CN118619556A - Polycondensate foam glass composite thermal insulation material and preparation method thereof - Google Patents

Abstract

The invention discloses a multi-coagulation foam glass composite heat insulation material and a preparation method thereof, and belongs to the technical field of composite heat insulation material preparation. The preparation method of the multi-coagulation foam glass composite heat insulation material comprises the following steps: step (1): grinding the broken glass, borax and limestone to obtain a mixed material; step (2): melting and foaming the mixed material, the foaming agent and the fluxing agent to obtain a foam melt, and mixing and stirring the foam melt, the hybrid heat insulation material and the modified toughening agent to obtain a composite foam melt; step (3): and cooling, annealing and cooling the composite foam melt to obtain the multi-coagulation foam glass composite heat insulation material. By adding the hybrid heat insulating material and the modified toughening agent to the cullet, the multi-coagulation foam glass composite heat insulating material with excellent heat insulating property, corrosion resistance and toughness can be obtained.

Description

Polycondensate foam glass composite thermal insulation material and preparation method thereof

Technical Field

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

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. 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. Some insulation materials have poor fire resistance and are easy to burn in the event of a fire, accelerating the spread of the fire and posing a threat to people and property.

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 mixing, 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.

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

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.

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

The invention provides a polycondensate foam glass composite thermal insulation material, which is composed of the following components in parts by weight: 32-46 parts of cullet, 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 acetaldehyde aqueous solution, aniline, 4-hydroxyphenylacetaldehyde, 5-aminoindole and glass fiber.

Preferably, the method for preparing the hybrid thermal insulation material comprises the following steps:

R1: Add titanium aluminum carbon powder and lithium fluoride to hydrochloric acid solution, heat and stir, centrifuge, wash with hydrochloric acid solution and lithium chloride solution respectively, wash with deionized water, then evenly disperse the centrifugal precipitate in deionized water to obtain a suspension, add the suspension to a container for freeze drying to obtain aerogel;

R2: Under the protection of nitrogen atmosphere, n-dodecanol and phosphorus oxychloride are dissolved in toluene, the mixture is heated after magnetic stirring, and the reaction is continued. After the reaction is completed, the reaction solution is quickly poured into cold acetonitrile, filtered, washed, and vacuum dried 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, and obtain a composite aerogel; add thermoplastic polyurethane elastomer into N,N-dimethylformamide, stir at high temperature, and add the composite aerogel after it is completely dissolved, and continue stirring under a nitrogen atmosphere. After the stirring is completed, pour it into deionized water, stir until flocs are precipitated, wash the flocs, and dry them to obtain a hybrid insulation material.

In the above process, aerogel is first prepared using titanium aluminum carbon powder and lithium fluoride, and then n-dodecanol is chemically modified using phosphorus oxychloride. The phosphorus-modified alkanol is then adsorbed into the aerogel skeleton through vacuum impregnation technology to prepare a thermally conductive and shape-stable composite aerogel. Finally, the composite aerogel and thermoplastic polyurethane elastomer are mixed using solvent blending to prepare a hybrid insulation material.

Preferably, 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 heating and stirring temperature is 35-40°C, and the heating and stirring time is 48-54h. During the washing process, the concentration of the hydrochloric acid solution is 1mol/L, the concentration of the lithium chloride solution is 1mol/L, the number of centrifugal washings is 3-5 times, the pH after washing with deionized water is 6, the freeze-drying temperature is -70 to -80°C, the pressure is 0-1Pa, and the time is 72-84h.

Preferably, in R2, the molar ratio of n-dodecanol to 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 washing times is 3-5 times, the vacuum drying temperature is 25°C, and the vacuum drying time is 20-24h.

Preferably, in R3, the mass ratio of phosphorus-modified alkanol and 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 melt adsorption time is 10-12 h, the amount ratio of thermoplastic polyurethane elastomer, N,N-dimethylformamide and composite aerogel is (30-40) g: (250-300) mL: (20-25) g, the stirring time is continued for 2-4 h, the flocculent is washed with ethanol, the washing times are 3-5 times, the drying temperature is 60-70° C., and the drying time is 20-30 h.

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

Q1: placing an acetaldehyde aqueous solution in a container equipped with a thermometer, a spherical condenser and a stirrer, adjusting the pH of the acetaldehyde aqueous solution with an aqueous sodium hydroxide solution, dissolving aniline in toluene, and then adding dropwise to the acetaldehyde aqueous solution, heating and stirring after the addition is completed, and then slowly adding 4-hydroxyphenylacetaldehyde, and then heating the container, reflux, washing, rotary evaporation, recrystallization, and vacuum drying to obtain an 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 heating reaction, wash, and vacuum dry to obtain intermediate product 2;

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

In the above process, acetaldehyde, aniline and 4-hydroxyphenylacetaldehyde are firstly reacted to synthesize an intermediate product 1 with an aldehyde group, which is then reacted with 5-aminoindole to synthesize an intermediate product 2, and the intermediate product 2 is used to modify the glass fiber to obtain a modified toughening agent.

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 30-45min, the heating temperature is 80-85°C, the reflux time is 5-6h, the vacuum drying temperature is 40-50°C, and the vacuum drying time is 12-15h.

