Multi-component foam glass composite thermal insulation material and its preparation method

Abstract

The present invention discloses a multi-setting foam glass composite thermal insulation material and a preparation method thereof, belonging to the technical field of composite thermal insulation material preparation. The preparation method of the multi-setting foam glass composite thermal insulation material comprises the following steps: Step (1): Grinding broken glass, borax and limestone to obtain a mixed material; Step (2): Melting and foaming the mixed material, a foaming agent and a flux to obtain a foam melt, and mixing and stirring the foam melt, a hybrid thermal insulation material and a modification toughening agent to obtain a composite foam melt; Step (3): Cooling, annealing and cooling the composite foam melt to obtain the multi-setting foam glass composite thermal insulation material. By adding the hybrid thermal insulation material and the modification toughening agent to the broken glass, a multi-setting foam glass composite thermal insulation material with excellent thermal insulation performance, corrosion resistance and toughness can be obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of composite thermal insulation material preparation, and in particular relates to a polycondensate foam glass composite thermal insulation material and a preparation method thereof. Background Art

[0002] The thermal conductivity of traditional insulation materials is relatively high, which makes it easy for heat to transfer through the material, resulting in poor insulation effect. The limitation is particularly obvious in situations where efficient insulation is required. In addition, some traditional insulation materials are prone to deformation, breakage and other problems when subjected to external pressure or impact, reducing their service life and thermal insulation performance. In addition, some insulation materials have poor fire resistance and are easy to burn in the event of a fire, accelerating the spread of fire and posing a threat to people and property.

[0003] Foam glass is an inorganic non-metallic glass material, which is made by mixing broken glass, foaming agent, modifying additives and foaming promoter, crushing and uniformly stirring, and then melting at high temperature, foaming, annealing and other technologies. Polycondensate foam glass has been optimized and innovated on this basis, by changing the structure and distribution of bubbles, or introducing other insulation materials for compounding, to improve its insulation performance.

[0004] A Chinese patent with authorization announcement number CN109678557B discloses a water glass-based SiO2 aerogel / carbon foam composite thermal insulation material, which is composed of a carbon foam reinforcement and a water glass-based SiO2 aerogel. The water glass-based SiO2 aerogel is uniformly filled in the voids in the carbon foam reinforcement. The density of the composite thermal insulation material is 1 to 10 Kg / m3, the thermal conductivity of the composite thermal insulation material is 0.02 to 0.05 W / m·K, the compressive strength of the composite thermal insulation material is 0.01 to 0.5 MPa, the carbon foam skeleton has an open-pore structure, the porosity is 90% to 99%, the pore size is 20 to 80 μm, and the specific surface area of the SiO2 aerogel is 400 to 1000 m2 / g. Carbon foam obtained by pyrolysis of melamine foam is used to prepare SiO2 aerogel / carbon foam composite insulation material through sol-gel method and normal pressure drying; this invention composites carbon foam and water glass-based SiO2 aerogel, which has low cost, simple preparation process, small material density, excellent hydrophobicity and low thermal conductivity. However, the insulation performance, toughness and corrosion resistance of the foam glass obtained by this method still have room for improvement. Summary of the invention

[0005] The object of the present invention is to provide a polycondensate foam glass composite thermal insulation material and a preparation method thereof, so as to solve the technical problems of poor thermal insulation performance, toughness and corrosion resistance of polycondensate foam glass materials in the prior art.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides a multi-set foam glass composite thermal insulation material, which is composed of the following components in parts by weight: 32-46 parts of crushed glass, 2-6 parts of borax, 1-3 parts of limestone, 1-5 parts of hybrid thermal insulation material, 2-4 parts of modified toughening agent, 0.8-1.3 parts of foaming agent, and 1-3 parts of flux; wherein, the hybrid thermal insulation material is prepared from titanium aluminum carbon powder, lithium fluoride, n-dodecanol, phosphorus oxychloride and thermoplastic polyurethane elastomer, and the modified toughening agent is prepared from aqueous acetaldehyde solution, aniline, 4-hydroxyphenylacetaldehyde, 5-aminoindole and glass fiber.

[0008] Preferably, the preparation method of the hybrid thermal insulation material includes the following steps:

[0009] R1: Add titanium aluminum carbon powder and lithium fluoride into hydrochloric acid solution, heat and stir, centrifuge, wash with hydrochloric acid solution and lithium chloride solution by centrifugation respectively, then wash with deionized water. Subsequently, uniformly disperse the centrifuged precipitate in deionized water to obtain a suspension, add it into a container for freeze-drying to obtain an aerogel;

[0010] R2: Under the protection of nitrogen atmosphere, dissolve n-dodecanol and phosphorus oxychloride in toluene, magnetically stir and mix, then heat the mixture and carry out continuous reaction. After the continuous reaction ends, quickly pour the reaction solution into cold acetonitrile, filter, wash, and vacuum dry to obtain phosphorus-modified alkanol;

[0011] R3: Add the phosphorus-modified alkanol and aerogel into a container, place it in a vacuum drying oven for melt adsorption to obtain a composite aerogel; add thermoplastic polyurethane elastomer into N,N-dimethylformamide, stir at high temperature, completely dissolve it, then add the composite aerogel, continue to stir under nitrogen atmosphere. After stirring ends, pour it into deionized water, stir until flocculates precipitate, wash the flocculates, and dry to obtain the hybrid thermal insulation material.

[0012] In the above process, first, an aerogel is prepared from titanium aluminum carbon powder and lithium fluoride, then n-dodecanol is chemically modified with phosphorus oxychloride, and then the phosphorus-modified alkanol is adsorbed onto the aerogel framework through vacuum impregnation technology to prepare a composite aerogel with stable thermal conductivity and shape. Finally, the composite aerogel and thermoplastic polyurethane elastomer are mixed by solvent blending to prepare the hybrid thermal insulation material.

[0013] Preferably, in R1, the dosage ratio of titanium aluminum carbon powder, lithium fluoride and hydrochloric acid solution is 2 g : (3 - 3.22) g : (40 - 45) mL, the concentration of the hydrochloric acid solution is 9 mol / L, the temperature of heating and stirring is 35 - 40 °C, the time of heating and stirring is 48 - 54 h. During the washing process, the concentration of the hydrochloric acid solution is 1 mol / L, the concentration of the lithium chloride solution is 1 mol / L, the number of centrifugal washing times is 3 - 5 times respectively, the pH after washing with deionized water is 6, the temperature of freeze-drying is -70 to -80 °C, the pressure is 0 - 1 Pa, and the time is 72 - 84 h.

[0014] Preferably, in R2, the molar ratio of dodecanol to phosphorus oxychloride is 1 : (2 - 2.4), the time of magnetic stirring is 2 - 3 h, the heating temperature is 60 - 70 °C, the heating time is 8 - 10 h, the number of washing times is 3 - 5 times, the temperature of vacuum drying is 25 °C, and the time of vacuum drying is 20 - 24 h.

