Thermal insulation wall material based on industrial waste fly ash and application of thermal insulation wall material in greenhouse technology
By optimizing fly ash insulation wall materials through modified copolymers and functional additives, the synergistic problem of fly ash's insulation performance and mechanical strength in greenhouses is solved, and efficient insulation performance and mechanical performance improvements are achieved, making it suitable for insulation wall materials in greenhouses.
Patent Information
- Application Number
- CN202510797304.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-16
- Publication Date
- 2025-09-16
AI Technical Summary
When fly ash is used as the insulation wall material of existing greenhouses, it is difficult to achieve the coordinated optimization of strength and thermal insulation performance. In addition, it has strong water absorption, which leads to a decrease in thermal insulation performance in high humidity environments, easily breeding mold and affecting the growth of crops.
Modified copolymers, functional additives and silicon-modified wood cellulose are used as components. The modified copolymers form a thermal resistance network, the functional additives fill the pores, the silicon-modified wood cellulose optimizes the pore structure, and multi-particle fly ash is combined to build a stable support structure to improve the mechanical properties and thermal insulation effect.
It significantly improves the stability and mechanical properties of insulation materials, reduces heat loss and water absorption, extends service life, and meets the insulation needs of greenhouses.
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Figure BDA0005450112290000171
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of building materials, and in particular to a thermal insulation wall material based on industrial waste fly ash and application thereof in a greenhouse process. Background Art
[0002] With the rapid development of industry, fly ash, a major solid waste generated by thermal power plants and other industrial enterprises, is being increasingly discharged. Large amounts of fly ash accumulation not only consume significant land resources but also pose a significant risk of soil, water, and atmospheric pollution. Therefore, achieving efficient and comprehensive utilization of fly ash has become an urgent environmental and resource challenge.
[0003] In the construction sector, greenhouse construction places high demands on the performance, cost, and environmental performance of insulation wall materials. High-quality insulation wall materials must significantly reduce greenhouse energy consumption and create a suitable environment for crop growth, while also meeting the goals of low cost and sustainable development. However, existing insulation wall materials commonly used in greenhouses have numerous drawbacks. Red bricks have limited insulation performance and are highly environmentally damaging. While polystyrene foam boards offer excellent thermal insulation, they lack material stability and experience significant aging under long-term environmental influences. Furthermore, they are prone to deformation under certain stresses. When fly ash is used in insulation wall materials, it is difficult to achieve a synergistic optimization of strength and insulation performance. Increasing the fly ash content can enhance insulation performance but significantly reduces the material's mechanical strength. Furthermore, due to its porous structure, fly ash is highly absorbent, resulting in poor waterproofing and moisture-proofing properties for wall materials made from fly ash. In the high humidity environment of greenhouses, the walls absorb large amounts of moisture, which not only reduces insulation performance but also fosters mold growth, adversely affecting crop growth. Moreover, under the influence of long-term temperature and humidity fluctuations, the microstructure of fly ash-based wall materials will change, making it difficult to maintain long-term and stable thermal insulation performance.
[0004] Therefore, it is of great practical significance to develop an environmentally friendly and economical wall material that can effectively utilize industrial waste fly ash and meet the insulation needs of greenhouses. Summary of the Invention
[0005] In order to solve the above problems, the present invention proposes a thermal insulation wall material based on industrial waste fly ash and its application in greenhouse technology.
[0006] The invention provides a thermal insulation wall material based on industrial waste fly ash, comprising the following raw materials in parts by weight: 30-50 parts of Portland cement, 8-12 parts of modified copolymer, 6-8 parts of functional additives, 15-25 parts of aggregate, 0.5-1 part of water reducer, 2-5 parts of foam stabilizer, 3-5 parts of silicon-modified wood cellulose, and 20-30 parts of deionized water.
[0007] Preferably, the modified copolymer is prepared by the following method:
[0008] Methyl palmitate is added to xylene and stirred, styrene-maleic anhydride copolymer is added and stirred, a modifier and benzoyl peroxide are added, the mixture is heated and stirred, and the mixture is poured into methanol for precipitation, filtered, washed, and dried to obtain a modified copolymer;
[0009] Preferably, the modified copolymer comprises the following components in parts by mass: 8-15 parts of methyl palmitate, 10-20 parts of styrene-maleic anhydride copolymer, 0.5-1 part of a modifier, 0.05-0.1 part of benzoyl peroxide, and 80-90 parts of xylene.
[0010] Preferably, the modifier is prepared by the following method:
[0011] Disperse 4-vinylaniline in toluene, stir, add itaconic anhydride and triethylamine, heat, reflux with stirring, and distill under reduced pressure to obtain an intermediate product; wherein, 4-vinylaniline 15-25 parts, itaconic anhydride 10-12 parts, triethylamine 0.1-0.2 parts, toluene 80-100 parts;
[0012] Dodecyltrichlorosilane is dispersed in DMF, stirred, the intermediate product and potassium carbonate are added, heated and stirred, and then the pH is adjusted, filtered, washed, and purified to obtain a modifier; wherein the modifier comprises 15-20 parts of dodecyltrichlorosilane, 25-30 parts of the intermediate product, 0.1-0.2 parts of potassium carbonate, and 100-110 parts of DMF.