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

Preferably, the method for preparing the multi-condensable 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, the foaming agent and the flux to obtain a foam melt, and mixing and stirring the foam melt, the hybrid thermal insulation material and the modified toughening agent to obtain a composite foam melt;

Step (3): cooling the composite foam melt, annealing, and cooling to obtain a multi-condensate foam glass composite insulation material.

Preferably, in step (1), ball milling is used for grinding, and the particle size of the ground mixture is controlled to be more than 95% under a 200-mesh sieve; in step (2), the temperature of melt foaming is 900-1000°C; in step (3), the cooling time is 3-5 minutes, and the temperature after cooling is 500-600°C.

In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

1. The present invention utilizes aerogel, phosphorus-modified alkanol and thermoplastic polyurethane elastomer to synthesize hybrid thermal insulation materials, and then utilizes acetaldehyde, aniline, 4-hydroxyphenylacetaldehyde, 5-aminoindole and glass fiber to synthesize a modified toughening agent. The synthesized polycondensate foam glass composite thermal insulation material utilizes broken glass, hybrid thermal insulation materials and modified toughening agents as raw materials, and has excellent thermal insulation performance, corrosion resistance and toughness.

2. The present invention utilizes titanium aluminum carbon powder, lithium fluoride, phosphorus oxychloride, n-dodecanol and thermoplastic polyurethane elastomer to prepare a hybrid thermal insulation material. 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 ambient temperature rises, the phase change material undergoes a phase change from solid to liquid, absorbing heat and lowering the ambient temperature; when the ambient temperature drops, the phase change material returns from liquid to solid, releasing the stored heat, which can effectively alleviate the fluctuation of ambient temperature and improve the thermal insulation performance of the hybrid thermal insulation material; and due to the formation of the hybrid thermal insulation The presence of aerogel structure and phosphorus-modified alkanol in the material forms a complex thermal resistance network inside it, thereby reducing the occurrence of heat conduction, thermal radiation and thermal convection; at the same time, the polyurethane segments contained in the thermoplastic polyurethane elastomer can resist the corrosion 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 insulation material. Using the hybrid insulation material as raw material to prepare polycondensate foam glass composite insulation material can effectively improve the thermal insulation and corrosion resistance of the material.

3. The present invention prepares a modified toughening agent by reacting acetaldehyde, aniline, 4-hydroxyphenylacetaldehyde, 5-aminoindole and glass fiber. The aldehyde group and the indole group react to form a special rose indole structure, which can provide more free volume. The increase in free volume indicates that the material can deform more easily when subjected to external force and absorb more energy. This energy absorption mechanism helps to reduce stress concentration and prevent the polycondensate foam glass composite insulation material from breaking when subjected to impact or stretching. The rose indole structure also has good flexibility and elasticity, so that the modified toughening agent can play a buffering role when the material is subjected to external force, reducing the direct impact it bears, and the presence of elasticity can also help the material return to its original state after deformation, maintaining the integrity and stability of the structure.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

FIG1 is a flow chart of a method for preparing a polycondensate foam glass composite thermal insulation material according to the present invention.

DETAILED DESCRIPTION

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

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

Titanium aluminum carbon powder was purchased from Suzhou Kaifa New Material Technology Co., Ltd.;

Lithium fluoride was purchased from Shandong Jinyufeng New Materials Co., Ltd., CAS No.: 7789-24-4;

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

Lithium chloride was purchased from Langfang Qianyao Technology Co., Ltd., CAS No.: 7447-41-8;

n-Dodecanol was purchased from Guangzhou Baosheng Chemical Co., Ltd., CAS No.: 112-53-8;

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

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

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

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

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

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

Acetaldehyde was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd., CAS number: 75-07-0;

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

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

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

Glass fiber was purchased from Langfang Kelan Fireproof Materials Co., Ltd., CAS number: 65997-17-3;

The cullet was purchased from Jinan Zhongmei New Material Technology Co., Ltd.;

Borax was purchased from Changsha Jianuo Chemical Co., Ltd., CAS number: 1303-96-4;

Limestone was purchased from Hebei Jiegui Mineral Products Co., Ltd., CAS number: 471-34-1;

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

Lithium carbonate was purchased from Hebei Mojin Biotechnology Co., Ltd., CAS number: 554-13-2.

Example 1

This embodiment discloses a method for preparing a hybrid thermal insulation material, comprising the following steps:

R1: 2 g titanium aluminum carbon powder and 3.11 g lithium fluoride were added to 42.5 mL 9 mol/L hydrochloric acid solution, heated and stirred at 40 ° C for 48 h, centrifuged, washed three times with 1 mol/L hydrochloric acid solution and 1 mol/L lithium chloride solution, respectively, and then washed with deionized water until pH = 6. The centrifugal precipitate was uniformly dispersed in deionized water to obtain a suspension, which was added to a container and freeze-dried (-80 ° C, 1 Pa) for 72 h to obtain an aerogel;

R2: Under nitrogen atmosphere, 1 g of n-dodecanol and 1.811 g of phosphorus oxychloride were dissolved in toluene, and the mixture was heated at 70°C for 10 h and continued to react after the reaction. After the reaction was completed, the reaction solution was quickly poured into cold acetonitrile, filtered, washed 3 times, and dried under vacuum at 25°C for 24 h to obtain phosphorus-modified alkanol;

R3: Add 17.5g of phosphorus-modified alkanol and 1g of aerogel into a container, place it in a vacuum drying oven (0.09MPa, 110℃) for melt adsorption for 12h to obtain a composite aerogel; add 35g of thermoplastic polyurethane elastomer into 275mL of N,N-dimethylformamide, stir at high temperature for 4h, and add 22.5g of composite aerogel after complete dissolution. Continue stirring under a nitrogen atmosphere. After stirring, pour it into deionized water and stir until flocs are precipitated. Wash the flocs with ethanol 3 times and dry them at 70℃ for 24h to obtain a hybrid insulation material.