[0015] Preferably, in R3, the mass ratio of phosphorus-modified alkanol to aerogel is (15 - 19) g : 1 g, the pressure of the vacuum drying oven is 0.06 - 0.09 MPa, the temperature is 100 - 110 °C, the melting adsorption time is 10 - 12 h, the dosage ratio of thermoplastic polyurethane elastomer, N,N-dimethylformamide and composite aerogel is (30 - 40) g : (250 - 300) mL : (20 - 25) g, the continuous stirring time is 2 - 4 h, ethanol is used to wash the flocculants, the number of washing times is 3 - 5 times, the drying temperature is 60 - 70 °C, and the drying time is 20 - 30 h.

[0016] Preferably, the preparation method of the modified toughening agent comprises the following steps:

[0017] Q1: Place the aqueous solution of acetaldehyde in a container equipped with a thermometer, a spherical condenser and a stirrer, adjust the pH of the aqueous solution of acetaldehyde with an aqueous solution of sodium hydroxide, dissolve aniline in toluene, and then add it dropwise to the aqueous solution of acetaldehyde. After the dropping is completed, heat and stir, then slowly add 4-hydroxyphenylacetaldehyde dropwise, and then heat the container, reflux, wash, rotary evaporate, recrystallize and vacuum dry to obtain intermediate product 1;

[0018] Q2: Add intermediate product 1 to a container, add ethanol at the same time, heat and stir, cool, add 5-aminoindole, continue to carry out the heating reaction, wash and vacuum dry to obtain intermediate product 2;

[0019] Q3: Dissolve intermediate product 2 in a container containing N,N-dimethylformamide solution, filter, add glass fiber, stir evenly to obtain a mixed solution, place the mixed solution in a mold, dry and cure to obtain the modified toughening agent.

[0020] In the above process, first, acetaldehyde, aniline, and 4-hydroxyphenylacetaldehyde were reacted to synthesize intermediate product 1 with an aldehyde group. Then, it was reacted with 5-aminoindole to synthesize intermediate product 2. Intermediate product 2 was used to modify glass fiber to obtain a modified toughening agent.

[0021] Preferably, in Q1, the molar ratio of acetaldehyde, aniline, toluene, and 4-hydroxyphenylacetaldehyde is (0.8 - 1.2):(0.4 - 0.6):(1.51 - 2.27):(0.4 - 0.6). The concentration of the acetaldehyde aqueous solution is 6 mol / L, the concentration of the sodium hydroxide aqueous solution is 1 mol / L, the pH is adjusted to 11, the heating and stirring temperature is 30 - 40 °C, the time is 30 - 45 min, the heating temperature is 80 - 85 °C, the reflux time is 5 - 6 h, the vacuum drying temperature is 40 - 50 °C, and the vacuum drying time is 12 - 15 h.

[0022] Preferably, in Q2, the molar ratio of intermediate product 1, ethanol, and 5-aminoindole is (1 - 2):(0.43 - 0.87):(1 - 2). The heating and stirring temperature is 90 - 95 °C, the time is 1 - 2 h, the heating reaction temperature is 70 - 75 °C, the reaction time is 2 - 3 h, the vacuum drying temperature is 80 - 90 °C, and the time is 10 - 12 h; in Q3, the dosage ratio of intermediate product 2, N,N-dimethylformamide, and glass fiber is (4.6 - 4.9) g:2 mL:(2 - 5) g. The drying temperature is 100 - 110 °C, the drying time is 1 - 2 h, and the curing process is: curing at 120 °C for 2 h, then heating to 140 °C for 2 h, further heating to 160 °C for 2 h, then curing at 180 °C for 2 h, and finally curing at 200 °C for 2 h.

[0023] Preferably, the preparation method of the multi-set foam glass composite thermal insulation material includes the following steps:

[0024] Step (1): Grind crushed glass, borax, and limestone to obtain a mixed material;

[0025] Step (2): Melt and foam the mixed material, foaming agent, and flux to obtain a foam melt. Mix and stir the foam melt, hybrid thermal insulation material, and modified toughening agent to obtain a composite foam melt;

[0026] Step (3): Cool, anneal, and cool the composite foam melt to obtain a multi-set foam glass composite thermal insulation material.

[0027] Preferably, in the step (1), ball milling is used for grinding, and the particle size of the ground mixed material is controlled such that the proportion passing through a 200-mesh sieve is more than 95%; in the step (2), the temperature for melting and foaming is 900 - 1000 °C; in the step (3), the cooling time is 3 - 5 min, and the temperature after cooling is 500 - 600 °C.

[0028] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0029] 1. The present invention synthesizes a hybrid thermal insulation material using aerogel, phosphorus-modified alkanol, and thermoplastic polyurethane elastomer, and then synthesizes a modified toughening agent using acetaldehyde, aniline, 4-hydroxyphenylacetaldehyde, 5-aminoindole, and glass fiber. Using broken glass, the hybrid thermal insulation material, and the modified toughening agent as raw materials, the synthesized multi-gel foam glass composite thermal insulation material has excellent thermal insulation performance, corrosion resistance, and toughness.

[0030] 2. The present invention prepares a hybrid thermal insulation material using titanium aluminum carbon powder, lithium fluoride, phosphorus oxychloride, n-dodecanol, and thermoplastic polyurethane elastomer. The synthesized hybrid thermal insulation material belongs to a phase change material. During the phase change process, the hybrid thermal insulation material can absorb or release a large amount of latent heat. When the environmental temperature rises, the phase change substance undergoes a phase change from solid to liquid, absorbing heat and reducing the environmental temperature; when the environmental temperature drops, the phase change substance returns from liquid to solid, releasing the stored heat, which can effectively alleviate the fluctuation of the environmental temperature and improve the thermal insulation performance of the hybrid thermal insulation material; and due to the presence of an aerogel structure and phosphorus-modified alkanol in the formed hybrid thermal insulation material, a complex thermal resistance network is formed inside, thereby reducing the occurrence of heat conduction, heat radiation, and heat convection; at the same time, the polyurethane segments contained in the thermoplastic polyurethane elastomer can resist the erosion of various chemical substances, and the large number of hydrogen bonds contained can also enhance the mechanical properties of the material. Therefore, the introduction of thermoplastic polyurethane elastomer enhances the structural stability and corrosion resistance of the hybrid thermal insulation material. Using the hybrid thermal insulation material as a raw material to prepare a multi-gel foam glass composite thermal insulation material can effectively improve the thermal insulation performance and corrosion resistance of the material.

[0031] 3. The present invention reacts acetaldehyde, aniline, 4-hydroxyphenylacetaldehyde, 5-aminoindole and glass fiber to prepare a modified toughening agent. The reaction between the aldehyde group and the indole group forms a special rose indole structure, which can provide more free volume. The increase in free volume indicates that the material can deform more easily and absorb more energy when subjected to external forces. This energy absorption mechanism helps to reduce stress concentration and prevent the polycondensed foam glass composite thermal insulation material from breaking when subjected to impact or tension. The rose indole structure also has good flexibility and elasticity, enabling the modified toughening agent to play a buffering role when the material is subjected to external forces, reducing the direct impact it bears, and the presence of elasticity can also help the material to return to its original state after deformation, maintaining the integrity and stability of the structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0033] Figure 1 It is a flowchart of the preparation method of the polycondensed foam glass composite thermal insulation material of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0034] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0035] The chemical reagents used in the examples and comparative examples are all commercially available products, and the manufacturers and CAS numbers are as follows:

[0036] The titanium aluminum carbon powder was purchased from Suzhou Kaifa New Material Technology Co., Ltd.