[0013] Preferably, the functional additive is prepared by the following method:
[0014] A1. Trimethylolpropane trimethacrylate and ethylene glycol bis(3-mercaptopropionate) were mixed and stirred, benzoyl peroxide solution and azodicarbonamide were added, and the mixture was heated with stirring and distilled under reduced pressure to obtain an intermediate;
[0015] A2. Disperse the intermediate in dimethyl sulfoxide, stir, add polyethylene glycol diacrylate and polycaprolactone diol, heat and stir, and distill under reduced pressure to obtain a functional additive.
[0016] Preferably, in step A1, the following components are included in parts by mass: 8-12 parts of trimethylolpropane trimethacrylate, 15-20 parts of ethylene glycol di(3-mercaptopropionate), 15-20 parts of benzoyl peroxide solution, and 2-3 parts of azodicarbonamide.
[0017] Preferably, in step A2, the following components are included in parts by mass: 15-25 parts of the intermediate, 1.5-4 parts of polyethylene glycol diacrylate, 0.5-0.8 parts of polycaprolactone diol, and 60-80 parts of dimethyl sulfoxide.
[0018] Preferably, the silicon-modified lignocellulose is prepared by the following method:
[0019] Adding rice husk ash to a sodium hydroxide solution, heating and stirring, centrifuging, separating insoluble matter, and obtaining a silicon solution; wherein the mass ratio of rice husk ash to sodium hydroxide solution is 1-3:8-12, and the concentration of the sodium hydroxide solution is 1-3 mol / L;
[0020] Add lignocellulose to silicon solution, adjust pH to 5-6, heat and stir for 3-5 hours, filter, wash and dry to obtain silicon-modified lignocellulose; wherein, lignocellulose is 8-15 parts and silicon solution is 50-60 parts.
[0021] Preferably, the aggregate is obtained by grinding fly ash and then grading and sieving, as follows:
[0022] Fly ash with a particle size of 5-10 μm accounts for 20-30%, fly ash with a particle size of 15-25 μm accounts for 40-50%, fly ash with a particle size of 40-60 μm accounts for 10-15%, and fly ash with a particle size of 80-100 μm accounts for 5-15%.
[0023] The present invention also provides a method for preparing a thermal insulation wall material based on industrial waste fly ash, comprising the following steps:
[0024] Aggregate, silicate cement, functional additives and deionized water are mixed and stirred; modified copolymer, silicon-modified wood cellulose, water reducer and foam stabilizer are added and stirred to obtain thermal insulation wall material.
[0025] The present invention also provides an application of the above-mentioned thermal insulation wall material based on industrial waste fly ash in greenhouse technology.
[0026] The present invention has the following beneficial effects:
[0027] The present invention comprises the following steps: 4-vinylaniline and itaconic anhydride are mixed and reacted, and then reacted with dodecyltrichlorosilane to prepare a modifier. The modifier contains active groups such as amino groups and amide groups in its molecular structure, which can provide additional reaction sites, making the reaction between methyl palmitate and styrene-maleic anhydride copolymer easier to proceed; on the other hand, the long-chain alkyl group in the modifier can interact with the hydrophobic part of methyl palmitate, thereby reducing the interfacial tension between methyl palmitate and styrene-maleic anhydride copolymer and promoting the reaction; the modifier is then added to the reaction process of methyl palmitate and styrene-maleic anhydride copolymer to prepare a modified copolymer; the alkyl chain segment of the modified copolymer can An efficient thermal resistance network is formed in the insulation material, effectively hindering heat transfer and significantly reducing heat loss; the flexible chain segments provided by methyl palmitate give the modified copolymer good flexibility, allowing the insulation material to expand and deform under different environmental conditions, effectively preventing cracks in the insulation layer and extending the service life of the insulation material; the silane group in the modifier can enhance the adhesion between the modified copolymer and the insulation material matrix and the surface of the insulated object, ensuring a firm bond between the insulation material and the base layer, effectively preventing it from falling off, and ensuring the stability and reliability of the insulation system; the modified copolymer has good chemical stability and weather resistance, and can maintain stable performance under different chemical environments and climatic conditions.