This embodiment discloses a method for preparing a modified toughening agent, comprising the following steps:

Q1: 1.60 mL of 6 mol/L acetaldehyde aqueous solution was placed in a container equipped with a thermometer, a spherical condenser and a stirrer, and the pH of the acetaldehyde aqueous solution was adjusted to 11 with a 1 mol/L sodium hydroxide aqueous solution. 1.33 g of aniline was dissolved in 5.67 mL of toluene, and then added dropwise to the acetaldehyde aqueous solution. After the addition was completed, the mixture was heated and stirred at 40°C for 45 min, and then 1.68 mL of 4-hydroxyphenylacetaldehyde was slowly added dropwise. The container was then heated to 85°C, refluxed for 6 h, washed, rotary evaporated, recrystallized, and vacuum dried at 50°C for 12 h to obtain intermediate 1;

Q2: 4.83 g of intermediate product 1 was added to a container, and 45 mL of ethanol was added at the same time. The mixture was heated and stirred at 95°C for 1 h, cooled, and 2.64 g of 5-aminoindole was added. The mixture was heated and reacted at 75°C for 3 h. The mixture was washed and vacuum dried at 85°C for 10 h to obtain intermediate product 2.

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, stir evenly to obtain a mixed solution, place the mixed solution in a mold, dry at 110°C for 2 h, and cure. The curing process is: cure at 120°C for 2 h, then heat to 140°C for 2 h, then heat to 160°C 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.

This embodiment discloses a method for preparing a polycondensate foam glass composite thermal insulation material, comprising the following steps:

Step (1): grinding 39 kg of broken glass, 4 kg of borax and 2 kg of limestone by ball milling to obtain a mixed material, wherein the particle size of the ground mixed material is controlled to be more than 95% under a 200-mesh sieve;

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, and 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;

Step (3): cooling the composite foam melt to 500° C. within 5 minutes, annealing, and cooling to obtain a polycondensate foam glass composite thermal insulation material.

Example 2

This embodiment discloses a method for preparing a hybrid thermal insulation material, comprising the following steps:

R1: 2 g titanium aluminum carbon powder and 3.07 g lithium fluoride were added to 40 mL 9 mol/L hydrochloric acid solution, heated and stirred at 40 ° C for 48 h, centrifuged, washed three times with 1 mol/L hydrochloric acid solution and 1 mol/L lithium chloride solution respectively, and then washed with deionized water until pH = 6. The centrifugal precipitate was then evenly dispersed in deionized water to obtain a suspension, which was added to a container and freeze-dried (-80 ° C, 1 Pa) for 72 h to obtain an aerogel;

R2: Under nitrogen atmosphere, 1 g of n-dodecanol and 1.646 g of phosphorus oxychloride were dissolved in toluene, and the mixture was heated at 70°C for 10 h and continued to react after the reaction. After the reaction was completed, the reaction solution was quickly poured into cold acetonitrile, filtered, washed 3 times, and dried under vacuum at 25°C for 24 h to obtain phosphorus-modified alkanol;

R3: Add 15g of phosphorus-modified alkanol and 1g of aerogel into a container, place it in a vacuum drying oven (0.09MPa, 110℃) for melt adsorption for 12h to obtain a composite aerogel; add 30g of thermoplastic polyurethane elastomer into 250mL of N,N-dimethylformamide, stir at high temperature for 4h, and add 22g of composite aerogel after complete dissolution. Continue stirring under a nitrogen atmosphere. After stirring, pour it into deionized water and stir until flocs are precipitated. Wash the flocs with ethanol 3 times and dry them at 70℃ for 24h to obtain a hybrid insulation material.

This embodiment discloses a method for preparing a modified toughening agent, comprising the following steps:

Q1: 1.28 mL of 6 mol/L acetaldehyde aqueous solution was placed in a container equipped with a thermometer, a spherical condenser and a stirrer, and the pH of the acetaldehyde aqueous solution was adjusted to 11 with a 1 mol/L sodium hydroxide aqueous solution. 1.06 g of aniline was dissolved in 4.53 mL of toluene, and then added dropwise to the acetaldehyde aqueous solution. After the addition was completed, the mixture was heated and stirred at 40°C for 45 min, and then 1.50 mL of 4-hydroxyphenylacetaldehyde was slowly added dropwise. The container was then heated to 85°C, refluxed for 6 h, washed, rotary evaporated, recrystallized, and vacuum dried at 50°C for 12 h to obtain intermediate 1;

Q2: 4.79 g of intermediate product 1 was added to a container, and 50 mL of ethanol was added at the same time. The mixture was heated and stirred at 95°C for 1 h, cooled, and 2.58 g of 5-aminoindole was added. The mixture was heated and reacted at 75°C for 3 h. The mixture was washed and vacuum dried at 85°C for 10 h to obtain intermediate product 2.