[0037] Lithium fluoride was purchased from Shandong Jinyufeng New Material Co., Ltd., CAS number: 7789-24-4;

[0038] Hydrochloric acid was purchased from Guangzhou Zhuohou Environmental Protection Technology Co., Ltd., CAS number: 7647-01-0;

[0039] Lithium chloride was purchased from Langfang Qianyao Technology Co., Ltd., CAS number: 7447-41-8;

[0040] 1-Dodecanol was purchased from Guangzhou Baosheng Chemical Co., Ltd., CAS No.: 112-53-8;

[0041] Phosphorus oxychloride was purchased from Shandong Xuchen Chemical Technology Co., Ltd., CAS No.: 10025-87-3;

[0042] Toluene was purchased from Jiangyin Fengda Chemical Co., Ltd., CAS No.: 108-88-3;

[0043] Acetonitrile was purchased from Shandong Youwang Chemical Products Co., Ltd., CAS No.: 75-05-8;

[0044] Thermoplastic polyurethane elastomer was purchased from Yixing Nanxin Qiangsheng Plastic Products Co., Ltd., CAS No.: 1211-14-9;

[0045] N,N-Dimethylformamide was purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd., CAS No.: 68-12-2;

[0046] Ethanol was purchased from Foshan Changxing New Materials Co., Ltd., CAS No.: 64-17-5;

[0047] Acetaldehyde was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd., CAS No.: 75-07-0;

[0048] Aniline was purchased from Jinan Jinhao Chemical Co., Ltd., CAS No.: 122-98-5;

[0049] 4-Hydroxyphenylacetaldehyde was purchased from Hubei Yangxin Pharmaceutical Technology Co., Ltd., CAS No.: 7339-87-9;

[0050] 5-Aminoindole was purchased from Hebei Zhentian Food Additive Co., Ltd., CAS No.: 5192-03-0;

[0051] Glass fiber was purchased from Langfang Kelan Fireproof Materials Co., Ltd., CAS No.: 65997-17-3;

[0052] Broken glass was purchased from Jinan Zhongmei New Materials Technology Co., Ltd.;

[0053] Borax was purchased from Changsha Jinuo Chemical Co., Ltd., CAS No.: 1303-96-4;

[0054] Limestone was purchased from Hebei Jiegui Mineral Products Co., Ltd., CAS No.: 471-34-1;

[0055] Sodium carbonate was purchased from Langfang Qianyao Technology Co., Ltd., CAS No.: 497-19-8;

[0056] Lithium carbonate was purchased from Hebei Mojin Biotechnology Co., Ltd., CAS No.: 554-13-2.

[0057] Example 1

[0058] This example discloses a preparation method of a hybrid thermal insulation material, comprising the following steps:

[0059] R1: Add 2 g of titanium aluminum carbon powder and 3.11 g of lithium fluoride into 42.5 mL of 9 mol / L hydrochloric acid solution, heat and stir at 40 °C for 48 h, centrifuge, wash with 1 mol / L hydrochloric acid solution and 1 mol / L lithium chloride solution by centrifugation for 3 times respectively, then wash with deionized water until the pH = 6. Subsequently, uniformly disperse the centrifuged precipitate in deionized water to obtain a suspension, add it into a container, freeze (-80 °C, 1 Pa) and dry for 72 h to obtain an aerogel;

[0060] R2: Under the protection of a nitrogen atmosphere, dissolve 1 g of dodecanol and 1.811 g of phosphorus oxychloride in toluene, magnetically stir and mix for 2 h, then heat the mixture, heat at 70 °C for 10 h, and carry out continuous reaction. After the continuous reaction ends, quickly pour the reaction solution into cold acetonitrile, filter, wash 3 times, and vacuum dry at 25 °C for 24 h to obtain a phosphorus-modified alkanol;

[0061] R3: Add 17.5 g of phosphorus-modified alkanol and 1 g of aerogel into a container, place it in a vacuum drying oven (0.09 MPa, 110 °C) for melt adsorption for 12 h to obtain a composite aerogel; add 35 g of thermoplastic polyurethane elastomer into 275 mL of N,N-dimethylformamide, stir at a high temperature for 4 h, after completely dissolving, add 22.5 g of the composite aerogel, continue to stir under a nitrogen atmosphere. After stirring ends, pour it into deionized water, stir until flocculates precipitate, wash the flocculates with ethanol for 3 times, and dry at 70 °C for 24 h to obtain a hybrid thermal insulation material.

[0062] This example discloses a preparation method of a modified toughening agent, comprising the following steps:

[0063] Q1: Place 1.60 mL of 6 mol / L aqueous acetaldehyde solution in a container equipped with a thermometer, a spherical condenser and a stirrer, adjust the pH of the aqueous acetaldehyde solution to 11 with 1 mol / L aqueous sodium hydroxide solution, dissolve 1.33 g of aniline in 5.67 mL of toluene, then dropwise add it into the aqueous acetaldehyde solution. After the dropping ends, heat and stir at 40 °C for 45 min, then slowly dropwise add 1.68 mL of 4-hydroxyphenylacetaldehyde, then heat the container to 85 °C, reflux for 6 h, wash, rotary evaporate, recrystallize, and vacuum dry at 50 °C for 12 h to obtain intermediate product 1;

[0064] Q2: Add 4.83 g of Intermediate Product 1 into a container, and simultaneously add 45 mL of ethanol. Heat and stir at 95 °C for 1 h, then cool. Add 2.64 g of 5-aminoindole and continue the heating reaction. React at 75 °C for 3 h, wash, and vacuum dry at 85 °C for 10 h to obtain Intermediate Product 2;

[0065] Q3: Dissolve 4.75 g of Intermediate Product 2 in a container containing 2 mL of N,N-dimethylformamide solution, filter, add 3.5 g of glass fiber, and stir evenly to obtain a mixed solution. Place the mixed solution in a mold and dry at 110 °C for 2 h, then cure. The curing process is as follows: cure at 120 °C for 2 h, then raise the temperature to 140 °C and cure for 2 h, then further raise the temperature to 160 °C and cure for 2 h, then cure at 180 °C for 2 h, and finally cure at 200 °C for 2 h to obtain a modified toughening agent.

