A new composite wall material containing resin-based microcapsules and a preparation method thereof

Abstract

This invention discloses a novel composite wall material containing resin-based microcapsules and its preparation method, belonging to the field of novel wall material technology. The wall material includes a composite substrate, resin-based microcapsules, thermal insulation filler, sound-absorbing filler, binder, modifier, and purified water. The preparation method includes: S1, resin-based microcapsule preparation; S2, raw material pretreatment; S3, mixing and stirring; S4, molding and curing. This invention achieves integrated improvement of the sound absorption and heat insulation functions of the wall material by targeted modification of raw materials, selecting resin-based microcapsules with specific structures, and synergistically modifying the thermal insulation filler, sound-absorbing filler, and other raw materials, and optimizing the preparation process parameters. At the same time, it significantly enhances the mechanical properties, moisture resistance, and durability of the wall material, simplifies the preparation process, reduces production costs, and is suitable for widespread use.

Description

Technical Field

[0001] This invention relates to the field of novel wall material technology, specifically to a novel composite wall material containing resin-based microcapsules and its preparation method. Background Technology

[0002] With the rapid development of the construction industry and the advancement of the "dual-carbon" policy, building energy conservation and environmental comfort have become one of the core directions of building material research and development. As a core component of the building envelope, wall materials directly affect building energy consumption due to their thermal insulation performance, while their sound absorption performance relates to the quality of the indoor acoustic environment. Therefore, the development of novel composite wall materials with both sound absorption and thermal insulation functions, and their preparation methods, has significant practical implications and application value. However, existing composite wall materials mostly adopt a single-function design, either focusing on thermal insulation or sound absorption and noise reduction, making it difficult to simultaneously meet the needs of both.

[0003] Resin-based microcapsules, as a novel functional material, possess a core-shell structure that encapsulates functional substances such as phase change energy storage, thermal insulation, and sound absorption within a shell. This not only protects the performance of the core material but also enables the sustained release and synergistic effect of its functions. Applying resin-based microcapsules to composite wall materials allows for the integration of sound absorption and thermal insulation functions through the core-shell structure of the microcapsules in conjunction with thermal insulation and sound-absorbing fillers, while simultaneously improving the mechanical properties and durability of the wall material. However, current research on the application of resin-based microcapsules in composite wall materials still faces technical challenges, including uneven microcapsule dispersion, insufficient functional utilization, complex preparation processes, and high costs, which limit their large-scale application. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a novel composite wall material containing resin-based microcapsules and its preparation method.

[0005] The technical solution of the present invention is as follows: a novel composite wall material containing resin-based microcapsules, comprising the following raw materials in parts by weight: 30-60 parts of composite substrate, 10-25 parts of resin-based microcapsules, 15-30 parts of thermal insulation filler, 8-20 parts of sound-absorbing filler, 5-12 parts of binder, 2-6 parts of modifier, and 10-20 parts of purified water. The composite substrate includes: 30-60 parts fly ash, 2-6 parts defoamer, and 10-20 parts water; The resin-based microcapsules have a core-shell structure, with the core being a phase change energy storage material and the shell being a copolymer of epoxy resin and polyurethane. The particle size of the resin-based microcapsules is 70~120μm, and the shell thickness is 5~15μm.

[0006] Furthermore, the thermal insulation filler is one of expanded perlite, aerogel, and glass wool, and the particle size of the thermal insulation filler is 100~300μm; The sound-absorbing filler is one of wood fiber or basalt fiber, and the fiber length of the sound-absorbing filler is 0.5~2.3mm; The adhesive is one of polyvinyl alcohol, sodium carboxymethyl cellulose, or acrylic emulsion; The modifier is one of the following: silane coupling agent and water-reducing agent.

[0007] Furthermore, the method for preparing the composite substrate is as follows: 1) Modification and activation; Fly ash is placed in a ball mill, and the milling speed is controlled at 300-400 r / min for 20-30 min to obtain activated fly ash. Then, sodium hydroxide solution is added to the activated fly ash, stirred evenly, and placed in a constant temperature curing chamber at 80-100℃ for 2-3 h to obtain alkali-activated fly ash. Finally, the alkali-activated fly ash is placed in an oven and dried at 105-110℃ for 2-3 h, then pulverized and passed through an 80-100 mesh sieve to obtain modified fly ash. The volume concentration of the sodium hydroxide solution is 10-15%, and the amount of sodium hydroxide solution added is 5-8% of the total mass of the activated fly ash. 2) Mixing raw materials; The modified fly ash obtained in step 1) is put into a mixing device, the mixing temperature is controlled at 25~30℃, and the mixture is stirred at a low speed of 300~500r / min for 5~10min until it is uniform; then the defoamer is added and the mixing continues for 5~8min to obtain the mixture; wherein, the defoamer is a silicone defoamer; 3) Mixing the paste; Add water to the mixture obtained in step 2), adjust the stirring speed to 800~1200 r / min, stir at high speed for 15~20 min to obtain the substrate slurry, control the consistency of the slurry to 150~180 mm, and the composite substrate can be obtained; Explanation: By mechanically activating and alkali-activating fly ash, the active components of fly ash are fully activated, significantly improving the compressive strength and durability of the substrate. By adding silane coupling agents and combining them with fly ash modification treatment, the interfacial bonding force between the substrate and resin-based microcapsules and sound-absorbing fillers is improved, avoiding delamination, hollowing, and cracking of the composite wall.