[0028] The present invention mixes trimethylolpropane trimethacrylate and ethylene glycol di(3-mercaptopropionate), and then reacts with polyethylene glycol diacrylate and polycaprolactone diol to prepare a functional additive; under the action of benzoyl peroxide solution and azodicarbonamide, a free radical polymerization reaction occurs to form a cross-linked network structure, thereby improving the overall performance of the material. The introduction of polyethylene glycol diacrylate can participate in the free radical polymerization reaction and increase the crosslinking density. The introduction of polycaprolactone diol has a compact molecular structure and can form a hydrophobic layer, thereby reducing the water absorption rate of the material; the prepared functional additive can be filled into the internal pores of the thermal insulation material, making the pore structure more uniform and fine, reducing air convection, thereby reducing thermal conductivity and enhancing thermal insulation performance; its flexible structure and cross-linking characteristics can enhance the toughness and strength of the thermal insulation material and improve mechanical properties.
[0029] The present invention makes high-value use of rice husk ash, reacts rice husk ash with sodium hydroxide solution to prepare silicon solution, and then uses the solution to modify lignocellulose. The surface pore structure of the modified lignocellulose becomes more regular and the pore size becomes smaller. This not only optimizes the heat conduction path of the material, further reduces the heat transfer efficiency, enhances the thermal insulation performance, but also reduces the heat loss caused by air convection. Silicon element is deposited on the surface of lignocellulose and chemically bonds with lignocellulose, which improves the structural strength of lignocellulose, significantly improves the mechanical properties of the thermal insulation material, and effectively extends the service life of the thermal insulation material. The present invention selects fly ash of different particle sizes to add to the thermal insulation material, and the small particle size fly ash is filled in the gaps of the large particle size fly ash to construct an orderly and complex pore structure, which greatly hinders the convection of air, greatly reduces the flow rate of air in the pores, effectively blocks the heat transfer path with air as the medium, and significantly improves the thermal insulation effect of the thermal insulation material. This combination of multiple particle sizes creates a stable support structure within the insulation material, significantly improving its mechanical properties. The hydroxyl groups on the functional additive's molecular chains chemically bond with active sites on the fly ash surface, forming a dense bond layer at the particle interface. This interface optimization not only reduces obstacles to heat transfer but also effectively reduces the channels for water penetration along the interface. The functional additive's multiple hydrophobic groups form a cross-linked network structure, reducing the chance of water molecules coming into contact with the material and preventing it from entering the interior, thereby reducing water absorption. DETAILED DESCRIPTION
[0030] Portland cement was purchased from Chengde Xishangxi Cement Co., Ltd., specification: PC42.5; fly ash was purchased from Chengde Yifeng Building Materials Co., Ltd.; wood cellulose was purchased from Tai'an Anfeng New Materials Technology Co., Ltd., model: AF51; magnesium lignin sulfonate was purchased from Shenyang Xingzhenghe Chemical Co., Ltd., solid content: 98%, model: MM-1; silicone resin polyether emulsion was purchased from Jining Tangyi Chemical Co., Ltd., model: FM-550; styrene-maleic anhydride copolymer was purchased from Wuhan Kemik Biomedical Technology Co., Ltd., content: 18%; polycaprolactone diol was purchased from Xuzhou Yihuiyang New Materials Co., Ltd., packaging specification 1000 molecular weight.
[0031] Example 1
[0032] A thermal insulation wall material based on industrial waste fly ash comprises the following raw materials in parts by weight: 30 parts of Portland cement, 8 parts of modified copolymer, 6 parts of functional additives, 15 parts of aggregate, 0.5 parts of water reducer, 2 parts of foam stabilizer, 3 parts of silicon-modified wood cellulose, and 20 parts of deionized water; wherein the water reducer is magnesium lignin sulfonate, and the foam stabilizer is silicone resin polyether emulsion.
[0033] Wherein, the modified copolymer is prepared by the following method:
[0034] Methyl palmitate was added to xylene, stirred at 80 rpm for 8 minutes, styrene-maleic anhydride copolymer was added, stirred for 5 minutes, and then a modifier and benzoyl peroxide were added. The mixture was heated to 80°C and stirred at 200 rpm for 8 hours. The mixture was poured into methanol for precipitation, filtered, washed with deionized water 3 times, and dried at 40°C for 8 hours to obtain a modified copolymer; wherein the modified copolymer comprises 8 parts of methyl palmitate, 10 parts of styrene-maleic anhydride copolymer, 0.5 parts of a modifier, 0.05 parts of benzoyl peroxide, and 80 parts of xylene.
[0035] Wherein, the modifier is prepared by the following method:
[0036] Disperse 4-vinylaniline in toluene, stir at 100 rpm for 10 minutes, add itaconic anhydride and triethylamine, heat to 60°C at 150 rpm, reflux and stir for 6 hours, and distill under reduced pressure to obtain an intermediate product; wherein, 4-vinylaniline 15 parts, itaconic anhydride 10 parts, triethylamine 0.1 parts, toluene 80 parts;
[0037] Dodecyltrichlorosilane was dispersed in DMF, stirred at 80 rpm for 8 minutes, the intermediate product and potassium carbonate were added, heated to 80°C, stirred at 100 rpm for 12 hours, then the pH was adjusted to 5, filtered, washed three times with deionized water, and silica gel was used as the stationary phase. Dichloromethane and methanol with a volume ratio of 10:1 were selected for elution, and reduced pressure distillation was performed to obtain a modifier; wherein, 15 parts of dodecyltrichlorosilane, 25 parts of the intermediate product, 0.1 part of potassium carbonate, and 100 parts of DMF were obtained.