[0066] This example discloses a preparation method of a multi-setting foam glass composite thermal insulation material, including the following steps:

[0067] Step (1): Grind 39 kg of crushed glass, 4 kg of borax, and 2 kg of limestone using a ball milling method to obtain a mixed material. Control the particle size of the ground mixed material so that the proportion passing through a 200-mesh sieve is more than 95%;

[0068] Step (2): Melt and foam the mixed material, 1.1 kg of sodium carbonate, and 2 kg of lithium carbonate at 900 °C to obtain a foam melt. Mix and stir the foam melt, 3 kg of hybrid thermal insulation material, and 3 kg of modified toughening agent to obtain a composite foam melt;

[0069] Step (3): Cool the composite foam melt. Cool to 500 °C in 5 min, anneal, and then cool to obtain the multi-setting foam glass composite thermal insulation material.

[0070] Example 2

[0071] This example discloses a preparation method of a hybrid thermal insulation material, including the following steps:

[0072] R1: Add 2 g of titanium aluminum carbon powder and 3.07 g of lithium fluoride into 40 mL of 9 mol / L hydrochloric acid solution. Heat and stir at 40 °C for 48 h, centrifuge, wash by centrifugation 3 times with 1 mol / L hydrochloric acid solution and 1 mol / L lithium chloride solution respectively, then wash with deionized water until the pH = 6. Subsequently, evenly disperse the centrifuged precipitate in deionized water to obtain a suspension. Add it into a container and freeze (-80 °C, 1 Pa) and dry for 72 h to obtain an aerogel;

[0073] R2: Under the protection of nitrogen atmosphere, 1 g of dodecanol and 1.646 g of phosphorus oxychloride are dissolved in toluene. After magnetic stirring and mixing for 2 h, the mixture is heated at 70 °C for 10 h and undergoes continuous reaction. After the continuous reaction ends, the reaction solution is quickly poured into cold acetonitrile, filtered, washed 3 times, and vacuum dried at 25 °C for 24 h to obtain phosphorus-modified alkanol;

[0074] R3: Add 15 g of phosphorus-modified alkanol and 1 g of aerogel into a container, place it in a vacuum drying oven (0.09 MPa, 110 °C) for melting adsorption for 12 h to obtain a composite aerogel; add 30 g of thermoplastic polyurethane elastomer into 250 mL of N,N-dimethylformamide, stir at high temperature for 4 h. After complete dissolution, add 22 g of the composite aerogel, and continue to stir under a nitrogen atmosphere. After stirring ends, pour it into deionized water, stir until flocculants precipitate, wash the flocculants 3 times with ethanol, and dry at 70 °C for 24 h to obtain a hybrid thermal insulation material.

[0075] This example discloses a preparation method of a modified toughening agent, including the following steps:

[0076] Q1: Place 1.28 mL of 6 mol / L aqueous acetaldehyde solution in a container equipped with a thermometer, a spherical condenser and a stirrer. Adjust the pH of the aqueous acetaldehyde solution to 11 with 1 mol / L aqueous sodium hydroxide solution. Dissolve 1.06 g of aniline in 4.53 mL of toluene, and then add it dropwise to the aqueous acetaldehyde solution. After the addition ends, heat and stir at 40 °C for 45 min. Subsequently, slowly add 1.50 mL of 4-hydroxyphenylacetaldehyde dropwise, then heat the container to 85 °C, reflux for 6 h, wash, rotary evaporate, recrystallize, and vacuum dry at 50 °C for 12 h to obtain intermediate product 1;

[0077] Q2: Add 4.79 g of intermediate product 1 into a container, and at the same time add 50 mL of ethanol. Heat and stir at 95 °C for 1 h, cool, add 2.58 g of 5-aminoindole, and continue the heating reaction at 75 °C for 3 h. Wash, and vacuum dry at 85 °C for 10 h to obtain intermediate product 2;

[0078] Q3: Dissolve 4.6 g of intermediate product 2 in a container equipped with 2 mL of N,N-dimethylformamide solution, filter, add 2 g of glass fiber, stir evenly to obtain a mixed solution. Place the mixed solution in a mold and dry at 110 °C for 2 h, then cure. The curing process is: cure at 120 °C for 2 h, then raise the temperature to 140 °C and cure for 2 h, then raise the temperature to 160 °C and cure for 2 h, then cure at 180 °C for 2 h, and finally cure at 200 °C for 2 h to obtain the modified toughening agent.

[0079] This example discloses a preparation method of a multi-coagulated foam glass composite thermal insulation material, including the following steps:

[0080] Step (1): Grind 32 kg of crushed glass, 2 kg of borax, and 1 kg of limestone using the ball milling method to obtain a mixed material, and control the particle size of the ground mixed material so that the proportion passing through a 200-mesh sieve is more than 95%;

[0081] Step (2): Melt and foam the mixed material, 0.8 kg of sodium carbonate, and 1 kg of lithium carbonate at 900 °C to obtain a foam melt. Mix and stir the foam melt, 1 kg of hybrid thermal insulation material, and 2 kg of modified toughening agent to obtain a composite foam melt;

[0082] Step (3): Cool the composite foam melt, cool it to 500 °C in 5 minutes, anneal it, and then cool it to obtain a multi-set foam glass composite thermal insulation material.

[0083] Example 3

[0084] This example discloses a preparation method of a hybrid thermal insulation material, including the following steps:

[0085] R1: Add 2 g of titanium aluminum carbon powder and 3.21 g of lithium fluoride to 45 mL of 9 mol / L hydrochloric acid solution, heat and stir at 40 °C for 48 h, centrifuge, wash the precipitate with 1 mol / L hydrochloric acid solution and 1 mol / L lithium chloride solution by centrifugation three times respectively, then wash it with deionized water until the pH = 6. Subsequently, uniformly disperse the centrifuged precipitate in deionized water to obtain a suspension, add it to a container, and freeze-dry it at (-80 °C, 1 Pa) for 72 h to obtain an aerogel;

[0086] R2: Under the protection of a nitrogen atmosphere, dissolve 1 g of n-dodecanol and 1.975 g of phosphorus oxychloride in toluene, magnetically stir and mix for 2 h, then heat the mixture, heat it at 70 °C for 10 h, and carry out continuous reaction. After the continuous reaction ends, quickly pour the reaction solution into cold acetonitrile, filter, wash it three times, and vacuum dry it at 25 °C for 24 h to obtain a phosphorus-modified alkanol;

[0087] R3: Add 19 g of phosphorus-modified alkanol and 1 g of aerogel to a container, place it in a vacuum drying oven (0.09 MPa, 110 °C) for melt adsorption for 12 h to obtain a composite aerogel; Add 40 g of thermoplastic polyurethane elastomer to 300 mL of N,N-dimethylformamide, stir at high temperature for 4 h, after complete dissolution, add 25 g of composite aerogel, continue to stir under a nitrogen atmosphere. After stirring ends, pour it into deionized water, stir until flocculates precipitate, wash the flocculates with ethanol three times, and dry it at 70 °C for 24 h to obtain a hybrid thermal insulation material.