[0008] Furthermore, the phase change energy storage material is one of paraffin, polyethylene glycol, or fatty acid, and the phase change temperature is 20~35℃; Note: This phase change temperature range matches the indoor temperature of the building, and can absorb or release heat through phase change when the room temperature changes, effectively regulating the indoor temperature and improving the thermal insulation and energy-saving effect of composite wall materials.

[0009] Furthermore, it also includes 2 to 5 parts of crack-resistant fiber, which is either polypropylene fiber or glass fiber, and the fiber length is 6 to 12 mm; Note: The addition of crack-resistant fibers helps to improve the interfacial bonding between the composite substrate, adhesive and resin-based microcapsules, thus preventing cracking of the composite wall material and extending its service life.

[0010] This invention also provides a method for preparing a novel composite wall material containing resin-based microcapsules, comprising the following steps: S1, Preparation of resin-based microcapsules; S1-1. Mix epoxy resin and polyurethane at a mass ratio of 3~5:1, then dilute with acetone solution to obtain shell solution; heat and melt phase change energy storage material, then add emulsifier, and stir and emulsify at 1500~2000r / min for 30~60min to obtain core emulsion. S1-2. Slowly drop the core emulsion from step S1-1 into the shell solution and adjust the pH of the mixed solution to 7.5-8.5. Use a gradient heating process to gradually heat the mixed solution from 50℃ to 65℃, controlling the heating rate at 3-5℃ / h, and react within this temperature range for 2-4h. After the reaction is complete, cool, centrifuge, and dry the reactants to obtain resin-based microcapsules. S2, Raw material pretreatment; The thermal insulation filler and sound-absorbing filler are placed in an oven and dried at 95~110℃ for 2~4 hours. Then, the dried thermal insulation filler and sound-absorbing filler are crushed and passed through an 80~100 mesh sieve. The sieved thermal insulation filler and sound-absorbing filler are mixed with composite substrate, binder and modifier to obtain pretreated material. S3. Mix and stir; Add the pretreated material obtained in step S2 into a mixing device, control the mixing temperature at 25~35℃, and mix at a speed of 300~500r / min for 5~10min; then add the resin-based microcapsules obtained in step S1-2 into the mixing device and continue mixing for 10~15min; finally add purified water into the mixing device and continue mixing at a speed of 800~1200r / min for 15~20min, and control the consistency of the mixed material to be 180~220mm to obtain a mixed slurry; S4. Molding and curing; Pour the mixed slurry obtained in step S3 into a mold, pre-press it at a frequency of 15-20 Hz for 3-5 minutes, and then compact it at a frequency of 25-30 Hz for 2-5 minutes to obtain a compacted blank. Then, let the compacted blank stand at room temperature for 24-48 hours before demolding. Place the demolded compacted blank in a curing chamber and cure it at a temperature of 20-25℃ and a relative humidity of 60-80% for 7-14 days, spraying water every 18-24 hours, controlling the spraying amount to 200-500 ml / m³ each time. 2 Composite wall materials can then be obtained.

[0011] Further, in step S1-1, the volume concentration of the acetone solution is 2-5%, and the amount added is 0.5-1.3% of the total mass of the shell solution; the emulsifier is sodium dodecylbenzenesulfonate, and the amount added is 1-3% of the total mass of the core emulsion. Furthermore, step S2 also includes modifying the dried thermal insulation filler and sound-absorbing filler, respectively. The modification method is as follows: The dried thermal insulation filler is added to a high-speed mixer, followed by the addition of silane coupling agent and anhydrous ethanol. The mixture is stirred at 80-90℃ and 300-500 r / min for 30-60 min. After cooling, the reaction mixture is dried to constant weight to obtain the modified thermal insulation filler. The mass ratio of silane coupling agent, anhydrous ethanol, and thermal insulation filler is 0.01-0.03:0.02-0.04:1. The dried sound-absorbing filler is added to a reactor, and then 2-4% of the total mass of the sound-absorbing filler is added to the reactor. The mixture is stirred for 20-40 minutes at 60-70℃ and 200-300 r / min. After filtration and drying, the modified sound-absorbing filler is obtained. The hydrophobic modifier is stearic acid. Explanation: By modifying the thermal insulation filler, active groups can be introduced onto its surface, significantly improving its compatibility and interfacial bonding with other raw materials, while also enhancing its moisture resistance and preventing a decrease in thermal insulation performance after moisture absorption. By modifying the sound-absorbing filler, a hydrophobic layer can be formed on its surface, reducing its hydrophilicity and preventing moisture absorption and clumping. At the same time, it will not block its internal pores, ensuring stable sound absorption performance and improving its compatibility with other raw materials.

[0012] Furthermore, in steps S1-2, the centrifugation speed is 2800~3200 r / min, the centrifugation time is 8~12 min; the drying temperature is 100~110℃, and the drying time is 1.5~2.5 h; Note: The above operations can significantly reduce the water content of resin-based microcapsules, preventing the performance of core phase change energy storage materials from deteriorating due to residual moisture.

[0013] Furthermore, in step S4, after the compacted billet has been cured for 3-5 days, the relative humidity inside the curing chamber is reduced to 50-60%. Note: Gradual dehumidification curing through compacted billets helps reduce the risk of shrinkage and cracking in the compacted billets and improves the dimensional stability of composite wall materials.