Q3: Dissolve 4.6 g of intermediate product 2 in a container containing 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, dry at 110°C for 2 h, and cure. The curing process is: cure at 120°C for 2 h, then heat to 140°C for 2 h, then heat to 160°C 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.

This embodiment discloses a method for preparing a polycondensate foam glass composite thermal insulation material, comprising the following steps:

Step (1): grinding 32 kg of broken glass, 2 kg of borax and 1 kg of limestone by ball milling to obtain a mixed material, wherein the particle size of the ground mixed material is controlled to be more than 95% under a 200-mesh sieve;

Step (2): melting and foaming the mixed material, 0.8 kg of sodium carbonate and 1 kg of lithium carbonate at 900° C. to obtain a foam melt, and mixing and stirring the foam melt, 1 kg of a hybrid thermal insulation material and 2 kg of a modified toughening agent to obtain a composite foam melt;

Step (3): cooling the composite foam melt to 500° C. within 5 minutes, annealing, and cooling to obtain a polycondensate foam glass composite thermal insulation material.

Example 3

This embodiment discloses a method for preparing a hybrid thermal insulation material, comprising the following steps:

R1: 2 g titanium aluminum carbon powder and 3.21 g lithium fluoride were added to 45 mL 9 mol/L hydrochloric acid solution, heated and stirred at 40 ° C for 48 h, centrifuged, washed with 1 mol/L hydrochloric acid solution and 1 mol/L lithium chloride solution for 3 times, washed with deionized water until pH = 6, and then the centrifugal precipitate was evenly dispersed in deionized water to obtain a suspension, which was added to a container and freeze-dried (-80 ° C, 1 Pa) for 72 h to obtain an aerogel;

R2: Under nitrogen atmosphere, 1 g of n-dodecanol and 1.975 g of phosphorus oxychloride were dissolved in toluene, and the mixture was heated at 70°C for 10 h and continued to react after the reaction. After the reaction was completed, the reaction solution was quickly poured into cold acetonitrile, filtered, washed 3 times, and dried under vacuum at 25°C for 24 h to obtain phosphorus-modified alkanol;

R3: Add 19g of phosphorus-modified alkanol and 1g of aerogel into a container, place it in a vacuum drying oven (0.09MPa, 110℃) for melt adsorption for 12h to obtain a composite aerogel; add 40g of thermoplastic polyurethane elastomer into 300mL of N,N-dimethylformamide, stir at high temperature for 4h, and add 25g of composite aerogel after complete dissolution. Continue stirring under a nitrogen atmosphere. After stirring, pour it into deionized water and stir until flocs are precipitated. Wash the flocs with ethanol 3 times and dry them at 70℃ for 24h to obtain a hybrid insulation material.

This embodiment discloses a method for preparing a modified toughening agent, comprising the following steps:

Q1: 1.92 mL of 6 mol/L acetaldehyde aqueous solution was placed in a container equipped with a thermometer, a spherical condenser and a stirrer, and the pH of the acetaldehyde aqueous solution was adjusted to 11 with a 1 mol/L sodium hydroxide aqueous solution. 1.59 g of aniline was dissolved in 6.80 mL of toluene, and then added dropwise to the acetaldehyde aqueous solution. After the addition was completed, the mixture was heated and stirred at 40°C for 45 min, and then 1.35 mL of 4-hydroxyphenylacetaldehyde was slowly added dropwise. The container was then heated to 85°C, refluxed for 6 h, washed, rotary evaporated, recrystallized, and vacuum dried at 50°C for 12 h to obtain intermediate 1;

Q2: 4.85 g of intermediate product 1 was added to a container, and 50 mL of ethanol was added at the same time. The mixture was heated and stirred at 95°C for 1 h, cooled, and 2.17 g of 5-aminoindole was added. The mixture was heated and reacted at 75°C for 3 h. The mixture was washed and vacuum dried at 85°C for 10 h to obtain intermediate product 2.

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, stir evenly to obtain a mixed solution, place the mixed solution in a mold, dry at 110°C for 2 h, and cure. The curing process is: cure at 120°C for 2 h, then heat to 140°C for 2 h, then heat to 160°C 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.

This embodiment discloses a method for preparing a polycondensate foam glass composite thermal insulation material, comprising the following steps:

Step (1): grinding 46 kg of broken glass, 6 kg of borax and 3 kg of limestone by ball milling to obtain a mixed material, wherein the particle size of the ground mixed material is controlled to be more than 95% under a 200-mesh sieve;

Step (2): melting and foaming the mixed material, 1.3 kg of sodium carbonate and 3 kg of lithium carbonate at 900° C. to obtain a foam melt, and mixing and stirring the foam melt, 2 kg of a hybrid thermal insulation material and 4 kg of a modified toughening agent to obtain a composite foam melt;

Step (3): cooling the composite foam melt to 500° C. within 5 minutes, annealing, and cooling to obtain a polycondensate foam glass composite thermal insulation material.

