphene oxide for subsequent reactions.

[0037] 2. Prepare nitrogen / phosphorus co-doped graphene oxide material: Weigh 100 g of graphene oxide; add 100 g of graphene oxide and 25 mL of phosphorus oxychloride to 250 mL of tetrahydrofuran, then ultrasonicate for 60 min at room temperature. At the same time, dissolve 35 mL of triethanolamine in 100 mL of tetrahydrofuran to form a triethanolamine solution, and slowly add the triethanolamine solution dropwise to the tetrahydrofuran containing graphene oxide and phosphorus oxychloride within 25 min while ultrasonication is in progress; after the ultrasonication process ends, add 5 g of 4,4'-diaminodiphenylmethane to the obtained solution, and then react at room temperature for 24 h; then through centrifugation, washing and drying, a nitrogen / phosphorus co-doped graphene oxide material is obtained.

[0038] 3. Preparation of antimony hydroxide-heteroatom doped graphene oxide composite material: Add the prepared nitrogen / phosphorus co-doped graphene oxide material and 8 g of SbCl3 to 200 mL of 2 mol / L hydrochloric acid solution, add the complexing agent sodium dodecylbenzenesulfonate (2 g) and the coprecipitant oxalic acid (2.5 g) under stirring, then heat to 50 °C, continue stirring for 4.5 h, and then through centrifugation, washing and drying, a antimony hydroxide-heteroatom doped graphene oxide composite material is obtained.

[0039] 4. Preparation of zinc-aluminum-cerium hydrotalcite material: Slowly stir and pour 23.82 mL of concentrated nitric acid into 800 mL of deionized water to form a nitric acid solution; successively weigh 24.4 g of ZnO, 37.5 g of Al(NO3)3·9H2O, and 43.4 g of Ce(NO3)3·6H2O and dissolve them in the nitric acid solution, where, n(Zn 2+ ): n(Al 3 + ): n(Ce 3+ ) = 3:1:1; ultrasonicate at room temperature for 20 min to obtain a mixed solution; Dissolve 32 g of NaOH and 5 mL of 68% concentrated nitric acid in 400 mL of water to obtain an alkali solution of NaOH and NaNO3; place the mixed solution under nitrogen protection, at a stirring rate of 500 r / min, slowly add 60 mL of the alkali solution to the mixed solution within 12 min; then quickly add 200 mL of the alkali solution to the mixed solution, and increase the stirring rate to 1000 r / min, stir for 8 min, and then slowly add the remaining 140 mL of the alkali solution to the mixed solution within 15 min, controlling the pH value of the reaction system to 9.5; finally, stir the obtained solution at 45 °C for 2 h, then crystallize at 90 °C for 8 h, and then through filtration, washing and drying, a zinc-aluminum-cerium hydrotalcite material is obtained.

[0040] 5. Preparation of polyurethane prepolymer: Heat 40 parts by weight of poly(ricinoleate adipate) polyol (average molecular weight of 2500) to 95 °C, then add 2.5 parts by weight of chain extender glycerol, maintain the vacuum degree at 0.05 - 0.1 MPa for dehydration, and then naturally cool to room temperature; add the dehydrated product to 30 parts by weight of HDI trimer in 5 portions with an interval of 10 min between each addition, and then react at 75 °C for 3.5 h; use the dibutylamine titration method to determine the mass content of -N=C=O in the prepolymer; when the actual measured value is close to the theoretical value, carry out vacuum degassing and store it in a sealed manner.

[0041] 6. Preparation of high-performance inorganic silicon-aluminum material: Weigh 20 parts by weight of polyurethane prepolymer and add it to 250 parts by weight of n-butanol solution, stir until completely dissolved, and let it stand for 3 hours; after it has started to semi-gel, add 35 parts by weight of quartz sand, 25 parts by weight of cement, 20 parts by weight of gypsum, 12 parts by weight of aluminum powder, 7 parts by weight of fly ash, 0.5 part by weight of antimony hydroxide-heteroatom-doped graphene oxide composite material, 0.5 part by weight of zinc-aluminum-cerium hydrotalcite material; and add 35 parts by weight of chain extender glycerol and 0.2 part by weight of catalyst dibutyltin dilaurate catalyst under stirring; continue to stir for 1.5 h, and then continue to react for 4 h, add terminator N,N-diethylamine; then heat at 60 °C for 3 h to remove organic solvents such as n-butanol; then heat-treat the obtained solid under inert gas protection at 600 °C for 4 h. At this time, the polyurethane forms a carbon skeleton after heat treatment, the antimony hydroxide-heteroatom-doped graphene oxide composite material forms an antimony oxide-heteroatom-doped graphene composite material after heat treatment, and the zinc-aluminum-cerium hydrotalcite material forms a metal oxide material after heat treatment; obtain the high-performance inorganic silicon-aluminum material of Example 1.