[0014] Compared with the prior art, the beneficial effects of the present invention are reflected in the following aspects: First, the process design of this invention is reasonable. By controlling the particle size and shell thickness of the resin-based microcapsules, combined with gradient heating reaction and gradient stirring processes, and by modifying the raw materials, the uniformity of microcapsule dispersion in wall materials is improved. The epoxy resin and polyurethane copolymer in the shell layer can effectively protect the core phase change energy storage material and prevent its leakage. Combined with the control of centrifugal drying parameters, the stability of the resin-based microcapsules is further improved, ensuring the long-term performance of heat insulation and energy storage functions. At the same time, the modified raw materials will not block the phase change heat conduction channels of the resin-based microcapsules, further improving the functional effect of the resin-based microcapsules. Secondly, this invention, through targeted modification of thermal insulation fillers and sound-absorbing fillers, and in conjunction with customized core-shell structured resin-based microcapsules, forms a synergistic system of "modified thermal insulation filler basic thermal insulation + resin-based microcapsule dynamic energy storage thermal insulation + modified sound-absorbing filler three-dimensional porous sound absorption," which solves the problems of mutual restriction between thermal insulation and sound absorption functions and limited performance of raw materials in the prior art. Third, this invention selects fly ash as the main raw material for the composite substrate, and combines it with a reasonable amount of resin-based microcapsules. The modifier dosage is small and the cost is low, which reduces the overall production cost. At the same time, the modified utilization of fly ash realizes the resource utilization of industrial waste, the phase change energy storage function of resin-based microcapsules can help reduce building energy consumption, and the moisture resistance of the modified material is further improved, reducing the later maintenance cost of building walls. Fourth, the composite wall material prepared by this invention has the characteristics of sound absorption, heat insulation, excellent mechanical properties, moisture resistance, and good durability. It can be widely used in the thermal insulation and sound absorption projects of interior walls, exterior walls, and roofs of various buildings, and has good market application prospects. Detailed Implementation

[0015] Example 1: A novel composite wall material containing resin-based microcapsules, comprising the following raw materials in parts by weight: 30 parts composite substrate, 10 parts resin-based microcapsules, 15 parts thermal insulation filler, 8 parts sound-absorbing filler, 5 parts adhesive, 2 parts modifier, 2 parts crack-resistant fiber, and 10 parts purified water. The composite substrate includes: 30 parts fly ash, 2 parts defoamer, and 10 parts water; The preparation method of the composite substrate is as follows: 1) Modification and activation; Fly ash was placed in a ball mill, and the milling speed was controlled at 300 r / min for 20 min to obtain activated fly ash. Then, sodium hydroxide solution was added to the activated fly ash, stirred evenly, and placed in a constant temperature curing chamber at 80℃ for 2 h to obtain alkali-activated fly ash. Finally, the alkali-activated fly ash was placed in an oven and dried at 105℃ for 2 h, then pulverized and passed through an 80-mesh sieve to obtain modified fly ash. The volume concentration of the sodium hydroxide solution was 10%, and the amount of sodium hydroxide solution added was 5% of the total mass of the activated fly ash. 2) Mixing raw materials; The modified fly ash obtained in step 1) is put into a mixing device, the mixing temperature is controlled at 25℃, and the mixture is stirred at a low speed of 300r / min for 5 minutes to mix evenly; then the defoamer is added and the mixing continues for 5 minutes to obtain a mixture; wherein, the defoamer is a silicone defoamer; 3) Mixing the paste; Add water to the mixture obtained in step 2), adjust the stirring speed to 800 r / min, stir at high speed for 15 min to obtain the substrate slurry, control the slurry consistency to 150 mm, and the composite substrate can be obtained. The resin-based microcapsules have a core-shell structure, with the core being a phase change energy storage material and the shell being a copolymer of epoxy resin and polyurethane. The resin-based microcapsules have a particle size of 70 μm and a shell thickness of 5 μm. The phase change energy storage material is paraffin wax, and the phase change temperature is 20℃. The thermal insulation filler is expanded perlite with a particle size of 100μm; The sound-absorbing filler is made of wood fiber with a fiber length of 0.5 mm; The adhesive is polyvinyl alcohol; The modifier is a silane coupling agent; The crack-resistant fiber is made of polypropylene and has a fiber length of 6mm.