Example 4

This embodiment discloses a method for preparing a hybrid thermal insulation material, comprising the following steps:

R1: 2 g titanium aluminum carbon powder and 3.01 g lithium fluoride were added to 43 mL 9 mol/L hydrochloric acid solution, heated and stirred at 40 ° C for 48 h, centrifuged, washed three times with 1 mol/L hydrochloric acid solution and 1 mol/L lithium chloride solution, respectively, and then washed with deionized water until pH = 6. The centrifugal precipitate was uniformly dispersed in deionized water to obtain a suspension, which was added to a container and freeze-dried (-80 ° C, 1 Pa) for 72 h to obtain an aerogel;

R2: Under nitrogen atmosphere, 1 g of n-dodecanol and 1.732 g of phosphorus oxychloride were dissolved in toluene, and the mixture was heated at 70°C for 10 h and continued to react after the reaction. After the reaction was completed, the reaction solution was quickly poured into cold acetonitrile, filtered, washed 3 times, and dried under vacuum at 25°C for 24 h to obtain phosphorus-modified alkanol;

R3: Add 16g of phosphorus-modified alkanol and 1g of aerogel into a container, place it in a vacuum drying oven (0.09MPa, 110℃) for melt adsorption for 12h to obtain a composite aerogel; add 32g of thermoplastic polyurethane elastomer into 280mL of N,N-dimethylformamide, stir at high temperature for 4h, and add 21g of composite aerogel after complete dissolution. Continue stirring under a nitrogen atmosphere. After stirring, pour it into deionized water and stir until flocs are precipitated. Wash the flocs with ethanol 3 times and dry them at 70℃ for 24h to obtain a hybrid insulation material.

This embodiment discloses a method for preparing a modified toughening agent, comprising the following steps:

Q1: 1.54 mL of 6 mol/L acetaldehyde aqueous solution was placed in a container equipped with a thermometer, a spherical condenser and a stirrer, and the pH of the acetaldehyde aqueous solution was adjusted to 11 with a 1 mol/L sodium hydroxide aqueous solution. 1.17 g of aniline was dissolved in 4.78 mL of toluene, and then added dropwise to the acetaldehyde aqueous solution. After the addition was completed, the mixture was heated and stirred at 40°C for 45 min, and then 2.00 mL of 4-hydroxyphenylacetaldehyde was slowly added dropwise. The container was then heated to 85°C, refluxed for 6 h, washed, rotary evaporated, recrystallized, and vacuum dried at 50°C for 12 h to obtain intermediate 1;

Q2: 4.89 g of intermediate product 1 was added to a container, and 35 mL of ethanol was added at the same time. The mixture was heated and stirred at 95°C for 1 h, cooled, and 2.09 g of 5-aminoindole was added. The mixture was heated and reacted at 75°C for 3 h. The mixture was washed and vacuum dried at 85°C for 10 h to obtain intermediate product 2.

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, dry at 110°C for 2 h, and cure. The curing process is: cure at 120°C for 2 h, then heat to 140°C for 2 h, then heat to 160°C 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.

This embodiment discloses a method for preparing a polycondensate foam glass composite thermal insulation material, comprising the following steps:

Step (1): grinding 44 kg of broken glass, 3 kg of borax and 2.5 kg of limestone by ball milling to obtain a mixed material, wherein the particle size of the ground mixed material is controlled to be more than 95% under a 200-mesh sieve;

Step (2): melting and foaming the mixed material, 1.2 kg of sodium carbonate and 1.5 kg of lithium carbonate at 900° C. to obtain a foam melt, and mixing and stirring the foam melt, 4 kg of a hybrid thermal insulation material and 2.5 kg of a modified toughening agent to obtain a composite foam melt;

Step (3): cooling the composite foam melt to 500° C. within 5 minutes, annealing, and cooling to obtain a polycondensate foam glass composite thermal insulation material.

Example 5

This embodiment discloses a method for preparing a hybrid thermal insulation material, comprising the following steps:

R1: 2 g titanium aluminum carbon powder and 3.05 g lithium fluoride were added to 44 mL 9 mol/L hydrochloric acid solution, heated and stirred at 40 ° C for 48 h, centrifuged, washed with 1 mol/L hydrochloric acid solution and 1 mol/L lithium chloride solution for 3 times, washed with deionized water until pH = 6, and then the centrifugal precipitate was evenly dispersed in deionized water to obtain a suspension, which was added to a container and freeze-dried (-80 ° C, 1 Pa) for 72 h to obtain an aerogel;

R2: Under nitrogen atmosphere, 1 g of n-dodecanol and 1.794 g of phosphorus oxychloride were dissolved in toluene, and the mixture was heated at 70°C for 10 h and continued to react after magnetic stirring for 2 h. After the reaction was completed, the reaction solution was quickly poured into cold acetonitrile, filtered, washed 3 times, and dried under vacuum at 25°C for 24 h to obtain phosphorus-modified alkanol;

R3: Add 18g of phosphorus-modified alkanol and 1g of aerogel into a container, place it in a vacuum drying oven (0.09MPa, 110℃) for melt adsorption for 12h to obtain a composite aerogel; add 38g of thermoplastic polyurethane elastomer into 290mL of N,N-dimethylformamide, stir at high temperature for 4h, and add 23g of composite aerogel after complete dissolution. Continue stirring under a nitrogen atmosphere. After stirring, pour it into deionized water and stir until flocs are precipitated. Wash the flocs with ethanol 3 times and dry them at 70℃ for 24h to obtain a hybrid insulation material.