[0042] Comparative Example 1: Comparative Example 1 includes the following steps: 1. Preparation of graphene oxide: Add 20 g of sodium nitrate to 500 mL of concentrated sulfuric acid. After the sodium nitrate is completely dissolved, place the solution in an ice-water bath and carry out mechanical stirring. While maintaining mechanical stirring, add 40 g of flake graphite, and then continue stirring for 60 min. While keeping the temperature of the reaction system below 4 °C, slowly add 120 g of potassium permanganate in 3 portions. After the addition of potassium permanganate is complete, continue stirring for 150 min. Then transfer the reaction vessel to an oil bath at 35 °C and continue stirring for 150 min. Then slowly add 1200 mL of water. After adding water, transfer the reaction vessel to a water bath at 90 °C and continue stirring for 45 min. Pour out the liquid in the reaction vessel and let it stand to cool. After the temperature of the liquid drops to 55 °C, slowly add 1000 mL of water. After adding water, slowly add 30% hydrogen peroxide solution until no gas is generated, and then obtain the filtered product through filtration. Wash the filtered product 6 times with 5% dilute hydrochloric acid and water, and then obtain graphene oxide after drying.

[0043] Repeat the above steps multiple times to obtain a sufficient amount of graphene oxide for subsequent reactions.

[0044] 2. Preparation of nitrogen / phosphorus co-doped graphene oxide material: Weigh 100 g of graphene oxide; add 100 g of graphene oxide and 25 mL of phosphorus oxychloride to 250 mL of tetrahydrofuran, and then ultrasonicate for 60 min at room temperature. At the same time, dissolve 35 mL of triethanolamine in 100 mL of tetrahydrofuran to form a triethanolamine solution, and slowly add the triethanolamine solution to the tetrahydrofuran containing graphene oxide and phosphorus oxychloride within 25 min while ultrasonicating. After the ultrasonication process ends, add 5 g of 4,4'-diaminodiphenylmethane to the obtained solution, and then react at room temperature for 24 h. Then obtain the nitrogen / phosphorus co-doped graphene oxide material through centrifugation, washing, and drying.

[0045] 3. Preparation of zinc-aluminum-cerium hydrotalcite material: Slowly stir and pour 23.82 mL of concentrated nitric acid into 800 mL of deionized water to form a nitric acid solution; successively weigh 24.4 g of ZnO, 37.5 g of Al(NO3)3·9H2O, and 43.4 g of Ce(NO3)3·6H2O and dissolve them in the nitric acid solution, where n(Zn 2+ ): n(Al 3 + ): n(Ce 3+ ) = 3:1:1; ultrasonicate for 20 min at room temperature to obtain a mixed solution; Dissolve 32 g of NaOH and 5 mL of 68% concentrated nitric acid in 400 mL of water to obtain an alkaline solution of NaOH and NaNO₃; place the mixed solution under nitrogen protection, and at a stirring rate of 500 r / min, slowly add 60 mL of the alkaline solution to the mixed solution within 12 min; then quickly add 200 mL of the alkaline solution to the mixed solution, increase the stirring rate to 1000 r / min, stir for 8 min, and then slowly add the remaining 140 mL of the alkaline solution to the mixed solution within 15 min, controlling the pH value of the reaction system to be 9.5; finally, stir the obtained solution at 45 °C for 2 h, then crystallize at 90 °C for 8 h, and then through filtration, washing and drying, a zinc-aluminum-cerium hydrotalcite material is obtained.