[0016] Example 2: This example describes the preparation method of the novel composite wall material containing resin-based microcapsules as described in Example 1, including the following steps: S1, Preparation of resin-based microcapsules; S1-1. Epoxy resin and polyurethane are mixed at a mass ratio of 3:1, and then diluted with acetone solution to obtain a shell solution. The phase change energy storage material is heated and melted, and then an emulsifier is added. The mixture is stirred and emulsified at 1500 r / min for 30 min to obtain a core emulsion. The volume concentration of the acetone solution is 2%, and the amount added is 0.5% of the total mass of the shell solution. The emulsifier is sodium dodecylbenzenesulfonate, and the amount added is 1% of the total mass of the core emulsion. S1-2. Slowly drop the core emulsion from step S1-1 into the shell solution, and adjust the pH of the mixed solution to 7.5. Use a gradient heating process to gradually increase the temperature of the mixed solution from 50℃ to 65℃, controlling the heating rate at 3℃ / h, and react within this temperature range for 2h. After the reaction is complete, cool, centrifuge, and dry the reactants to obtain resin-based microcapsules. The centrifugation speed is 2800 r / min, the centrifugation time is 8 min, the drying temperature is 100℃, and the drying time is 1.5h. S2, Raw material pretreatment; The thermal insulation filler and sound-absorbing filler were placed in an oven and dried at 95℃ for 2 hours. The dried thermal insulation filler and sound-absorbing filler were then modified. The modification method was as follows: the dried thermal insulation filler was added to a high-speed mixer, followed by the sequential addition of a silane coupling agent and anhydrous ethanol. The mixture was stirred at 80℃ and 300 r / min for 30 minutes. After cooling, the reactants were dried to constant weight to obtain the modified thermal insulation filler. The mass ratio of the silane coupling agent, anhydrous ethanol, and thermal insulation filler was 0.0. The ratio of the dried sound-absorbing filler to the total mass of the filler is 1:0.02:1. The dried sound-absorbing filler is added to a reactor, followed by the addition of a hydrophobic modifier at 2% of the total mass of the filler. The mixture is stirred for 20 minutes at 60℃ and 200 r / min, then filtered and dried to obtain the modified sound-absorbing filler. The hydrophobic modifier is stearic acid. The modified thermal insulation filler and the modified sound-absorbing filler are then pulverized and passed through an 80-mesh sieve. The sieved thermal insulation filler and sound-absorbing filler are mixed with the composite substrate, binder, and modifier to obtain the pretreated material. S3. Mix and stir; Add the pretreated material obtained in step S2 into the mixing equipment, control the mixing temperature at 25°C, and mix at a speed of 300 r / min for 5 min; then add the resin-based microcapsules obtained in steps S1-2 into the mixing equipment and continue mixing for 10 min; finally add pure water into the mixing equipment and continue mixing at a speed of 800 r / min for 15 min, and control the consistency of the mixed material to 180 mm to obtain a mixed slurry; S4. Molding and curing; The mixed slurry obtained in step S3 is poured into a mold, pre-pressed at a frequency of 15Hz for 3 minutes, and then compacted at a frequency of 25Hz for 2 minutes to obtain a compacted blank. The compacted blank is then allowed to stand at room temperature for 24 hours before demolding. The demolded compacted blank is placed in a curing chamber and cured for 7 days at a temperature of 20℃ and a relative humidity of 60%, with water sprayed every 18 hours, controlling the spray volume to be 200 ml / m³ each time. 2 After the compacted blank is cured for 3 days, the relative humidity inside the curing box is reduced to 50%; then the composite wall material can be obtained.

[0017] Example 3: A novel composite wall material containing resin-based microcapsules, comprising the following raw materials in parts by weight: 45 parts composite substrate, 20 parts resin-based microcapsules, 22 parts thermal insulation filler, 15 parts sound-absorbing filler, 8 parts adhesive, 4 parts modifier, 4 parts crack-resistant fiber, and 15 parts purified water. The composite substrate includes: 40 parts fly ash, 4 parts defoamer, and 16 parts water; The preparation method of the composite substrate is as follows: 1) Modification and activation; Fly ash was placed in a ball mill, and the milling speed was controlled at 350 r / min for 25 min to obtain activated fly ash. Then, sodium hydroxide solution was added to the activated fly ash, stirred evenly, and placed in a constant temperature curing chamber at 90℃ for 3 h to obtain alkali-activated fly ash. Finally, the alkali-activated fly ash was placed in an oven and dried at 108℃ for 3 h, then pulverized and passed through a 90-mesh sieve to obtain modified fly ash. The volume concentration of the sodium hydroxide solution was 13%, and the amount of sodium hydroxide solution added was 7% of the total mass of the activated fly ash. 2) Mixing raw materials; The modified fly ash obtained in step 1) is put into a mixing device, the mixing temperature is controlled at 27℃, and the mixture is stirred at a low speed of 460r / min for 7 minutes to mix evenly; then the defoamer is added and the mixing continues for 7 minutes to obtain the mixture; wherein, the defoamer is a silicone defoamer; 3) Mixing the paste; Add water to the mixture obtained in step 2), adjust the stirring speed to 1050 r / min, stir at high speed for 16 min to obtain the substrate slurry, control the consistency of the slurry to 168 mm, and the composite substrate can be obtained. The resin-based microcapsules have a core-shell structure, with the core being a phase change energy storage material and the shell being a copolymer of epoxy resin and polyurethane. The resin-based microcapsules have a particle size of 90 μm and a shell thickness of 12 μm. The phase change energy storage material is polyethylene glycol, and the phase change temperature is 28℃. Thermal insulation filler aerogel, with a particle size of 200μm; The sound-absorbing filler is made of basalt fiber with a fiber length of 1.5 mm; The binder is sodium carboxymethyl cellulose; Modifier is one type of water-reducing agent; The crack-resistant fiber is glass fiber with a fiber length of 9mm.