[0088] This example discloses a preparation method of a modified toughening agent, including the following steps:

[0089] Q1: Place 1.92 mL of 6 mol / L aqueous acetaldehyde solution in a container equipped with a thermometer, a spherical condenser, and a stirrer. Adjust the pH of the aqueous acetaldehyde solution to 11 with 1 mol / L aqueous sodium hydroxide solution. Dissolve 1.59 g of aniline in 6.80 mL of toluene, and then add it dropwise to the aqueous acetaldehyde solution. After the addition is complete, heat and stir at 40 °C for 45 min. Subsequently, slowly add 1.35 mL of 4-hydroxyphenylacetaldehyde dropwise, and then heat the container to 85 °C and reflux for 6 h. Wash, rotary evaporate, recrystallize, and dry under vacuum at 50 °C for 12 h to obtain intermediate product 1;

[0090] Q2: Add 4.85 g of intermediate product 1 to a container, and at the same time add 50 mL of ethanol. Heat and stir at 95 °C for 1 h, cool, add 2.17 g of 5-aminoindole, and continue the heating reaction at 75 °C for 3 h. Wash and dry under vacuum at 85 °C for 10 h to obtain intermediate product 2;

[0091] Q3: Dissolve 4.9 g of intermediate product 2 in a container containing 2 mL of N,N-dimethylformamide solution, filter, add 5 g of glass fiber, and stir evenly to obtain a mixed solution. Place the mixed solution in a mold and dry at 110 °C for 2 h, and then cure. The curing process is as follows: cure at 120 °C for 2 h, then raise the temperature to 140 °C and cure for 2 h, further raise the temperature to 160 °C and cure for 2 h, then cure at 180 °C for 2 h, and finally cure at 200 °C for 2 h to obtain the modified toughening agent.

[0092] This example discloses a preparation method of a multi-setting foam glass composite thermal insulation material, which includes the following steps:

[0093] Step (1): Grind 46 kg of broken glass, 6 kg of borax, and 3 kg of limestone by ball milling to obtain a mixed material. Control the particle size of the ground mixed material so that the proportion passing through a 200-mesh sieve is more than 95%;

[0094] Step (2): Melt and foam the mixed material, 1.3 kg of sodium carbonate, and 3 kg of lithium carbonate at 900 °C to obtain a foam melt. Mix and stir the foam melt, 2 kg of hybrid thermal insulation material, and 4 kg of modified toughening agent to obtain a composite foam melt;

[0095] Step (3): Cool the composite foam melt, cool it to 500 °C in 5 min, anneal, and cool to obtain the multi-setting foam glass composite thermal insulation material.

[0096] Example 4

[0097] This example discloses a preparation method of a hybrid thermal insulation material, which includes the following steps:

[0098] R1: Add 2 g of titanium aluminum carbon powder and 3.01 g of lithium fluoride to 43 mL of 9 mol / L hydrochloric acid solution, heat and stir at 40 °C for 48 h, centrifuge, wash by centrifugation 3 times with 1 mol / L hydrochloric acid solution and 1 mol / L lithium chloride solution respectively, then wash with deionized water until the pH = 6. Subsequently, evenly disperse the centrifuged precipitate in deionized water to obtain a suspension, add it to a container and freeze-dry (-80 °C, 1 Pa) for 72 h to obtain an aerogel;

[0099] R2: Under the protection of a nitrogen atmosphere, dissolve 1 g of dodecanol and 1.732 g of phosphorus oxychloride in toluene, magnetically stir and mix for 2 h, then heat the mixture, heat at 70 °C for 10 h and carry out continuous reaction. After the continuous reaction ends, quickly pour the reaction solution into cold acetonitrile, filter, wash 3 times, and vacuum dry at 25 °C for 24 h to obtain phosphorus-modified alkanol;

[0100] R3: Add 16 g of phosphorus-modified alkanol and 1 g of aerogel to a container, place it in a vacuum drying oven (0.09 MPa, 110 °C) for melt adsorption for 12 h to obtain a composite aerogel; add 32 g of thermoplastic polyurethane elastomer to 280 mL of N,N-dimethylformamide, stir at high temperature for 4 h, after completely dissolving, add 21 g of the composite aerogel, continue to stir under a nitrogen atmosphere. After stirring ends, pour it into deionized water, stir until flocculants precipitate, wash the flocculants 3 times with ethanol, and dry at 70 °C for 24 h to obtain a hybrid thermal insulation material.

[0101] This example discloses a preparation method of a modified toughening agent, including the following steps:

[0102] Q1: Place 1.54 mL of 6 mol / L aqueous acetaldehyde solution in a container equipped with a thermometer, a spherical condenser and a stirrer, adjust the pH of the aqueous acetaldehyde solution to 11 with 1 mol / L aqueous sodium hydroxide solution, dissolve 1.17 g of aniline in 4.78 mL of toluene, then add it dropwise to the aqueous acetaldehyde solution. After the addition is completed, heat and stir at 40 °C for 45 min, then slowly add 2.00 mL of 4-hydroxyphenylacetaldehyde dropwise, then heat the container to 85 °C, reflux for 6 h, wash, rotary evaporate, recrystallize, and vacuum dry at 50 °C for 12 h to obtain intermediate product 1;

[0103] Q2: Add 4.89 g of intermediate product 1 to a container, simultaneously add 35 mL of ethanol, heat and stir at 95 °C for 1 h, cool, add 2.09 g of 5-aminoindole, continue to carry out the heating reaction, react at 75 °C for 3 h, wash, and vacuum dry at 85 °C for 10 h to obtain intermediate product 2;

[0104] Q3: Dissolve 4.7 g of intermediate product 2 in a container containing 2 mL of N,N-dimethylformamide solution, filter, add 3 g of glass fiber, stir evenly to obtain a mixed solution. Place the mixed solution in a mold and dry it at 110 °C for 2 h, then cure it. The curing process is as follows: cure at 120 °C for 2 h, then raise the temperature to 140 °C and cure for 2 h, further raise the temperature to 160 °C and cure for 2 h, then cure at 180 °C for 2 h, and finally cure at 200 °C for 2 h to obtain a modified toughening agent.

[0105] This example discloses a preparation method of a multi-setting foam glass composite thermal insulation material, including the following steps:

[0106] Step (1): Grind 44 kg of crushed glass, 3 kg of borax, and 2.5 kg of limestone using a ball mill to obtain a mixed material. Control the particle size of the ground mixed material so that the proportion passing through a 200-mesh sieve is more than 95%;

[0107] Step (2): Melt and foam the mixed material, 1.2 kg of sodium carbonate, and 1.5 kg of lithium carbonate at 900 °C to obtain a foam melt. Mix and stir the foam melt, 4 kg of hybrid thermal insulation material, and 2.5 kg of modified toughening agent to obtain a composite foam melt;

[0108] Step (3): Cool the composite foam melt, cool it to 500 °C in 5 min, anneal it, and then cool it to obtain a multi-setting foam glass composite thermal insulation material.