[0046] 5. Preparation of polyurethane prepolymer: Heat 40 parts by weight of poly(adipic acid castor oil ester) polyol (average molecular weight of 2500) to 95 °C, then add 2.5 parts by weight of chain extender glycerol, maintain the vacuum degree at 0.05 - 0.1 MPa for dehydration, and then naturally cool to room temperature; add the dehydrated product to 30 parts by weight of HDI trimer in 5 times, with an interval of 10 min between additions, and then react at 75 °C for 3.5 h; use the di-n-butylamine titration method to measure the mass content of -N=C=O in the prepolymer; when the actual measured value is close to the theoretical value, perform vacuum degassing and store it sealed.

[0047] 6. Preparation of inorganic silicon-aluminum material: Weigh 20 parts by weight of the polyurethane prepolymer and add it to 250 parts by weight of n-butanol solution, stir until completely dissolved, and let it stand for 3 hours; after it has started semi-gelatinization, add 35 parts by weight of quartz sand, 25 parts by weight of cement, 20 parts by weight of gypsum, 12 parts by weight of aluminum powder, 7 parts by weight of fly ash, 0.5 part by weight of heteroatom-doped graphene oxide composite material, 0.5 part by weight of zinc-aluminum-cerium hydrotalcite material; and add 35 parts by weight of chain extender glycerol and 0.2 part by weight of catalyst dibutyltin dilaurate catalyst under stirring; continue to stir for 1.5 h, and then continue to react for 4 h, add terminator N,N-diethylamine; then heat at 60 °C for 3 h to remove organic solvents such as n-butanol; then heat-treat the obtained solid under inert gas protection at 600 °C for 4 h. At this time, the polyurethane forms a carbon skeleton after heat treatment, the heteroatom-doped graphene oxide composite material forms a heteroatom-doped graphene composite material after heat treatment, and the zinc-aluminum-cerium hydrotalcite material forms a metal oxide material after heat treatment; the inorganic silicon-aluminum material of Comparative Example 1 is obtained.

[0048] The main difference between Comparative Example 1 and Example 1 is that the nitrogen / phosphorus co-doped graphene oxide material prepared in Comparative Example 1 is not combined with antimony hydroxide.

[0049] Comparative Example 2 Comparative Example 2 includes the following steps: 1. Preparation of graphene oxide: Add 20 g of sodium nitrate to 500 mL of concentrated sulfuric acid. After the sodium nitrate is completely dissolved, place the solution in an ice-water bath and carry out mechanical stirring. While maintaining mechanical stirring, add 40 g of flake graphite, and then continue stirring for 60 min. While keeping the temperature of the reaction system below 4 °C, slowly add 120 g of potassium permanganate in 3 portions. After the addition of potassium permanganate is complete, continue stirring for 150 min. Then transfer the reaction vessel to an oil bath at 35 °C and continue stirring for 150 min. Then slowly add 1200 mL of water. After adding water, transfer the reaction vessel to a water bath at 90 °C and continue stirring for 45 min. Pour out the liquid in the reaction vessel and let it stand to cool. After the temperature of the liquid drops to 55 °C, slowly add 1000 mL of water. After adding water, slowly add 30% hydrogen peroxide solution until no gas is generated, and then obtain the filtered product through filtration. Wash the filtered product 6 times with 5% dilute hydrochloric acid and water, and then obtain graphene oxide after drying.

[0050] Repeat the above steps multiple times to obtain a sufficient amount of graphene oxide for subsequent reactions.

[0051] 2. Preparation of antimony hydroxide-graphene oxide composite material: Add the prepared graphene oxide material and 8 g of SbCl3 to 200 mL of 2 mol / L hydrochloric acid solution. Add the complexing agent sodium dodecylbenzenesulfonate (2 g) and the coprecipitant oxalic acid (2.5 g) under stirring, then heat to 50 °C and continue stirring for 4.5 h, and then obtain the antimony hydroxide-graphene oxide composite material through centrifugation, washing, and drying.