[0038] Among them, the functional additive is prepared by the following method:
[0039] A1. Trimethylolpropane trimethacrylate and ethylene glycol bis(3-mercaptopropionate) were mixed, stirred at 100 rpm for 10 min, benzoyl peroxide solution and azodicarbonamide were added, heated to 70° C., stirred at 200 rpm for 6 h, and distilled under reduced pressure to obtain an intermediate; wherein, 8 parts of trimethylolpropane trimethacrylate, 15 parts of ethylene glycol bis(3-mercaptopropionate), 15 parts of benzoyl peroxide solution, and 2 parts of azodicarbonamide were prepared by mixing benzoyl peroxide and toluene in a mass ratio of 5:80;
[0040] A2. Disperse the intermediate in dimethyl sulfoxide, stir at 60 rpm for 5 min, add polyethylene glycol diacrylate and polycaprolactone diol, stir at 80 rpm for 8 min, heat to 50°C, stir at 200 rpm for 4 h, and distill under reduced pressure to obtain a functional additive; wherein, the intermediate is 15 parts, polyethylene glycol diacrylate is 1.5 parts, polycaprolactone diol is 0.5 parts, and dimethyl sulfoxide is 60 parts.
[0041] Among them, silicon-modified lignocellulose is prepared by the following method:
[0042] Add rice husk ash to a sodium hydroxide solution, heat to 80°C, stir at 100 rpm for 2 hours, and centrifuge at 6000 rpm for 5 minutes to separate insoluble matter to obtain a silicon solution; wherein the mass ratio of rice husk ash to sodium hydroxide solution is 1:8, and the concentration of the sodium hydroxide solution is 1 mol / L;
[0043] Add lignocellulose to the silicon solution, adjust the pH to 5, heat to 40°C, stir at 80 rpm for 3 hours, filter, wash with deionized water until neutral, and dry at 60°C for 6 hours to obtain silicon-modified lignocellulose; wherein, lignocellulose is 8 parts and silicon solution is 50 parts.
[0044] Among them, the aggregate is obtained by grinding fly ash and then grading and screening, as follows:
[0045] 20% of the fly ash is of 5 μm particle size, 50% of the fly ash is of 15 μm particle size, 15% of the fly ash is of 40 μm particle size, and 15% of the fly ash is of 80 μm particle size.
[0046] A method for preparing a thermal insulation wall material based on industrial waste fly ash comprises the following steps:
[0047] Aggregate, silicate cement, functional additives and deionized water were mixed and stirred at 100 rpm for 10 minutes; modified copolymer, silicon-modified wood cellulose, water reducer and foam stabilizer were added and stirred at 100 rpm for 20 minutes to obtain a thermal insulation wall material.
[0048] Example 2
[0049] A thermal insulation wall material based on industrial waste fly ash comprises the following raw materials in parts by weight: 50 parts of Portland cement, 12 parts of modified copolymer, 8 parts of functional additives, 25 parts of aggregate, 1 part of water reducer, 5 parts of foam stabilizer, 5 parts of silicon-modified wood cellulose, and 30 parts of deionized water; wherein the water reducer is magnesium lignin sulfonate, and the foam stabilizer is silicone resin polyether emulsion.
[0050] Wherein, the modified copolymer is prepared by the following method:
[0051] Methyl palmitate was added to xylene, stirred at 100 rpm for 10 minutes, styrene-maleic anhydride copolymer was added, stirred for 8 minutes, then a modifier and benzoyl peroxide were added, heated to 100°C, stirred at 300 rpm for 12 hours, poured into methanol for precipitation, filtered, washed three times with deionized water, and dried at 60°C for 12 hours to obtain a modified copolymer; wherein the modified copolymer comprises 15 parts of methyl palmitate, 20 parts of styrene-maleic anhydride copolymer, 1 part of modifier, 0.1 part of benzoyl peroxide, and 90 parts of xylene.
[0052] Wherein, the modifier is prepared by the following method:
[0053] Disperse 4-vinylaniline in toluene, stir at 120 rpm for 15 minutes, add itaconic anhydride and triethylamine, heat to 70°C at 200 rpm, reflux and stir for 8 hours, and distill under reduced pressure to obtain an intermediate product; wherein, 4-vinylaniline 25 parts, itaconic anhydride 12 parts, triethylamine 0.2 parts, toluene 100 parts;
[0054] Dodecyltrichlorosilane was dispersed in DMF, stirred at 100 rpm for 12 min, the intermediate product and potassium carbonate were added, heated to 100°C, stirred at 150 rpm for 16 h, then the pH was adjusted to 5, filtered, washed three times with deionized water, and silica gel was used as the stationary phase. Dichloromethane and methanol with a volume ratio of 10:1 were selected for elution, and reduced pressure distillation was performed to obtain a modifier; wherein, 20 parts of dodecyltrichlorosilane, 30 parts of the intermediate product, 0.2 parts of potassium carbonate, and 110 parts of DMF were obtained.