[0109] Example 5

[0110] This example discloses a preparation method of a hybrid thermal insulation material, including the following steps:

[0111] R1: Add 2 g of titanium aluminum carbon powder and 3.05 g of lithium fluoride to 44 mL of 9 mol / L hydrochloric acid solution, heat and stir at 40 °C for 48 h, centrifuge, wash with 1 mol / L hydrochloric acid solution and 1 mol / L lithium chloride solution by centrifugation 3 times respectively, then wash with deionized water until the pH = 6. Subsequently, evenly disperse the centrifuged precipitate in deionized water to obtain a suspension, add it to a container and freeze-dry (-80 °C, 1 Pa) for 72 h to obtain an aerogel;

[0112] R2: Under the protection of a nitrogen atmosphere, dissolve 1 g of n-dodecanol and 1.794 g of phosphorus oxychloride in toluene, magnetically stir and mix for 2 h, then heat the mixture, heat at 70 °C for 10 h, and carry out continuous reaction. After the continuous reaction ends, quickly pour the reaction solution into cold acetonitrile, filter, wash 3 times, and vacuum dry at 25 °C for 24 h to obtain a phosphorus-modified alkanol;

[0113] R3: Add 18 g of phosphorus-modified alkanol and 1 g of aerogel into a container, place it in a vacuum drying oven (0.09 MPa, 110 °C) for melt adsorption for 12 h to obtain a composite aerogel; add 38 g of thermoplastic polyurethane elastomer into 290 mL of N,N-dimethylformamide, stir at a high temperature for 4 h. After complete dissolution, add 23 g of the composite aerogel, continue stirring under a nitrogen atmosphere. After the stirring ends, pour it into deionized water, stir until flocculates precipitate, wash the flocculates 3 times with ethanol, and dry at 70 °C for 24 h to obtain a hybrid thermal insulation material.

[0114] This example discloses a preparation method of a modified toughening agent, which includes the following steps:

[0115] Q1: Place 1.79 mL of 6 mol / L aqueous acetaldehyde solution in a container equipped with a thermometer, a spherical condenser and a stirrer, adjust the pH of the aqueous acetaldehyde solution to 11 with 1 mol / L aqueous sodium hydroxide solution. Dissolve 1.48 g of aniline in 6.25 mL of toluene, and then add it dropwise to the aqueous acetaldehyde solution. After the dropping ends, heat and stir at 40 °C for 45 min. Subsequently, slowly add 1.64 mL of 4-hydroxyphenylacetaldehyde dropwise, then heat the container to 85 °C, reflux for 6 h, wash, rotary evaporate, recrystallize, and vacuum dry at 50 °C for 12 h to obtain Intermediate Product 1;

[0116] Q2: Add 4.73 g of Intermediate Product 1 into a container, and at the same time add 42 mL of ethanol, heat and stir at 95 °C for 1 h, cool, add 1.98 g of 5-aminoindole, continue the heating reaction, react at 75 °C for 3 h, wash, and vacuum dry at 85 °C for 10 h to obtain Intermediate Product 2;

[0117] Q3: Dissolve 4.8 g of Intermediate Product 2 in a container containing 2 mL of N,N-dimethylformamide solution, filter, add 4 g of glass fiber, stir evenly to obtain a mixed solution. Place the mixed solution in a mold and dry at 110 °C for 2 h, then cure. The curing process is: cure at 120 °C for 2 h, then raise the temperature to 140 °C and cure for 2 h, then raise the temperature to 160 °C and cure for 2 h, then cure at 180 °C for 2 h, and finally cure at 200 °C for 2 h to obtain the modified toughening agent.

[0118] This example discloses a preparation method of a multi-coagulation foam glass composite thermal insulation material, which includes the following steps:

[0119] Step (1): Grind 38 kg of broken glass, 5 kg of borax and 1.5 kg of limestone by ball milling to obtain a mixed material. Control the particle size of the ground mixed material so that the proportion passing through a 200-mesh sieve is more than 95%;

[0120] Step (2): Melt and foam the mixed materials, 1 kg of sodium carbonate, and 2.5 kg of lithium carbonate at 900 °C to obtain a foam melt. Mix and stir the foam melt, 5 kg of the hybrid thermal insulation material, and 3.1 kg of the modified toughening agent to obtain a composite foam melt;

[0121] Step (3): Cool the composite foam melt. Cool it to 500 °C in 5 minutes, anneal, and then cool to obtain the multi-set foam glass composite thermal insulation material.

[0122] Example 6

[0123] This example discloses a preparation method of a hybrid thermal insulation material, including the following steps:

[0124] R1: Add 2 g of titanium aluminum carbon powder and 3.20 g of lithium fluoride to 41 mL of 9 mol / L hydrochloric acid solution, heat and stir at 40 °C for 48 h, centrifuge, wash with 1 mol / L hydrochloric acid solution and 1 mol / L lithium chloride solution by centrifugation 3 times respectively, then wash with deionized water until the pH = 6. Subsequently, evenly disperse the centrifuged precipitate in deionized water to obtain a suspension, add it to a container, freeze (-80 °C, 1 Pa) and dry for 72 h to obtain an aerogel;

[0125] R2: Under the protection of a nitrogen atmosphere, dissolve 1 g of dodecanol and 1.903 g of phosphorus oxychloride in toluene, magnetically stir and mix for 2 h, then heat the mixture, heat at 70 °C for 10 h, and carry out continuous reaction. After the continuous reaction ends, quickly pour the reaction solution into cold acetonitrile, filter, wash 3 times, and vacuum dry at 25 °C for 24 h to obtain a phosphorus-modified alkanol;

[0126] R3: Add 17 g of the phosphorus-modified alkanol and 1 g of the aerogel to a container, place it in a vacuum drying oven (0.09 MPa, 110 °C) for melting adsorption for 12 h to obtain a composite aerogel; Add 36 g of thermoplastic polyurethane elastomer to 260 mL of N,N-dimethylformamide, stir at a high temperature for 4 h, after complete dissolution, add 24 g of the composite aerogel, continue to stir under a nitrogen atmosphere. After stirring ends, pour it into deionized water, stir until flocculates precipitate, wash the flocculates with ethanol 3 times, and dry at 70 °C for 24 h to obtain the hybrid thermal insulation material.

[0127] This example discloses a preparation method of a modified toughening agent, including the following steps:

[0128] Q1: Place 1.67 mL of 6 mol / L aqueous acetaldehyde solution in a container equipped with a thermometer, a spherical condenser, and a stirrer. Adjust the pH of the aqueous acetaldehyde solution to 11 with 1 mol / L aqueous sodium hydroxide solution. Dissolve 1.22 g of aniline in 5.24 mL of toluene, and then add it dropwise to the aqueous acetaldehyde solution. After the addition is complete, heat and stir at 40 °C for 45 min. Subsequently, slowly add 1.97 mL of 4-hydroxyphenylacetaldehyde dropwise, and then heat the container to 85 °C and reflux for 6 h. Wash, rotary evaporate, recrystallize, and dry in vacuo at 50 °C for 12 h to obtain intermediate product 1;

[0129] Q2: Add 4.75 g of intermediate product 1 to a container, and at the same time add 48 mL of ethanol. Heat and stir at 95 °C for 1 h, cool, add 1.79 g of 5-aminoindole, and continue the heating reaction. React at 75 °C for 3 h, wash, and dry in vacuo at 85 °C for 10 h to obtain intermediate product 2;

[0130] Q3: Dissolve 4.85 g of intermediate product 2 in a container containing 2 mL of N,N-dimethylformamide solution, filter, add 4.5 g of glass fiber, stir evenly to obtain a mixed solution. Place the mixed solution in a mold and dry at 110 °C for 2 h, then cure. The curing process is as follows: cure at 120 °C for 2 h, then raise the temperature to 140 °C and cure for 2 h, then raise the temperature to 160 °C and cure for 2 h, then cure at 180 °C for 2 h, and finally cure at 200 °C for 2 h to obtain the modified toughening agent.