[0052] 4. Preparation of zinc-aluminum-cerium hydrotalcite material: Slowly stir and pour 23.82 mL of concentrated nitric acid into 800 mL of deionized water to form a nitric acid solution; successively weigh 24.4 g of ZnO, 37.5 g of Al(NO3)3·9H2O, and 43.4 g of Ce(NO3)3·6H2O and dissolve them in the nitric acid solution, where n(Zn 2+ ): n(Al 3 + ): n(Ce 3+ ) = 3:1:1; ultrasonically irradiate for 20 min at room temperature to obtain a mixed solution; Dissolve 32 g of NaOH and 5 mL of 68% concentrated nitric acid in 400 mL of water to obtain an alkaline solution of NaOH and NaNO₃; place the mixed solution under nitrogen protection, and at a stirring rate of 500 r / min, slowly add 60 mL of the alkaline solution to the mixed solution within 12 min; then quickly add 200 mL of the alkaline solution to the mixed solution, increase the stirring rate to 1000 r / min, stir for 8 min, and then slowly add the remaining 140 mL of the alkaline solution to the mixed solution within 15 min, controlling the pH value of the reaction system to 9.5; finally, stir the obtained solution at 45 °C for 2 h, then crystallize at 90 °C for 8 h, and then filter, wash, and dry to obtain the zinc-aluminum-cerium hydrotalcite material.

[0053] 5. Preparation of polyurethane prepolymer: Heat 40 parts by weight of poly(adipic acid castor oil ester) polyol (average molecular weight of 2500) to 95 °C, then add 2.5 parts by weight of chain extender glycerol, maintain the vacuum degree at 0.05 - 0.1 MPa for dehydration, and then naturally cool to room temperature; add the dehydrated product to 30 parts by weight of HDI trimer in 5 portions at intervals of 10 min, and then react at 75 °C for 3.5 h; use the dibutylamine titration method to determine the mass content of -N=C=O in the prepolymer; when the actual measured value is close to the theoretical value, perform vacuum degassing and store it sealed.

[0054] 6. Preparation of inorganic silicon-aluminum material: Weigh 20 parts by weight of the polyurethane prepolymer and add it to 250 parts by weight of n-butanol solution, stir until completely dissolved, and let it stand for 3 hours; after it has started to semi-gel, add 35 parts by weight of quartz sand, 25 parts by weight of cement, 20 parts by weight of gypsum, 12 parts by weight of aluminum powder, 7 parts by weight of fly ash, 0.5 part by weight of antimony hydroxide-graphene oxide composite material, 0.5 part by weight of zinc-aluminum-cerium hydrotalcite material; and add 35 parts by weight of chain extender glycerol and 0.2 part by weight of catalyst dibutyltin dilaurate catalyst under stirring; continue to stir for 1.5 h, then continue to react for 4 h, and add terminator N,N-diethylamine; then heat at 60 °C for 3 h to remove organic solvents such as n-butanol; then subject the obtained solid to heat treatment at 600 °C for 4 h under inert gas protection. At this time, the polyurethane forms a carbon skeleton after heat treatment, the antimony hydroxide-graphene oxide composite material forms an antimony oxide-graphene composite material after heat treatment, and the zinc-aluminum-cerium hydrotalcite material forms a metal oxide material after heat treatment; obtain the inorganic silicon-aluminum material of Comparative Example 2.

[0055] Comparative Example 3: The steps of Comparative Example 3 are similar to those of Example 1, except that Comparative Example 3 does not include the step of preparing the zinc-aluminum-cerium hydrotalcite material.

[0056] Comparative Example 4: Comparative Example 4 includes the following steps: 1. Preparation of graphene oxide: Add 20 g of sodium nitrate to 500 mL of concentrated sulfuric acid. After the sodium nitrate is completely dissolved, place the solution in an ice-water bath and carry out mechanical stirring. While maintaining mechanical stirring, add 40 g of flake graphite, and then continue stirring for 60 min. While keeping the temperature of the reaction system below 4 °C, slowly add 120 g of potassium permanganate in 3 portions. After the addition of potassium permanganate is complete, continue stirring for 150 min. Then transfer the reaction vessel to an oil bath at 35 °C and continue stirring for 150 min. Then slowly add 1200 mL of water. After adding water, transfer the reaction vessel to a water bath at 90 °C and continue stirring for 45 min. Pour out the liquid in the reaction vessel and let it stand to cool. After the temperature of the liquid drops to 55 °C, slowly add 1000 mL of water. After adding water, slowly add 30% hydrogen peroxide solution until no gas is generated, and then obtain the filtered product through filtration. Wash the filtered product 6 times with 5% dilute hydrochloric acid and water, and then obtain graphene oxide after drying.

[0057] Repeat the above steps multiple times to obtain a sufficient amount of graphene oxide for subsequent reactions.