This embodiment discloses a method for preparing a modified toughening agent, comprising the following steps:

Q1: 1.79 mL of 6 mol/L acetaldehyde aqueous solution was placed in a container equipped with a thermometer, a spherical condenser and a stirrer, and the pH of the acetaldehyde aqueous solution was adjusted to 11 with a 1 mol/L sodium hydroxide aqueous solution. 1.48 g of aniline was dissolved in 6.25 mL of toluene, and then added dropwise to the acetaldehyde aqueous solution. After the addition was completed, the mixture was heated and stirred at 40°C for 45 min, and then 1.64 mL of 4-hydroxyphenylacetaldehyde was slowly added dropwise. The container was then heated to 85°C, refluxed for 6 h, washed, rotary evaporated, recrystallized, and vacuum dried at 50°C for 12 h to obtain intermediate 1;

Q2: 4.73 g of intermediate product 1 was added to a container, and 42 mL of ethanol was added at the same time. The mixture was heated and stirred at 95°C for 1 h, cooled, and 1.98 g of 5-aminoindole was added. The mixture was heated and reacted at 75°C for 3 h. The mixture was washed and vacuum dried at 85°C for 10 h to obtain intermediate product 2.

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, dry at 110°C for 2 h, and cure. The curing process is: cure at 120°C for 2 h, then heat to 140°C for 2 h, then heat to 160°C 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.

This embodiment discloses a method for preparing a polycondensate foam glass composite thermal insulation material, comprising the following steps:

Step (1): grinding 38 kg of broken glass, 5 kg of borax and 1.5 kg of limestone by ball milling to obtain a mixed material, wherein the particle size of the ground mixed material is controlled to be more than 95% under a 200-mesh sieve;

Step (2): melting and foaming the mixed material, 1 kg of sodium carbonate and 2.5 kg of lithium carbonate at 900° C. to obtain a foam melt, and mixing and stirring the foam melt, 5 kg of hybrid thermal insulation material and 3.1 kg of modified toughening agent to obtain a composite foam melt;

Step (3): cooling the composite foam melt to 500° C. within 5 minutes, annealing, and cooling to obtain a polycondensate foam glass composite thermal insulation material.

Example 6

This embodiment discloses a method for preparing a hybrid thermal insulation material, comprising the following steps:

R1: 2 g titanium aluminum carbon powder and 3.20 g lithium fluoride were added to 41 mL 9 mol/L hydrochloric acid solution, heated and stirred at 40 ° C for 48 h, centrifuged, washed three times with 1 mol/L hydrochloric acid solution and 1 mol/L lithium chloride solution, respectively, and then washed with deionized water until pH = 6. The centrifugal precipitate was uniformly dispersed in deionized water to obtain a suspension, which was added to a container and freeze-dried (-80 ° C, 1 Pa) for 72 h to obtain an aerogel;

R2: Under nitrogen atmosphere, 1 g of n-dodecanol and 1.903 g of phosphorus oxychloride were dissolved in toluene, and the mixture was heated at 70°C for 10 h and continued to react after the reaction. After the reaction was completed, the reaction solution was quickly poured into cold acetonitrile, filtered, washed 3 times, and dried under vacuum at 25°C for 24 h to obtain phosphorus-modified alkanol;

R3: Add 17g of phosphorus-modified alkanol and 1g of aerogel into a container, place it in a vacuum drying oven (0.09MPa, 110℃) for melt adsorption for 12h to obtain a composite aerogel; add 36g of thermoplastic polyurethane elastomer into 260mL of N,N-dimethylformamide, stir at high temperature for 4h, and add 24g of composite aerogel after complete dissolution. Continue stirring under a nitrogen atmosphere. After stirring, pour it into deionized water and stir until flocs are precipitated. Wash the flocs with ethanol 3 times and dry them at 70℃ for 24h to obtain a hybrid insulation material.

This embodiment discloses a method for preparing a modified toughening agent, comprising the following steps:

Q1: 1.67 mL of 6 mol/L acetaldehyde aqueous solution was placed in a container equipped with a thermometer, a spherical condenser and a stirrer, and the pH of the acetaldehyde aqueous solution was adjusted to 11 with a 1 mol/L sodium hydroxide aqueous solution. 1.22 g of aniline was dissolved in 5.24 mL of toluene, and then added dropwise to the acetaldehyde aqueous solution. After the addition was completed, the mixture was heated and stirred at 40°C for 45 min, and then 1.97 mL of 4-hydroxyphenylacetaldehyde was slowly added dropwise. The container was then heated to 85°C, refluxed for 6 h, washed, rotary evaporated, recrystallized, and vacuum dried at 50°C for 12 h to obtain intermediate 1;

Q2: 4.75 g of intermediate product 1 was added to a container, and 48 mL of ethanol was added at the same time. The mixture was heated and stirred at 95°C for 1 h, cooled, and 1.79 g of 5-aminoindole was added. The mixture was heated and reacted at 75°C for 3 h. The mixture was washed and vacuum dried at 85°C for 10 h to obtain intermediate product 2.

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, dry at 110°C for 2 h, and cure. The curing process is: cure at 120°C for 2 h, then heat to 140°C for 2 h, then heat to 160°C 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.

This embodiment discloses a method for preparing a polycondensate foam glass composite thermal insulation material, comprising the following steps:

Step (1): grinding 40 kg of broken glass, 4.5 kg of borax and 2.75 kg of limestone by ball milling to obtain a mixed material, wherein the particle size of the ground mixed material is controlled to be more than 95% under a 200-mesh sieve;

Step (2): melting and foaming the mixed material, 0.9 kg of sodium carbonate and 2.9 kg of lithium carbonate at 900° C. to obtain a foam melt, and mixing and stirring the foam melt, 3.5 kg of a hybrid thermal insulation material and 3.7 kg of a modified toughening agent to obtain a composite foam melt;

Step (3): cooling the composite foam melt to 500° C. within 5 minutes, annealing, and cooling to obtain a polycondensate foam glass composite thermal insulation material.