[0131] This example discloses a preparation method of a multi-setting foam glass composite thermal insulation material, which includes the following steps:

[0132] Step (1): Grind 40 kg of broken glass, 4.5 kg of borax, and 2.75 kg of limestone by ball milling to obtain a mixed material. Control the particle size of the ground mixed material so that the proportion passing through a 200-mesh sieve is more than 95%;

[0133] Step (2): Melt and foam the mixed material, 0.9 kg of sodium carbonate, and 2.9 kg of lithium carbonate at 900 °C to obtain a foam melt. Mix and stir the foam melt, 3.5 kg of hybrid thermal insulation material, and 3.7 kg of modified toughening agent to obtain a composite foam melt;

[0134] Step (3): Cool the composite foam melt, cool it to 500 °C in 5 min, anneal, and cool to obtain the multi-setting foam glass composite thermal insulation material.

[0135] Comparative Example 1

[0136] Compared with Example 1, in Comparative Example 1, during the preparation of the hybrid thermal insulation material, titanium aluminum carbon powder is not added, and other conditions remain unchanged.

[0137] Comparative Example 2

[0138] Comparative Example 2 is compared with Example 1. In the process of preparing the hybrid thermal insulation material in Comparative Example 2, dodecyl alcohol is not added, and other conditions remain unchanged.

[0139] Comparative Example 3

[0140] Comparative Example 3 is compared with Example 1. In the process of preparing the hybrid thermal insulation material in Comparative Example 3, thermoplastic polyurethane elastomer is not added, and other conditions remain unchanged.

[0141] Comparative Example 4

[0142] Comparative Example 4 is compared with Example 1. In the process of preparing the modified toughening agent in Comparative Example 4, 4-hydroxyphenylacetaldehyde is not added, and other conditions remain unchanged.

[0143] Comparative Example 5

[0144] Comparative Example 5 is compared with Example 1. In the process of preparing the modified toughening agent in Comparative Example 5, 5-aminoindole is not added, and other conditions remain unchanged.

[0145] Comparative Example 6

[0146] Comparative Example 6 is compared with Example 1. In the process of preparing the multi-set foam glass composite thermal insulation material in Comparative Example 6, the hybrid thermal insulation material is not added, and other conditions remain unchanged.

[0147] Comparative Example 7

[0148] Comparative Example 7 is compared with Example 1. In the process of preparing the multi-set foam glass composite thermal insulation material in Comparative Example 7, the modified toughening agent is not added, and other conditions remain unchanged.

[0149] Testing of thermal insulation performance, toughness, and corrosion resistance

[0150] The properties of the multi-set foam glass composite thermal insulation materials prepared in Examples 1-6 and Comparative Examples 1-7 were tested. The thermal insulation performance of the samples was measured according to GB / T 10296-2008, the toughness of the samples was measured according to GB / T 38686-2020, and the corrosion resistance of the samples was measured according to GB / T 28416-2012. The test results are shown in Table 1:

[0151] Table 1 Test results of thermal insulation performance, toughness, and corrosion resistance

[0152] Item Thermal Conductivity / W / (m·K) Compressive Strength / MPa <![CDATA[Sample weight loss / g / m 2 > Example 1 0.034 5.46 10.23 Example 2 0.036 5.42 10.28 Example 3 0.035 5.34 10.34 Example 4 0.037 5.27 10.41 Example 5 0.039 5.31 10.56 Example 6 0.038 5.28 10.37 Comparative Example 1 0.046 5.03 14.68 Comparative Example 2 0.048 5.01 15.23 Comparative Example 3 0.049 4.96 14.82 Comparative Example 4 0.042 4.65 12.61 Comparative Example 5 0.041 4.36 12.15 Comparative Example 6 0.053 4.91 17.79 Comparative Example 7 0.045 4.48 13.46

[0153] As can be seen from the test results in Table 1, the preparation methods adopted in Examples 1-6 of the present invention endow the multi-set foam glass composite thermal insulation material with excellent thermal insulation performance, toughness and corrosion resistance. By comparing Comparative Example 1 with Examples 1-6, it can be seen that adding titanium aluminum carbon powder can improve the thermal insulation performance and corrosion resistance of the multi-set foam glass composite thermal insulation material; by comparing Comparative Example 2 with Examples 1-6, it can be seen that adding n-dodecanol can improve the thermal insulation performance and corrosion resistance of the multi-set foam glass composite thermal insulation material; by comparing Comparative Example 3 with Examples 1-6, it can be seen that adding thermoplastic polyurethane elastomer can improve the thermal insulation performance and corrosion resistance of the multi-set foam glass composite thermal insulation material; by comparing Comparative Example 4 with Examples 1-6, it can be seen that adding hydroxybenzeneacetaldehyde can improve the toughness of the multi-set foam glass composite thermal insulation material; by comparing Comparative Example 5 with Examples 1-6, it can be seen that adding 5-aminoindole can improve the toughness of the multi-set foam glass composite thermal insulation material; by comparing Comparative Example 6 with Examples 1-6, it can be seen that adding hybrid thermal insulation material can improve the thermal insulation performance and corrosion resistance of the multi-set foam glass composite thermal insulation material; by comparing Comparative Example 7 with Examples 1-6, it can be seen that adding modified toughening agent can improve the toughness of the multi-set foam glass composite thermal insulation material.