[0058] 2. Preparation of nitrogen / phosphorus co-doped graphene oxide material: Weigh 100 g of graphene oxide; add 100 g of graphene oxide and 25 mL of phosphorus oxychloride to 250 mL of tetrahydrofuran, and then ultrasonicate at room temperature for 60 min. At the same time, dissolve 35 mL of triethanolamine in 100 mL of tetrahydrofuran to form a triethanolamine solution, and slowly add the triethanolamine solution to the tetrahydrofuran containing graphene oxide and phosphorus oxychloride within 25 min while ultrasonicating. After the ultrasonication process ends, add 5 g of 4,4'-diaminodiphenylmethane to the obtained solution, and then react at room temperature for 24 h. Then obtain the nitrogen / phosphorus co-doped graphene oxide material through centrifugation, washing, and drying.

[0059] 3. Preparation of antimony hydroxide-heteroatom doped graphene oxide composite material: Add the prepared nitrogen / phosphorus co-doped graphene oxide material and 8 g of SbCl3 to 200 mL of 2 mol / L hydrochloric acid solution. While stirring, add the complexing agent sodium dodecylbenzenesulfonate (2 g) and the coprecipitant oxalic acid (2.5 g), then heat to 50 °C and continue stirring for 4.5 h. Then obtain the antimony hydroxide-heteroatom doped graphene oxide composite material through centrifugation, washing, and drying.

[0060] 4. Preparation of zinc-aluminum-cerium hydrotalcite material: Slowly stir 23.82 mL of concentrated nitric acid and pour it into 800 mL of deionized water to form a nitric acid solution; successively weigh 24.4 g of ZnO, 37.5 g of Al(NO3)3·9H2O, and 43.4 g of Ce(NO3)3·6H2O and dissolve them in the nitric acid solution. Among them, n(Zn 2+ ): n(Al 3 + ): n(Ce 3+ ) = 3:1:1; ultrasonicate for 20 min at room temperature to obtain a mixed solution; Dissolve 32 g of NaOH and 5 mL of 68% concentrated nitric acid in 400 mL of water to obtain an alkali solution of NaOH and NaNO3; place the mixed solution under nitrogen protection, and at a stirring rate of 500 r / min, slowly add 60 mL of the alkali solution to the mixed solution within 12 min; then quickly add 200 mL of the alkali solution to the mixed solution, increase the stirring rate to 1000 r / min, stir for 8 min, and then slowly add the remaining 140 mL of the alkali solution to the mixed solution within 15 min, controlling the pH value of the reaction system to be 9.5; finally, stir the obtained solution at 45°C for 2 h, then crystallize at 90°C for 8 h, and then obtain the zinc-aluminum-cerium hydrotalcite material through filtration, washing, and drying.

[0061] 6. Preparation of inorganic silicon-aluminum material: Weigh 35 parts by weight of quartz sand, 25 parts by weight of cement, 20 parts by weight of gypsum, 12 parts by weight of aluminum powder, 7 parts by weight of fly ash, 0.5 part by weight of antimony hydroxide-heteroatom-doped graphene oxide composite material, and 0.5 part by weight of zinc-aluminum-cerium hydrotalcite material in water to form a slurry and cure it in a mold to obtain the inorganic silicon-aluminum material of Comparative Example 4.