[0018] Example 4: This example describes the preparation method of the novel composite wall material containing resin-based microcapsules as described in Example 3, including the following steps: S1, Preparation of resin-based microcapsules; S1-1. Epoxy resin and polyurethane are mixed at a mass ratio of 4:1, and then diluted with acetone solution to obtain a shell solution. The phase change energy storage material is heated and melted, and then an emulsifier is added. The mixture is stirred and emulsified at 1750 r / min for 45 min to obtain a core emulsion. The volume concentration of the acetone solution is 4%, and the amount added is 0.8% of the total mass of the shell solution. The emulsifier is sodium dodecylbenzenesulfonate, and the amount added is 2% of the total mass of the core emulsion. S1-2. Slowly drop the core emulsion from step S1-1 into the shell solution, and adjust the pH of the mixed solution to 8. Use a gradient heating process to gradually increase the temperature of the mixed solution from 50℃ to 65℃, controlling the heating rate at 4℃ / h, and react within this temperature range for 3h. After the reaction is complete, cool, centrifuge, and dry the reactants to obtain resin-based microcapsules; wherein, the centrifugation speed is 3000r / min, the centrifugation time is 11min, the drying temperature is 106℃, and the drying time is 2h. S2, Raw material pretreatment; The thermal insulation filler and sound-absorbing filler were placed in an oven and dried at 105℃ for 3 hours. The dried thermal insulation filler and sound-absorbing filler were then modified. The modification method was as follows: the dried thermal insulation filler was added to a high-speed mixer, followed by the sequential addition of a silane coupling agent and anhydrous ethanol. The mixture was stirred at 85℃ and 400 r / min for 45 minutes. After cooling, the reaction mixture was dried to constant weight to obtain the modified thermal insulation filler. The mass ratio of the silane coupling agent, anhydrous ethanol, and thermal insulation filler was 0.0. 2:0.03:1; The dried sound-absorbing filler is added to a reactor, and then 3% of the total mass of the sound-absorbing filler is added to the reactor. The mixture is stirred for 30 minutes at 65℃ and 250r / min, filtered, and dried to obtain the modified sound-absorbing filler. The hydrophobic modifier is stearic acid. The modified thermal insulation filler and the modified sound-absorbing filler are then pulverized and passed through a 90-mesh sieve. The sieved thermal insulation filler and sound-absorbing filler are mixed with the composite substrate, binder, and modifier to obtain the pretreated material. S3. Mix and stir; Add the pretreated material obtained in step S2 into the mixing equipment, control the mixing temperature at 30°C, and mix at a speed of 400 r / min for 7 min; then add the resin-based microcapsules obtained in steps S1-2 into the mixing equipment and continue mixing for 13 min; finally add pure water into the mixing equipment and continue mixing at a speed of 1000 r / min for 18 min, and control the consistency of the mixed material to 200 mm to obtain a mixed slurry; S4. Molding and curing; The mixed slurry obtained in step S3 is poured into a mold, pre-pressed at a frequency of 17Hz for 4 minutes, and then compacted at a frequency of 28Hz for 4 minutes to obtain a compacted blank. The compacted blank is then allowed to stand at room temperature for 35 hours before demolding. The demolded compacted blank is then placed in a curing chamber and cured for 10 days at a temperature of 23℃ and a relative humidity of 70%, with water sprayed every 20 hours at a rate of 300 ml / m³. 2 After the compacted blank has been cured for 4 days, the relative humidity inside the curing box is reduced to 55%; the composite wall material can then be obtained.

[0019] Example 5: A novel composite wall material containing resin-based microcapsules, comprising the following raw materials in parts by weight: 60 parts composite substrate, 25 parts resin-based microcapsules, 30 parts thermal insulation filler, 20 parts sound-absorbing filler, 12 parts adhesive, 6 parts modifier, 5 parts crack-resistant fiber, and 20 parts purified water. The composite substrate includes: 60 parts fly ash, 6 parts defoamer, and 20 parts water; The preparation method of the composite substrate is as follows: 1) Modification and activation; Fly ash was placed in a ball mill, and the milling speed was controlled at 400 r / min for 30 min to obtain activated fly ash. Then, sodium hydroxide solution was added to the activated fly ash, stirred evenly, and placed in a constant temperature curing chamber at 100℃ for 3 h to obtain alkali-activated fly ash. Finally, the alkali-activated fly ash was placed in an oven and dried at 110℃ for 3 h, then pulverized and passed through a 100-mesh sieve to obtain modified fly ash. The volume concentration of the sodium hydroxide solution was 15%, and the amount of sodium hydroxide solution added was 8% of the total mass of the activated fly ash. 2) Mixing raw materials; The modified fly ash obtained in step 1) is put into a mixing device, the mixing temperature is controlled at 30℃, and the mixture is stirred at a low speed of 500r / min for 10min until it is uniform; then the defoamer is added and the mixing continues for 8min to obtain the mixture; wherein, the defoamer is a silicone defoamer; 3) Mixing the paste; Add water to the mixture obtained in step 2), adjust the stirring speed to 1200 r / min, stir at high speed for 20 min to obtain the substrate slurry, control the consistency of the slurry to 180 mm, and the composite substrate can be obtained. The resin-based microcapsules have a core-shell structure, with the core being a phase change energy storage material and the shell being a copolymer of epoxy resin and polyurethane. The resin-based microcapsules have a particle size of 120 μm and a shell thickness of 15 μm. The phase change energy storage material is fatty acid, and the phase change temperature is 35℃. The insulation filler is glass wool with a particle size of 300μm; The sound-absorbing filler is basalt fiber with a fiber length of 2.3 mm; The adhesive is an acrylic emulsion; The modifier is a water-reducing agent; The crack-resistant fiber is glass fiber with a fiber length of 12mm.