[0055] Among them, the functional additive is prepared by the following method:
[0056] A1. Trimethylolpropane trimethacrylate and ethylene glycol bis(3-mercaptopropionate) were mixed, stirred at 200 rpm for 15 min, benzoyl peroxide solution and azodicarbonamide were added, heated to 90° C., stirred at 300 rpm for 8 h, and distilled under reduced pressure to obtain an intermediate; wherein, 12 parts of trimethylolpropane trimethacrylate, 20 parts of ethylene glycol bis(3-mercaptopropionate), 20 parts of benzoyl peroxide solution, and 3 parts of azodicarbonamide were prepared by mixing benzoyl peroxide and toluene in a mass ratio of 8:80;
[0057] A2. Disperse the intermediate in dimethyl sulfoxide, stir at 80 rpm for 8 min, add polyethylene glycol diacrylate and polycaprolactone diol, stir at 100 rpm for 10 min, heat to 60°C, stir at 300 rpm for 6 h, and distill under reduced pressure to obtain a functional additive; wherein, the intermediate is 25 parts, polyethylene glycol diacrylate is 4 parts, polycaprolactone diol is 0.8 parts, and dimethyl sulfoxide is 80 parts.
[0058] Among them, silicon-modified lignocellulose is prepared by the following method:
[0059] Add rice husk ash to a sodium hydroxide solution, heat to 100°C, stir at 150 rpm for 4 hours, and centrifuge at 8000 rpm for 8 minutes to separate insoluble matter to obtain a silicon solution; wherein the mass ratio of rice husk ash to sodium hydroxide solution is 3:12, and the concentration of the sodium hydroxide solution is 3 mol / L;
[0060] Add lignocellulose to the silicon solution, adjust the pH to 6, heat to 50°C, stir at 120 rpm for 5 hours, filter, wash with deionized water until neutral, and dry at 80°C for 8 hours to obtain silicon-modified lignocellulose; wherein, the content of lignocellulose is 15 parts and the content of silicon solution is 60 parts.
[0061] Among them, the aggregate is obtained by grinding fly ash and then grading and screening, as follows:
[0062] 30% of the fly ash is of 10 μm particle size, 50% of the fly ash is of 25 μm particle size, 10% of the fly ash is of 60 μm particle size, and 10% of the fly ash is of 100 μm particle size.
[0063] A method for preparing a thermal insulation wall material based on industrial waste fly ash comprises the following steps:
[0064] Aggregate, silicate cement, functional additives and deionized water were mixed and stirred at 150 rpm for 15 minutes; modified copolymer, silicon-modified wood cellulose, water reducer and foam stabilizer were added and stirred at 150 rpm for 30 minutes to obtain a thermal insulation wall material.
[0065] Example 3
[0066] A thermal insulation wall material based on industrial waste fly ash comprises the following raw materials in parts by weight: 40 parts of Portland cement, 10 parts of modified copolymer, 7 parts of functional additives, 20 parts of aggregate, 0.8 parts of water reducer, 4 parts of foam stabilizer, 4 parts of silicon-modified wood cellulose, and 25 parts of deionized water; wherein the water reducer is magnesium lignin sulfonate, and the foam stabilizer is silicone resin polyether emulsion.
[0067] Wherein, the modified copolymer is prepared by the following method:
[0068] Methyl palmitate was added to xylene, stirred at 90 rpm for 9 minutes, styrene-maleic anhydride copolymer was added, stirred for 7 minutes, then a modifier and benzoyl peroxide were added, heated to 90°C, stirred at 260 rpm for 10 hours, poured into methanol for precipitation, filtered, washed with deionized water 3 times, and dried at 50°C for 10 hours to obtain a modified copolymer; wherein, methyl palmitate was 12 parts, styrene-maleic anhydride copolymer was 15 parts, modifier was 0.8 parts, benzoyl peroxide was 0.08 parts, and xylene was 85 parts.
[0069] Wherein, the modifier is prepared by the following method:
[0070] Disperse 4-vinylaniline in toluene, stir at 110 rpm for 13 minutes, add itaconic anhydride and triethylamine, heat to 65°C at 180 rpm, reflux and stir for 7 hours, and distill under reduced pressure to obtain an intermediate product; wherein, 4-vinylaniline 20 parts, itaconic anhydride 11 parts, triethylamine 0.1 parts, toluene 90 parts;
[0071] Dodecyltrichlorosilane was dispersed in DMF, stirred at 90 rpm for 10 min, the intermediate product and potassium carbonate were added, heated to 90°C, stirred at 130 rpm for 14 h, then the pH was adjusted to 5, filtered, washed three times with deionized water, and silica gel was used as the stationary phase. Dichloromethane and methanol with a volume ratio of 10:1 were selected for elution, and reduced pressure distillation was performed to obtain a modifier; wherein, 18 parts of dodecyltrichlorosilane, 28 parts of the intermediate product, 0.15 parts of potassium carbonate, and 105 parts of DMF were obtained.