[0062] Thermal conductivity and flame retardancy test: Manufacture walls with the products of Example 1 and Comparative Examples 1-4 respectively, and after curing for 30 days, detect and evaluate their performance with reference to the CECS standard, and detect the compressive strength and thermal conductivity; place the walls in a closed environment, control the daytime temperature to be 65°C and the nighttime temperature to be 23°C for 20 days, and detect the thermal conductivity again. The test results are shown in Table 1 below; Conduct combustion tests on the products of Example 1 and Comparative Examples 1-4, and the test results are shown in Table 1 below; Table 1 Example <![CDATA[Thermal conductivity 1 W / (m·K)]]> <![CDATA[Thermal conductivity 2 W / (m·K)]]> Flame retardant grade Example 1 0.024 0.028 V-0 Comparative Example 1 0.025 0.031 V-1 Comparative Example 2 0.024 0.029 V-1 Comparative Example 3 0.026 0.032 V-1 Comparative Example 4 0.048 0.057 V-0 Comparing the results of Comparative Example 1 and Comparative Examples 1-4, it can be seen that by adding the silicon-aluminum material to the polyurethane hydrogel while carrying out chain extension, the silicon-aluminum material can be combined with the polyurethane network structure to obtain a porous structure containing unconnected pores, which is beneficial to the improvement of the heat insulation performance; however, the carbon skeleton formed after the carbonization of polyurethane may lead to a decrease in the flame retardant performance. The antimony hydroxide-heteroatom-doped graphene oxide composite material and the zinc-aluminum-cerium hydrotalcite material prepared in this application both have good hydrophilic properties, and they can be combined with the polyurethane chain segments (hydrophilic polyester polyol or hydrophilic polyether polyol is also used in the polyurethane). The antimony oxide-heteroatom-doped graphene composite material and the metal oxide material obtained after the high-temperature treatment of the antimony hydroxide-heteroatom-doped graphene oxide composite material and the zinc-aluminum-cerium hydrotalcite material both have good flame retardant properties.

[0063] After considering the specification and the practice disclosed herein, those skilled in the art will readily conceive of other embodiments of the present disclosure. The present disclosure is intended to cover any variations, uses, or adaptations of the present disclosure, which follow the general principles of the present disclosure and include the common general knowledge or conventional technical means in the technical field not disclosed in the present disclosure.

Claims

1. A high-performance inorganic silicon-aluminum material, characterized in that, The high-performance inorganic silicon-aluminum material comprises the following components: A carbon skeleton material formed by carbonizing a polymer material, quartz sand, cement, gypsum, aluminum powder, fly ash, and a flame retardant additive.

2. The high-performance inorganic silicon-aluminum material according to claim 1, characterized in that, The mass ratio of the quartz sand, cement, gypsum, aluminum powder, fly ash, and flame retardant additive is selected from (25 - 40):(15 - 35):(15 - 25):(10 - 15):(5 - 10):(0.5 - 1).

3. The high-performance inorganic silicon-aluminum material according to claim 1, wherein The polymer material is selected from polyurethane.

4. The high-performance inorganic silicon-aluminum material according to claim 1, wherein, The flame retardant additive includes the following two: An antimony oxide-heteratom doped graphene composite material; A metal oxide material formed by heat-treating hydrotalcite.

5. A method for preparing the high-performance inorganic silicon-aluminum material according to any one of claims 1-4, characterized in that, The method comprises the following steps: Step 1: Prepare an antimony hydroxide-heteratom doped graphene oxide composite material; Step 2: Prepare a zinc-aluminum-cerium hydrotalcite material; Step 3: Prepare a polyurethane prepolymer; and add the polyurethane prepolymer to an organic solvent to form a polyurethane hydrogel; Step 4: Add quartz sand, cement, gypsum, aluminum powder, fly ash, and the antimony hydroxide-heteratom doped graphene oxide composite material prepared in Step 1 and the zinc-aluminum-cerium hydrotalcite material prepared in Step 2 to the polyurethane hydrogel respectively. Add a chain extender and a catalyst under stirring, continue stirring for 1 - 2 h and then stop stirring, then continue reacting for 3 - 5 h and add a terminator, and then remove the organic solvent in the reaction system by heating; Step 5: Heat-treat the product obtained in Step 4 under the protection of an inert gas at 450°C - 650°C to obtain the high-performance inorganic silicon-aluminum material; wherein, the polyurethane forms a carbon skeleton after heat treatment, the antimony hydroxide-heteratom doped graphene oxide composite material forms an antimony oxide-heteratom doped graphene composite material after heat treatment, and the zinc-aluminum-cerium hydrotalcite material forms a metal oxide material after heat treatment.