[0020] Example 6: This example describes the preparation method of the novel composite wall material containing resin-based microcapsules as described in Example 5, including the following steps: S1, Preparation of resin-based microcapsules; S1-1. Epoxy resin and polyurethane are mixed at a mass ratio of 5:1, and then diluted with acetone solution to obtain a shell solution. The phase change energy storage material is heated and melted, and then an emulsifier is added. The mixture is stirred and emulsified at 2000 r / min for 60 min to obtain a core emulsion. The volume concentration of the acetone solution is 5%, and the amount added is 1.3% of the total mass of the shell solution. The emulsifier is sodium dodecylbenzenesulfonate, and the amount added is 3% of the total mass of the core emulsion. S1-2. Slowly add the core emulsion from step S1-1 to the shell solution, and adjust the pH of the mixed solution to 8.5. Use a gradient heating process to gradually increase the temperature of the mixed solution from 50℃ to 65℃, controlling the heating rate at 5℃ / h, and react within this temperature range for 4h. After the reaction is complete, cool, centrifuge, and dry the reactants to obtain resin-based microcapsules. The centrifugation speed is 3200 r / min, the centrifugation time is 12 min, the drying temperature is 110℃, and the drying time is 2.5h. S2, Raw material pretreatment; The thermal insulation filler and sound-absorbing filler were placed in an oven and dried at 110℃ for 4 hours. The dried thermal insulation filler and sound-absorbing filler were then modified. The modification method was as follows: the dried thermal insulation filler was added to a high-speed mixer, followed by the sequential addition of a silane coupling agent and anhydrous ethanol. The mixture was stirred at 90℃ and 500 r / min for 60 minutes. After cooling, the reaction mixture was dried to constant weight to obtain the modified thermal insulation filler. The mass ratio of the silane coupling agent, anhydrous ethanol, and thermal insulation filler was 0.0. 3:0.04:1; The dried sound-absorbing filler is added to the reactor, and then 4% of the total mass of the sound-absorbing filler is added to the reactor. The mixture is stirred at 70℃ and 300r / min for 40min, filtered, and dried to obtain the modified sound-absorbing filler. The hydrophobic modifier is stearic acid. The modified thermal insulation filler and the modified sound-absorbing filler are then pulverized and passed through a 100-mesh sieve. The sieved thermal insulation filler and sound-absorbing filler are mixed with the composite substrate, binder, and modifier to obtain the pretreated material. S3. Mix and stir; Add the pretreated material obtained in step S2 into a mixing device, control the mixing temperature at 35°C, and mix at a speed of 500 r / min for 10 min; then add the resin-based microcapsules obtained in steps S1-2 into the mixing device and continue mixing for 15 min; finally add pure water into the mixing device and continue mixing at a speed of 1200 r / min for 20 min, and control the consistency of the mixed material to 220 mm to obtain a mixed slurry; S4. Molding and curing; The mixed slurry obtained in step S3 is poured into a mold, pre-pressed at a frequency of 20Hz for 5 minutes, and then compacted at a frequency of 30Hz for 5 minutes to obtain a compacted blank. The compacted blank is then allowed to stand at room temperature for 48 hours before demolding. The demolded compacted blank is then placed in a curing chamber and cured for 14 days at a temperature of 25℃ and a relative humidity of 80%, with water sprayed every 24 hours at a rate of 500 ml / m³. 2 After the compacted blank has been cured for 5 days, the relative humidity inside the curing box is reduced to 60%; the composite wall material can then be obtained.

[0021] The performance of the composite wall materials prepared in Examples 2, 4 and 6 were tested respectively, and the results are shown in Table 1.

[0022] Table 1: Properties of composite wall materials prepared in Examples 2, 4, and 6

[0023] As shown in Table 1, the composite wall materials prepared in Examples 2, 4, and 6 all meet and outperform conventional substrates in terms of core performance indicators: compressive strength ≥3.9MPa (far exceeding the standard lower limit of 3.5MPa), interfacial bonding strength with resin-based microcapsules ≥1.3MPa (meeting the compatibility requirement of ≥1.2MPa), particle uniformity deviation ≤4%, no obvious bubbles in the slurry, and dense internal structure; the preparation process of the present invention can effectively activate the substrate activity, improve interfacial compatibility, and has strong process stability and small performance fluctuations; moreover, the performance of Example 6 is better than that of Examples 2 and 4, and Example 6 is the best example.

[0024] Comparative Experiment 1: Investigating the effect of resin-based microcapsule addition amount on the performance of composite wall materials Comparative Example 1-1: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of resin-based microcapsules added is 5 parts; Comparative Examples 1-2: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of resin-based microcapsules added is 15 parts; Comparative Examples 1-3: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of resin-based microcapsules added is 25 parts; Comparative Examples 1-4: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of resin-based microcapsules added is 35 parts; The properties of the composite wall materials prepared in Comparative Examples 1-1, 1-2, 1-3, and 1-4 were tested respectively, and the test results are shown in Table 2.

[0025] Table 2: Properties of composite wall materials prepared in Comparative Examples 1-1, 1-2, 1-3, and 1-4

[0026] Table 2 shows that the amount of resin-based microcapsules added is negatively correlated with thermal conductivity and positively correlated with sound absorption. When the addition amount increases from 5% to 25%, the thermal insulation effect is significantly improved and the moisture absorption rate decreases. However, when the dosage reaches 35 parts, the porosity inside the wall is too high and the bonding points of the matrix are insufficient, resulting in a sharp drop in compressive strength to 3.7 MPa, which is lower than the standard lower limit (≥3.5 MPa).