[0072] Among them, the functional additive is prepared by the following method:
[0073] A1. Trimethylolpropane trimethacrylate and ethylene glycol bis(3-mercaptopropionate) were mixed, stirred at 150 rpm for 13 min, benzoyl peroxide solution and azodicarbonamide were added, heated to 85° C., stirred at 260 rpm for 7 h, and distilled under reduced pressure to obtain an intermediate; wherein, 11 parts of trimethylolpropane trimethacrylate, 18 parts of ethylene glycol bis(3-mercaptopropionate), 28 parts of benzoyl peroxide solution, and 3 parts of azodicarbonamide were used, and the benzoyl peroxide solution was prepared by mixing benzoyl peroxide and toluene in a mass ratio of 7:80;
[0074] A2. Disperse the intermediate in dimethyl sulfoxide, stir at 70 rpm for 6 min, add polyethylene glycol diacrylate and polycaprolactone diol, stir at 90 rpm for 10 min, heat to 55 ° C, stir at 300 rpm for 6 h, and distill under reduced pressure to obtain a functional additive; wherein, the intermediate is 20 parts, polyethylene glycol diacrylate is 3 parts, polycaprolactone diol is 0.7 parts, and dimethyl sulfoxide is 70 parts.
[0075] Among them, silicon-modified lignocellulose is prepared by the following method:
[0076] Add rice husk ash to a sodium hydroxide solution, heat to 90°C, stir at 130 rpm for 3 hours, and centrifuge at 7000 rpm for 6 minutes to separate insoluble matter to obtain a silicon solution; wherein the mass ratio of rice husk ash to sodium hydroxide solution is 2:11, and the concentration of the sodium hydroxide solution is 2 mol / L;
[0077] Add lignocellulose to the silicon solution, adjust the pH to 6, heat to 45°C, stir at 100 rpm for 4 hours, filter, wash with deionized water until neutral, and dry at 70°C for 7 hours to obtain silicon-modified lignocellulose; wherein, the content of lignocellulose is 12 parts and the content of silicon solution is 55 parts.
[0078] Among them, the aggregate is obtained by grinding fly ash and then grading and screening, as follows:
[0079] Fly ash with a particle size of 10 μm accounts for 25%, fly ash with a particle size of 20 μm accounts for 45%, fly ash with a particle size of 50 μm accounts for 15%, and fly ash with a particle size of 100 μm accounts for 15%.
[0080] A method for preparing a thermal insulation wall material based on industrial waste fly ash comprises the following steps:
[0081] Aggregate, silicate cement, functional additives and deionized water were mixed and stirred at 130 rpm for 12 minutes; modified copolymer, silicon-modified wood cellulose, water reducer and foam stabilizer were added and stirred at 130 rpm for 25 minutes to obtain a thermal insulation wall material.
[0082] Comparative Example 1
[0083] Comparative Example 1 is the same as Example 1, except that the preparation method of the modifier is different, as follows:
[0084] The modifier is prepared by the following method:
[0085] Disperse 4-vinylaniline in toluene, stir at 100 rpm for 10 minutes, add itaconic anhydride and triethylamine, heat to 60°C at 150 rpm, reflux and stir for 6 hours, and distill under reduced pressure to obtain a modifier; wherein, 4-vinylaniline is 15 parts, itaconic anhydride is 10 parts, triethylamine is 0.1 parts, and toluene is 80 parts.
[0086] Comparative Example 2
[0087] Comparative Example 2 is the same as Example 1, except that the preparation method of the functional additive is different, as follows:
[0088] Functional additives are prepared by the following method:
[0089] A1. Trimethylolpropane trimethacrylate and ethylene glycol bis(3-mercaptopropionate) were mixed, stirred at 100 rpm for 10 min, benzoyl peroxide solution and azodicarbonamide were added, heated to 70° C., stirred at 200 rpm for 6 h, and distilled under reduced pressure to obtain an intermediate; wherein, 8 parts of trimethylolpropane trimethacrylate, 15 parts of ethylene glycol bis(3-mercaptopropionate), 15 parts of benzoyl peroxide solution, and 2 parts of azodicarbonamide were prepared, and the benzoyl peroxide solution was prepared by mixing benzoyl peroxide and toluene in a mass ratio of 5:80;
[0090] A2. Disperse the intermediate in dimethyl sulfoxide, stir at 60 rpm for 5 min, add polyethylene glycol diacrylate, stir at 800 rpm for 8 min, heat to 50°C, stir at 200 rpm for 4 h, and distill under reduced pressure to obtain a functional additive; wherein, the intermediate is 15 parts, polyethylene glycol diacrylate is 2.0 parts, and dimethyl sulfoxide is 60 parts.