6. The method according to claim 5, characterized in that Step 1 includes: Step 1-1: Provide graphene oxide; add the graphene oxide and phosphorus oxychloride to tetrahydrofuran, then ultrasonicate at room temperature for 45 - 120 min. At the same time, dissolve triethanolamine in tetrahydrofuran to form a triethanolamine solution, and slowly add the triethanolamine solution to the tetrahydrofuran containing graphene oxide and phosphorus oxychloride while ultrasonication; Step 1-2: After the ultrasonication process ends, add 4,4'-diaminodiphenylmethane to the solution obtained in Step 1-1, and then react at room temperature for 20 - 30 h; then centrifuge, wash, and dry to obtain a nitrogen / phosphorus co-doped graphene oxide material; Step 1-3: Add the nitrogen / phosphorus co-doped graphene oxide material prepared in Step 1-2 and an antimony salt to an acidic solution, add a complexing agent and a coprecipitating agent under stirring, then heat to 45°C - 55°C, continue stirring for 3 - 5 h, and then centrifuge, wash, and dry to obtain an antimony hydroxide-heteratom doped graphene oxide composite material.

7. The method according to claim 5, wherein Step 2 includes: Step 2-1: Slowly stir and pour concentrated nitric acid into water to form a nitric acid solution; successively weigh ZnO, Al(NO3)3·9H2O, and Ce(NO3)3·6H2O and dissolve them in the nitric acid solution, and ultrasonicate for 10 - 30 min at room temperature to obtain the mixed solution of Step 2-1; Step 2-2: Prepare an alkali solution mixed with NaOH and NaNO3; place the mixed solution of Step 2-1 under nitrogen protection, and at a stirring rate of 300 - 500 r / min, slowly add part of the alkali solution to the mixed solution within 5 - 15 min; then quickly add another part of the alkali solution to the mixed solution, and increase the stirring rate to 700 - 1000 r / min and stir for 3 - 10 min, and then slowly add the remaining part of the alkali solution to the mixed solution within 5 - 15 min, and control the pH value of the reaction system to be 9 - 10; Step 2-3: Stir the solution obtained in Step 2-2 at 40°C - 50°C for 1 - 3 h, then crystallize at 85°C - 95°C for 6 - 10 h, and then obtain the zinc-aluminum-cerium hydrotalcite material through filtration, washing, and drying.

8. The method according to claim 5, wherein Step 3 includes: Step 3-1: Heat the hydrophilic polyester polyol or hydrophilic polyether polyol to 90°C - 110°C, then add a chain extender, maintain the vacuum degree at 0.05 - 0.1 MPa, carry out dehydration, and then naturally cool to room temperature; Step 3-2: Add the dehydrated hydrophilic polyester polyol or hydrophilic polyether polyol to the polyisocyanate in 3 - 5 times, the addition intervals are selected from 5 - 15 min, and then react at 70°C - 85°C for 2 - 4 h; obtain a polyurethane prepolymer through vacuum degassing; Step 3-3: Dissolve the polyurethane prepolymer in an organic solvent to obtain a polyurethane hydrogel.

9. The method according to any one of claims 5 - 8, characterized in that The method satisfies at least one of the following conditions: In Step 3-1, the hydrophilic polyester polyol or hydrophilic polyether polyol is selected from at least one of polytetrahydrofuran diol, polyethylene adipate diol, polyethylene adipate-1,4-butanediol ester diol, polyethylene glycol, and castor oil polyadipate polyol; and the average molecular weight of the hydrophilic polyester polyol or hydrophilic polyether polyol is selected from 1000 to 4000 g / mol; In Step 3-1 and Step 4, the chain extender is selected from at least one of 1,4-butanediol, diethylene glycol, trimethylolpropane, ethylene glycol, glycerol, 1,4-cyclohexanediol, and resorcinol hydroxy ether; In Step 3-2, the polyisocyanate is selected from at least one of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, benzylidene diisocyanate, methylcyclohexyl diisocyanate, tetramethylbenzylidene diisocyanate, IPDI trimer, HDI trimer, TDI trimer, and MDI trimer; In Step 5, the catalyst is selected from tin-based catalysts, titanium-based catalysts, germanium-based catalysts, or metallocene catalysts; In step 5, the terminator is selected from at least one of n-butanol, cyclohexanol, ethanolamine, diethanolamine, N,N-diethylamine, and N,N-dibutylamine; In steps 1-3, the antimony salt is selected from antimony trichloride; the complexing agent is selected from sodium dodecylbenzenesulfonate, and the coprecipitant is selected from oxalic acid.

10. Use of the high-performance inorganic silicon-aluminum material according to any one of claims 1-4, or the high-performance inorganic silicon-aluminum material prepared by the method according to any one of claims 5-9, in the preparation of a thermal insulation and flame retardant material.