[0027] It is evident that the optimal range for the addition amount of resin-based microcapsules is 15-20 parts. Within this range, a perfect balance is achieved between dynamic thermal insulation and energy storage and the strength of the matrix structure, which can both regulate room temperature through phase change and ensure the load-bearing capacity and crack resistance of the wall.

[0028] Comparative Experiment 2: Investigating the Effect of Fly Ash Activation Time on the Properties of Composite Wall Materials Comparative Example 2-1: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the fly ash activation time is 10 min; Comparative Example 2-2: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the activation time of fly ash is 25 min; Comparative Examples 2-3: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the fly ash activation time is 40 min; Comparative Examples 2-4: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the fly ash activation time is 55 min; The properties of the composite wall materials prepared in Comparative Examples 2-1, 2-2, 2-3, and 2-4 were tested respectively, and the test results are shown in Table 3.

[0029] Table 3: Properties of composite wall materials prepared in Comparative Examples 2-1, 2-2, 2-3, and 2-4

[0030] The data in Table 3 shows that: The effect of activation time on compressive strength shows a relationship of first increasing and then decreasing. When the fly ash activation time is 10 min, the fly ash particles are not fully stripped, and the release of activated SiO2 / Al2O3 is insufficient, resulting in a loose matrix. When the fly ash activation time is 25-40 min, it enters the golden activation zone, the specific surface area increases, the alkali activation reaction is complete, and the intensity peak appears around 40 min. When the activation time of fly ash is 55 min, excessive grinding leads to finer particles, which increases the water demand and damages the density of the slurry. At the same time, hard agglomerates are easily formed between particles, resulting in a decrease in macroscopic compressive strength to 4.1 MPa. It can be seen that the optimal activation time for fly ash is 25-35 minutes. This time period can ensure the full activation of the physical structure while avoiding particle agglomeration.

[0031] Comparative Experiment 3: Investigating the effect of modifier dosage on the properties of composite wall materials Comparative Example 3-1: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of modifier used is 1 part; Comparative Example 3-2: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of modifier used is 3 parts; Comparative Example 3-3: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of modifier used is 5 parts; Comparative Examples 3-4: In this example, the preparation method of the composite wall material is the same as that in Example 2, except that the amount of modifier used is 7 parts; The properties of the composite wall materials prepared in Comparative Examples 3-1, 3-2, 3-3, and 3-4 were tested respectively, and the test results are shown in Table 4.

[0032] Table 4: Properties of composite wall materials prepared in Comparative Examples 3-1, 3-2, 3-3, and 3-4

[0033] The data in Table 4 shows that: The amount of modifier directly affects the moisture absorption rate and the material skeleton density; When the amount of modifier is less than 3 parts, the surface coating is incomplete, and moisture can easily penetrate into the interior, causing the sound-absorbing fibers to expand and clump, the pores to collapse, and the sound absorption coefficient to drop sharply. When the amount of modifier exceeds 5 parts, although the moisture absorption rate is extremely low, the excessive organic hydrophobic agent will replace the bonding sites of the inorganic substrate, resulting in the formation of a weak interface layer inside the wall material, thereby reducing the compressive strength to 3.9 MPa and potentially accelerating aging in the later stage. It can be seen that the optimal range for the amount of modifier is 2 to 4 parts. Within this range, the material has sufficient hydrophobicity to maintain a long-term stable porous sound-absorbing structure.

Claims

1. A novel composite wall material containing resin-based microcapsules, characterized in that, The raw materials include the following parts by weight: 30-60 parts of composite substrate, 10-25 parts of resin-based microcapsules, 15-30 parts of thermal insulation filler, 8-20 parts of sound-absorbing filler, 5-12 parts of binder, 2-6 parts of modifier, and 10-20 parts of purified water. The composite substrate comprises: 30-60 parts fly ash, 2-6 parts defoamer, and 10-20 parts water; The resin-based microcapsules have a core-shell structure, with the core being a phase change energy storage material and the shell being a copolymer of epoxy resin and polyurethane. The particle size of the resin-based microcapsules is 70~120μm, and the shell thickness is 5~15μm.

2. The novel composite wall material containing resin-based microcapsules according to claim 1, characterized in that, The thermal insulation filler is one of expanded perlite, aerogel, and glass wool, and the particle size of the thermal insulation filler is 100~300μm; The sound-absorbing filler is one of wood fiber and basalt fiber, and the fiber length of the sound-absorbing filler is 0.5~2.3mm; The adhesive is one of polyvinyl alcohol, sodium carboxymethyl cellulose, and acrylic emulsion; The modifier is one of a silane coupling agent or a water-reducing agent.