[0091] Comparative Example 3
[0092] Comparative Example 3 is the same as Example 1, except that the preparation method of the functional additive is different, as follows:
[0093] Functional additives are prepared by the following method:
[0094] A1. Trimethylolpropane trimethacrylate and ethylene glycol bis(3-mercaptopropionate) were mixed, stirred at 100 rpm for 10 min, benzoyl peroxide solution and azodicarbonamide were added, heated to 70° C., stirred at 200 rpm for 6 h, and distilled under reduced pressure to obtain an intermediate; wherein, 8 parts of trimethylolpropane trimethacrylate, 15 parts of ethylene glycol bis(3-mercaptopropionate), 15 parts of benzoyl peroxide solution, and 2 parts of azodicarbonamide were prepared, and the benzoyl peroxide solution was prepared by mixing benzoyl peroxide and toluene in a mass ratio of 5:80;
[0095] A2. Disperse the intermediate in dimethyl sulfoxide, stir at 60 rpm for 5 min, add polycaprolactone diol, stir at 800 rpm for 8 min, heat to 50°C, stir at 200 rpm for 4 h, and distill under reduced pressure to obtain a functional additive; wherein, the intermediate is 15 parts, polycaprolactone diol is 2.0 parts, and dimethyl sulfoxide is 60 parts.
[0096] Comparative Example 4
[0097] Comparative Example 4 is the same as Example 1, except that the preparation method of silicon-modified lignocellulose is different, as follows:
[0098] Silicon-modified lignocellulose is prepared by the following method:
[0099] The modified lignocellulose was added to a sodium hydroxide solution, heated to 80° C., stirred at 100 rpm for 2 h, and centrifuged at 6000 rpm for 5 min to obtain the modified lignocellulose; wherein the mass ratio of the lignocellulose to the sodium hydroxide solution was 1:8, and the concentration of the sodium hydroxide solution was 1 mol / L.
[0100] Comparative Example 5
[0101] Comparative Example 5 is the same as Example 1, except that fly ash with a particle size of 15 μm is used as the aggregate.
[0102] Performance Testing
[0103] The following performance tests were performed on the thermal insulation wall materials prepared in Examples 1-3 and Comparative Examples 1-5:
[0104] Compressive strength: tested according to GB / T50081-2019. The sample material was molded at 0.8MPa, demolded after 1 hour, cured at 25℃ for 7 days, dried at 60℃ for 5 hours, and its 28d compressive strength was tested;
[0105] Thermal conductivity: Tested in accordance with GB / T10295-2008. The sample material was cast into a mold with a diameter of 10 mm and a thickness of 5 mm. The mold was cured for 7 days at a temperature of 20°C and a relative humidity of 70%, and then dried to constant weight.
[0106] Interface bonding strength: Tested according to the chemical industry standard HG / T4567-2013. A 1mm thick insulation material sample is scraped into a 70mm×70mm×20mm mortar block frame. The sample is cured for 14 days at a temperature of 20°C and a relative humidity of 70%. The bonding strength test is then conducted on the insulation material sample.
[0107] Aging performance: The sample material was compression molded at 0.8 MPa, demoulded after 1 hour, cured at 25°C for 7 days, dried at 60°C for 5 hours, and then irradiated with a xenon arc lamp to accelerate material aging until cracks appeared in the material, and the aging time was recorded.
[0108] Water absorption rate: The sample material was compression molded at 0.8 MPa, demolded after 1 hour, cured at 25°C for 7 days, and dried at 60°C for 5 hours. The dried material was cut into cubic specimens with a size of 50 mm × 50 mm × 50 mm, and the dry mass m0 was recorded; the specimen was completely immersed in distilled water at 25°C, with the water level 50 mm higher than the top surface of the specimen. Soak for 24 hours, take out the specimen, absorb the surface moisture with filter paper, and record the wet mass m1. The water absorption rate was calculated according to the following formula: Water absorption rate (%) = (m1-m0) / m0×100%.
[0109] The test results are as follows:
[0110] Table 1 Material performance test results
[0111]
[0112] According to the comparative analysis of Example 1 and Comparative Example 1, the hydrophobic alkyl chain of dodecyltrichlorosilane completes the directional self-assembly on the surface of the thermal insulation material through the siloxane bond, and the steric hindrance effect of its long-chain alkyl group can effectively suppress the molecular thermal vibration, thereby reducing the thermal conductivity of the material. At the same time, the silane group is chemically coupled with the hydroxyl group on the surface of the substrate, significantly improving the interfacial bonding strength.