Comparative Example 1

Comparative Example 1 Compared with Example 1, in the process of preparing the hybrid thermal insulation material in Comparative Example 1, no titanium aluminum carbon powder is added, and other conditions remain unchanged.

Comparative Example 2

Comparative Example 2 Compared with Example 1, in the process of preparing the hybrid thermal insulation material in Comparative Example 2, no n-dodecanol was added, and other conditions remained unchanged.

Comparative Example 3

Comparative Example 3 Compared with Example 1, in the process of preparing the hybrid thermal insulation material in Comparative Example 3, no thermoplastic polyurethane elastomer is added, and other conditions remain unchanged.

Comparative Example 4

Comparative Example 4 Compared with Example 1, in the process of preparing the modified toughening agent in Comparative Example 4, 4-hydroxyphenylacetaldehyde was not added, and other conditions remained unchanged.

Comparative Example 5

Comparative Example 5 Compared with Example 1, in the process of preparing the modified toughening agent in Comparative Example 5, 5-aminoindole was not added, and other conditions remained unchanged.

Comparative Example 6

Compared with Example 1, in Comparative Example 6, during the preparation of the polycondensate foam glass composite thermal insulation material, no hybrid thermal insulation material is added, and other conditions remain unchanged.

Comparative Example 7

Compared with Example 1, in Comparative Example 7, during the preparation of the polycondensate foam glass composite insulation material, no modified toughening agent was added, and other conditions remained unchanged.

Thermal insulation, toughness and corrosion resistance tests

The performance of the polycondensate foam glass composite insulation materials prepared in Examples 1-6 and Comparative Examples 1-7 was tested. The 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:

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

project Thermal conductivity/W/(m·K) Compressive strength/MPa Sample weight loss/g/ ^m2 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

It can be seen from the test results in Table 1 that the preparation methods adopted in Examples 1-6 of the present invention enable the polycondensate foam glass composite insulation material to have excellent insulation performance, toughness and corrosion resistance. From the comparison between comparative example 1 and examples 1-6, it can be seen that the addition of titanium aluminum carbon powder can improve the thermal insulation performance and corrosion resistance of the polycondensate foam glass composite insulation material; from the comparison between comparative example 2 and examples 1-6, it can be seen that the addition of n-dodecanol can improve the thermal insulation performance and corrosion resistance of the polycondensate foam glass composite insulation material; from the comparison between comparative example 3 and examples 1-6, it can be seen that the addition of thermoplastic polyurethane elastomer can improve the thermal insulation performance and corrosion resistance of the polycondensate foam glass composite insulation material; from the comparison between comparative example 4 and examples 1-6, it can be seen that the addition of hydroxyphenylacetaldehyde can improve the toughness of the polycondensate foam glass composite insulation material; from the comparison between comparative example 5 and examples 1-6, it can be seen that the addition of 5-aminoindole can improve the toughness of the polycondensate foam glass composite insulation material; from the comparison between comparative example 6 and examples 1-6, it can be seen that the addition of hybrid insulation material can improve the thermal insulation performance and corrosion resistance of the polycondensate foam glass composite insulation material; from the comparison between comparative example 7 and examples 1-6, it can be seen that the addition of modified toughening agent can improve the toughness of the polycondensate foam glass composite insulation material.

The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. The multi-coagulation foam glass composite heat insulation material is characterized by comprising 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 heat insulation material, 2-4 parts of modified toughening agent, 0.8-1.3 parts of foaming agent and 1-3 parts of fluxing agent; the hybrid heat 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 solution of acetaldehyde, aniline, 4-hydroxyphenylacetaldehyde, 5-aminoindole and glass fiber.

2. The multiple-gel foam glass composite heat insulating material according to claim 1, wherein the preparation method of the hybrid heat insulating material comprises the following steps:

R1: adding titanium aluminum carbon powder and lithium fluoride into hydrochloric acid solution, heating, stirring, centrifuging, respectively centrifugally washing with the hydrochloric acid solution and the lithium chloride solution, washing with deionized water, uniformly dispersing centrifugal precipitate into deionized water to obtain suspension, adding the suspension into a container, and freeze-drying to obtain aerogel;

R2: under the protection of nitrogen atmosphere, n-dodecanol and phosphorus oxychloride are dissolved in toluene, the mixture is heated after being magnetically stirred and mixed, continuous reaction is carried out, after the continuous reaction is finished, reaction liquid is rapidly poured into cold acetonitrile, and phosphorus modified alkanol is obtained after filtration, washing and vacuum drying;

R3: adding phosphorus modified alkanol and aerogel into a container, and placing the container in a vacuum drying oven for melt adsorption to obtain composite aerogel; adding the thermoplastic polyurethane elastomer into N, N-dimethylformamide, stirring at high temperature, adding the composite aerogel after complete dissolution, continuously stirring under nitrogen atmosphere, pouring the mixture into deionized water after stirring, stirring until flocculate is separated out, washing the flocculate, and drying to obtain the hybrid heat insulation material.