3. The novel composite wall material containing resin-based microcapsules according to claim 1, characterized in that, The method for preparing the composite substrate is as follows: 1) Modification and activation; The fly ash is placed in a ball mill, and the milling speed is controlled at 300-400 r / min for 20-30 min to obtain activated fly ash. Then, sodium hydroxide solution is added to the activated fly ash, stirred evenly, and placed in a constant temperature curing chamber. The mixture is kept at 80-100℃ for 2-3 h to obtain alkali-activated fly ash. Finally, the alkali-activated fly ash is placed in an oven and dried at 105-110℃ for 2-3 h, then pulverized and passed through an 80-100 mesh sieve to obtain modified fly ash. The volume concentration of the sodium hydroxide solution is 10-15%, and the amount of sodium hydroxide solution added is 5-8% of the total mass of the activated fly ash. 2) Mixing raw materials; The modified fly ash obtained in step 1) is put into a mixing device, the mixing temperature is controlled at 25~30℃, and the mixture is stirred at a low speed of 300~500r / min for 5~10min until it is uniformly mixed; then the defoamer is added and the mixing continues for 5~8min to obtain a mixture; wherein, the defoamer is a silicone defoamer; 3) Mixing the paste; Add water to the mixture obtained in step 2), adjust the stirring speed to 800~1200r / min, and stir at high speed for 15~20min to obtain the substrate slurry. Control the consistency of the slurry to 150~180mm to obtain the composite substrate.

4. The novel composite wall material containing resin-based microcapsules according to claim 1, characterized in that, The phase change energy storage material is one of paraffin wax, polyethylene glycol, and fatty acid, and the phase change temperature is 20~35℃.

5. The novel composite wall material containing resin-based microcapsules according to claim 1, characterized in that, It also includes 2 to 5 parts of crack-resistant fiber, which is one of polypropylene fiber and glass fiber, with a fiber length of 6 to 12 mm.

6. A method for preparing a novel composite wall material containing resin-based microcapsules as described in any one of claims 1 to 5, characterized in that, Includes the following steps: S1, Preparation of resin-based microcapsules; S1-1. The epoxy resin and polyurethane are mixed at a mass ratio of 3~5:1, and then diluted with acetone solution to obtain a shell solution; the phase change energy storage material is heated and melted, and then an emulsifier is added. The mixture is stirred and emulsified at 1500~2000r / min for 30~60min to obtain a core emulsion. S1-2. Slowly drip the core emulsion described in step S1-1 into the shell solution, and adjust the pH of the mixed solution to 7.5~8.

5. Use a gradient heating process to gradually heat the mixed solution from 50℃ to 65℃, control the heating rate to 3~5℃ / h, and react within this temperature range for 2~4h. After the reaction is completed, cool, centrifuge, and dry the reactants to obtain resin-based microcapsules. S2, Raw material pretreatment; The thermal insulation filler and sound absorption filler are placed in an oven and dried at 95~110℃ for 2~4 hours. Then, the dried thermal insulation filler and sound absorption filler are crushed and passed through an 80~100 mesh sieve. The sieved thermal insulation filler and sound absorption filler are mixed with the composite substrate, binder and modifier to obtain the pretreated material. S3. Mix and stir; Add the pretreated material obtained in step S2 into a mixing device, control the mixing temperature at 25~35℃, and mix at a speed of 300~500r / min for 5~10min; then add the resin-based microcapsules obtained in step S1-2 into the mixing device and continue mixing for 10~15min; finally add purified water into the mixing device and continue mixing at a speed of 800~1200r / min for 15~20min, and control the consistency of the mixed material to be 180~220mm to obtain a mixed slurry; S4. Molding and curing; The mixed slurry obtained in step S3 is poured into a mold, pre-pressed at a frequency of 15-20 Hz for 3-5 min, and then compacted at a frequency of 25-30 Hz for 2-5 min to obtain a compacted blank; then the compacted blank is left to stand at room temperature for 24-48 h, demolded, and placed in a curing box for curing under conditions of a temperature of 20-25°C and a relative humidity of 60-80% for 7-14 d, with water sprayed every 18-24 h, the spraying amount being controlled to be 200-500 ml / m 2 , to obtain the composite wall material.

7. The method for preparing a novel composite wall material containing resin-based microcapsules according to claim 6, characterized in that, In step S1-1, the volume concentration of the acetone solution is 2-5%, and the amount added is 0.5-1.3% of the total mass of the shell solution; the emulsifier is sodium dodecylbenzenesulfonate, and the amount added is 1-3% of the total mass of the core emulsion.

8. The method for preparing a novel composite wall material containing resin-based microcapsules according to claim 6, characterized in that, Step S2 also includes modifying the dried thermal insulation filler and sound-absorbing filler, respectively. The modification method is as follows: The dried thermal insulation filler is added to a high-speed mixer, followed by the addition of silane coupling agent and anhydrous ethanol. The mixture is stirred at 80-90°C and 300-500 r / min for 30-60 min. After cooling, the reaction mixture is dried to constant weight to obtain the modified thermal insulation filler. The mass ratio of the silane coupling agent, anhydrous ethanol, and thermal insulation filler is 0.01-0.03:0.02-0.04:

1. The dried sound-absorbing filler is added to a reaction vessel, and then 2-4% of the total mass of the sound-absorbing filler is added to the reaction vessel. The mixture is stirred for 20-40 minutes at 60-70℃ and 200-300 r / min. After filtration and drying, the modified sound-absorbing filler is obtained. The hydrophobic modifier is stearic acid.

9. The method for preparing a novel composite wall material containing resin-based microcapsules according to claim 6, characterized in that, In steps S1-2, the centrifugation speed is 2800~3200 r / min, the centrifugation time is 8~12 min; the drying temperature is 100~110℃, and the drying time is 1.5~2.5 h.

10. The method for preparing a novel composite wall material containing resin-based microcapsules according to claim 6, characterized in that, The phase change energy storage material is one of paraffin wax, polyethylene glycol, and fatty acids.

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