[0154] As described above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

[0155] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor limit the present invention to only the specific embodiments. Obviously, according to the content of this specification, many modifications and changes can be made. This specification selects and specifically describes these embodiments to better explain the principle and practical application of the present invention, so that those skilled in the art in the technical field can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. Multi-condensed foam glass composite thermal insulation material, characterized in that, It is composed of the following components in parts by weight: 32 - 46 parts of broken glass, 2 - 6 parts of borax, 1 - 3 parts of limestone, 1 - 5 parts of hybrid thermal insulation material, 2 - 4 parts of modified toughening agent, 0.8 - 1.3 parts of foaming agent, and 1 - 3 parts of flux; wherein, the hybrid thermal insulation material is prepared from titanium aluminum carbon powder, lithium fluoride, n - dodecanol, phosphorus oxychloride and thermoplastic polyurethane elastomer, and the modified toughening agent is prepared from aqueous acetaldehyde solution, aniline, 4 - hydroxyphenylacetaldehyde, 5 - aminoindole and glass fiber; The hybrid thermal insulation material is prepared by the following steps: R1: Add titanium aluminum carbon powder and lithium fluoride into hydrochloric acid solution, heat and stir, centrifuge, wash by centrifugation with hydrochloric acid solution and lithium chloride solution respectively, then wash with deionized water. Subsequently, evenly disperse the centrifuged precipitate in deionized water to obtain a suspension, add it into a container for freeze - drying to obtain an aerogel; R2: Under the protection of nitrogen atmosphere, dissolve n - dodecanol and phosphorus oxychloride in toluene, magnetically stir and mix, then heat the mixture and carry out continuous reaction. After the continuous reaction ends, quickly pour the reaction solution into cold acetonitrile, filter, wash, and vacuum - dry to obtain phosphorus - modified alkanol; R3: Add phosphorus - modified alkanol and aerogel into a container, place it in a vacuum drying oven for melt adsorption to obtain a composite aerogel; add thermoplastic polyurethane elastomer into N, N - dimethylformamide, stir at high temperature until completely dissolved, then add the composite aerogel, continue to stir under nitrogen atmosphere. After stirring ends, pour it into deionized water, stir until flocculants precipitate, wash the flocculants, and dry to obtain the hybrid thermal insulation material.

2. The multi-setting foam glass composite thermal insulation material according to claim 1, wherein In R1, the dosage ratio of titanium aluminum carbon powder, lithium fluoride and hydrochloric acid solution is 2g:(3 - 3.22)g:(40 - 45)mL, the concentration of hydrochloric acid solution is 9mol / L, the temperature of heating and stirring is 35 - 40°C, the time of heating and stirring is 48 - 54h. During the washing process, the concentration of hydrochloric acid solution is 1mol / L, the concentration of lithium chloride solution is 1mol / L, the number of centrifugal washing times is 3 - 5 times, the pH after washing with deionized water is 6, the temperature of freeze - drying is - 70~ - 80°C, the pressure is 0 - 1Pa, and the time is 72 - 84h.

3. The multi-condensed foam glass composite thermal insulation material according to claim 1, characterized in that In R2, the molar ratio of n - dodecanol and phosphorus oxychloride is 1:(2 - 2.4), the magnetic stirring time is 2 - 3h, the heating temperature is 60 - 70°C, the heating time is 8 - 10h, the number of washing times is 3 - 5 times, the vacuum drying temperature is 25°C, and the vacuum drying time is 20 - 24h.

4. The multi-condensed foam glass composite thermal insulation material according to claim 1, wherein In the R3, the mass ratio of the phosphorus-modified alkanol to the aerogel is (15 - 19) g:1 g, the pressure in the vacuum drying oven is 0.06 - 0.09 MPa, the temperature is 100 - 110 °C, the melting adsorption time is 10 - 12 h, the dosage ratio of the thermoplastic polyurethane elastomer, N,N-dimethylformamide and the composite aerogel is (30 - 40) g:(250 - 300) mL:(20 - 25) g, the continuous stirring time is 2 - 4 h, the flocculants are washed with ethanol, the number of washing times is 3 - 5 times, the drying temperature is 60 - 70 °C, and the drying time is 20 - 30 h.

5. The multi-condensed foam glass composite thermal insulation material according to claim 1, wherein The preparation method of the modified toughening agent includes the following steps: Q1: Place the aqueous solution of acetaldehyde in a container equipped with a thermometer, a spherical condenser and a stirrer, adjust the pH of the aqueous solution of acetaldehyde with the aqueous solution of sodium hydroxide, dissolve aniline in toluene, and then dropwise add it to the aqueous solution of acetaldehyde. After the dropping is completed, heat and stir, then slowly dropwise add 4-hydroxyphenylacetaldehyde, and then heat the container, reflux, wash, rotary evaporate, recrystallize, and vacuum dry to obtain Intermediate Product 1; Q2: Add Intermediate Product 1 to a container, add ethanol at the same time, heat and stir, cool, add 5-aminoindole, continue to carry out the heating reaction, wash, and vacuum dry to obtain Intermediate Product 2; Q3: Dissolve Intermediate Product 2 in a container containing N,N-dimethylformamide solution, filter, add glass fiber, stir evenly to obtain a mixed solution, place the mixed solution in a mold, dry, and cure to obtain the modified toughening agent.

6. The multi-condensed foam glass composite thermal insulation material according to claim 5, characterized in that, In the Q1, the molar ratio of acetaldehyde, aniline, toluene and 4-hydroxyphenylacetaldehyde is (0.8 - 1.2):(0.4 - 0.6):(1.51 - 2.27):(0.4 - 0.6), the concentration of the aqueous solution of acetaldehyde is 6 mol / L, the concentration of the aqueous solution of sodium hydroxide is 1 mol / L, adjust the pH = 11, the heating and stirring temperature is 30 - 40 °C, the time is 30 - 45 min, the heating temperature is 80 - 85 °C, the reflux time is 5 - 6 h, the vacuum drying temperature is 40 - 50 °C, and the vacuum drying time is 12 - 15 h.

7. The multi-condensed foam glass composite thermal insulation material according to claim 5, characterized in that, In the Q2, the molar ratio of Intermediate Product 1, ethanol and 5-aminoindole is (1 - 2):(0.43 - 0.87):(1 - 2), the heating and stirring temperature is 90 - 95 °C, the time is 1 - 2 h, the heating reaction temperature is 70 - 75 °C, the reaction time is 2 - 3 h, the vacuum drying temperature is 80 - 90 °C, and the time is 10 - 12 h; in the Q3, the dosage ratio of Intermediate Product 2, N,N-dimethylformamide and glass fiber is (4.6 - 4.9) g:2 mL:(2 - 5) g, the drying temperature is 100 - 110 °C, the drying time is 1 - 2 h, and the curing process is: cure at 120 °C for 2 h, then raise the temperature to 140 °C and cure for 2 h, then raise the temperature to 160 °C and cure for 2 h, then cure at 180 °C for 2 h, and finally cure at 200 °C for 2 h.

8. The preparation method of the multi-coagulation foam glass composite thermal insulation material according to any one of claims 1-7, characterized in that, It includes the following steps: Step (1): Grind the crushed glass, borax and limestone to obtain a mixed material; Step (2): Melting and foaming the mixed materials, foaming agent and flux to obtain a foam melt, and mixing and stirring the foam melt, hybrid thermal insulation material and modified toughening agent to obtain a composite foam melt; Step (3): Cooling, annealing and cooling the composite foam melt to obtain a multi-set foam glass composite thermal insulation material.

9. The preparation method of the multi-setting foam glass composite thermal insulation material according to claim 8, characterized in that, In the said step (1), ball milling method is used for grinding, and the particle size of the mixed materials after grinding is controlled such that the proportion passing through a 200-mesh sieve is more than 95%; in the said step (2), the temperature for melting and foaming is 900 - 1000 °C; in the said step (3), the cooling time is 3 - 5 min, and the temperature after cooling is 500 - 600 °C.

Images