3. The multi-coagulation foam glass composite heat-insulating material according to claim 2, wherein the ratio of the amounts of titanium aluminum carbon powder, lithium fluoride and hydrochloric acid solution in R1 is 2g: (3-3.22) g: (40-45) mL, wherein the concentration of the hydrochloric acid solution is 9mol/L, the temperature of heating and stirring is 35-40 ℃, the time of heating and stirring is 48-54h, the concentration of the hydrochloric acid solution is 1mol/L, the concentration of the lithium chloride solution is 1mol/L in the washing process, the times of centrifugal washing are 3-5 times respectively, the pH value after washing with deionized water is=6, the temperature of freeze drying is-70 to-80 ℃, the pressure is 0-1Pa, and the time is 72-84h.

4. The multiple-gel foam glass composite heat insulating material according to claim 2, wherein the molar ratio of n-dodecanol to phosphorus oxychloride in R2 is 1: (2-2.4), the magnetic stirring time is 2-3h, the heating temperature is 60-70 ℃, the heating time is 8-10h, the washing times are 3-5 times, the vacuum drying temperature is 25 ℃, and the vacuum drying time is 20-24h.

5. The multiple-gel foam glass composite heat insulating material according to claim 2, wherein the mass ratio of phosphorus-modified alkanol to aerogel in R3 is (15-19) g:1g, the pressure of a vacuum drying oven is 0.06-0.09MPa, the temperature is 100-110 ℃, the melt adsorption time is 10-12h, and the dosage ratio of the thermoplastic polyurethane elastomer, the N, N-dimethylformamide and the composite aerogel is (30-40) g: (250-300) mL: (20-25) g, continuing stirring for 2-4h, washing the flocculate with ethanol for 3-5 times, and drying at 60-70deg.C for 20-30h.

6. The multiple-gel foam glass composite heat insulating material according to claim 1, wherein the preparation method of the modified toughening agent comprises the following steps:

q1: placing an aqueous solution of acetaldehyde in a container provided with a thermometer, a spherical condenser and a stirrer, regulating the pH of the aqueous solution of acetaldehyde by using an aqueous solution of sodium hydroxide, dissolving aniline in toluene, then dropwise adding the aqueous solution of acetaldehyde, heating and stirring after the dropwise adding is finished, then slowly dropwise adding 4-hydroxyphenylacetaldehyde, heating the container, refluxing, washing, steaming, recrystallizing, and drying in vacuum to obtain an intermediate product 1;

Q2: adding the intermediate product 1 into a container, adding ethanol, heating, stirring, cooling, adding 5-aminoindole, continuously performing heating reaction, washing, and vacuum drying to obtain an intermediate product 2;

Q3: dissolving the intermediate product 2 in a container filled with N, N-dimethylformamide solution, filtering, adding glass fibers, uniformly stirring to obtain a mixed solution, placing the mixed solution in a mold, drying, and solidifying to obtain the modified toughening agent.

7. The multiple-gel foam glass composite heat insulating material according to claim 6, wherein the molar ratio of acetaldehyde, aniline, toluene, and 4-hydroxyphenylacetaldehyde in Q1 is (0.8 to 1.2): (0.4-0.6): (1.51-2.27): (0.4-0.6), the concentration of the aqueous solution of acetaldehyde is 6mol/L, the concentration of the aqueous solution of sodium hydroxide is 1mol/L, the pH=11 is regulated, the heating and stirring temperature is 30-40 ℃, the heating time is 30-45min, the heating temperature is 80-85 ℃, the reflux time is 5-6h, the vacuum drying temperature is 40-50 ℃, and the vacuum drying time is 12-15h.

8. The multiple-gel foam glass composite heat insulating material according to claim 6, wherein in Q2, the molar ratio of intermediate 1, ethanol and 5-aminoindole is (1-2): (0.43-0.87): (1-2) heating and stirring at 90-95 ℃ for 1-2h, heating and reacting at 70-75 ℃ for 2-3h, and vacuum drying at 80-90 ℃ for 10-12h; in the Q3, the dosage ratio of the intermediate product 2, N-dimethylformamide to the glass fiber is (4.6-4.9) g:2mL: (2-5) g, wherein the drying temperature is 100-110 ℃, the drying time is 1-2h, and the curing process is as follows: after curing at 120 ℃ for 2 hours, the temperature is raised to 140 ℃ for 2 hours, then to 160 ℃ for 2 hours, then to 180 ℃ for 2 hours, and finally to 200 ℃ for 2 hours.

9. The method for producing a multi-gel foam glass composite heat insulating material according to any one of claims 1 to 8, comprising the steps of:

step (1): grinding the broken glass, borax and limestone to obtain a mixed material;

step (2): melting and foaming the mixed material, the foaming agent and the fluxing agent to obtain a foam melt, and mixing and stirring the foam melt, the hybrid heat insulation material and the modified toughening agent to obtain a composite foam melt;

Step (3): and cooling, annealing and cooling the composite foam melt to obtain the multi-coagulation foam glass composite heat insulation material.

10. The method for producing a multi-gel foam glass composite heat insulating material according to claim 9, wherein in the step (1), the grinding is performed by a ball milling method, and the particle size of the ground mixture is controlled to be 200 mesh with a undersize ratio of 95% or more; in the step (2), the temperature of melting foaming is 900-1000 ℃; in the step (3), the cooling time is 3-5min, and the temperature after cooling is 500-600 ℃.