[0113] Combining the experimental data of Example 1 with Comparative Examples 2 and 3, it is found that the synergistic effect of polyethylene glycol diacrylate and polycaprolactone diol can form a three-dimensional interpenetrating network structure through free radical copolymerization, thereby realizing efficient loading of functional additives; the introduction of polycaprolactone diol can enhance the pore connectivity of the material, thereby providing a controllable path for water diffusion; the introduction of ethylene glycol diacrylate increases the degree of crosslinking, and its molecular chain extension is limited, thereby generating nanoscale pores, which inhibit liquid water penetration by capillary action. The reaction product of trimethylolpropane trimethacrylate and ethylene glycol di(3-mercaptopropionate) can construct a rigid-flexible composite skeleton. This structure suppresses the free path of gas molecules through the nano-confinement effect, and gas heat conduction is effectively blocked, thereby achieving better thermal insulation performance.
[0114] Comparative test data from Example 1 and Comparative Examples 4 and 5 indicate that a composite system of silicon-modified wood cellulose and fly ash with a multi-grade particle size ratio can construct a three-dimensional interpenetrating network structure with gradient pores through the hydrogen bond complexation between the hydroxyl groups of the wood fibers and the Al-O-Si bonds on the surface of the fly ash particles, thereby reducing the thermal conductivity of the material. Furthermore, the stress dispersion effect of the fly ash and the bridging toughening mechanism of the silicon-modified wood cellulose synergistically enhance the mechanical properties of the thermal insulation material, providing support for industrial-scale applications.
[0115] The heat-insulating wall material based on industrial waste fly ash prepared by the present invention is used to build a greenhouse, which can achieve that the greenhouse wall is almost perpendicular to the ground, thereby reducing the floor area of the same type of greenhouse and saving land.
[0116] This specific embodiment is merely an explanation of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art may make non-creative modifications to this embodiment as needed. However, as long as such modifications are within the scope of the claims of the present invention, they are protected by patent law.
Claims
1. A thermal insulation wall material based on industrial waste fly ash, characterized in that: Including the following raw materials by weight: 30-50 parts of Portland cement, 8-12 parts of modified copolymer, 6-8 parts of functional additives, 15-25 parts of aggregate, 0.5-1 part of water reducer, 2-5 parts of foam stabilizer, 4-6 parts of silicon-modified wood cellulose, and 20-30 parts of deionized water.
2. The thermal insulation wall material based on industrial waste fly ash according to claim 1, characterized in that: The modified copolymer is prepared by the following method: Methyl palmitate is added to xylene and stirred, styrene-maleic anhydride copolymer is added and stirred, a modifier and benzoyl peroxide are added, the mixture is heated and stirred, and the mixture is poured into methanol for precipitation, filtered, washed, and dried to obtain a modified copolymer.
3. The thermal insulation wall material based on industrial waste fly ash according to claim 2, characterized in that: The modified copolymer comprises the following components in parts by mass: 8-15 parts of methyl palmitate, 10-20 parts of styrene-maleic anhydride copolymer, 0.5-1 part of a modifier, 0.05-0.1 part of benzoyl peroxide, and 80-90 parts of xylene.
4. The thermal insulation wall material based on industrial waste fly ash according to claim 2, characterized in that: The modifier is prepared by the following method: Disperse 4-vinylaniline in toluene, stir, add itaconic anhydride and triethylamine, heat, reflux with stirring, and distill under reduced pressure to obtain an intermediate product; wherein, 4-vinylaniline 15-25 parts, itaconic anhydride 10-12 parts, triethylamine 0.1-0.2 parts, toluene 80-100 parts; Dodecyltrichlorosilane is dispersed in DMF, stirred, the intermediate product and potassium carbonate are added, heated and stirred, and then the pH is adjusted, filtered, washed, and purified to obtain a modifier; wherein the modifier comprises 15-20 parts of dodecyltrichlorosilane, 25-30 parts of the intermediate product, 0.1-0.2 parts of potassium carbonate, and 100-110 parts of DMF.
5. The thermal insulation wall material based on industrial waste fly ash according to claim 1, characterized in that: The functional additive is prepared by the following method: A1. Trimethylolpropane trimethacrylate and ethylene glycol bis(3-mercaptopropionate) were mixed and stirred, benzoyl peroxide solution and azodicarbonamide were added, and the mixture was heated with stirring and distilled under reduced pressure to obtain an intermediate; A2. Disperse the intermediate in dimethyl sulfoxide, stir, add polyethylene glycol diacrylate and polycaprolactone diol, heat and stir, and distill under reduced pressure to obtain a functional additive.
6. The thermal insulation wall material based on industrial waste fly ash according to claim 5, characterized in that: In step A1, the following components are included in parts by mass: 8-12 parts of trimethylolpropane trimethacrylate, 15-20 parts of ethylene glycol di(3-mercaptopropionate), 15-20 parts of benzoyl peroxide solution, and 2-3 parts of azodicarbonamide; in step A2, the following components are included in parts by mass: 15-25 parts of the intermediate, 1.5-4 parts of polyethylene glycol diacrylate, 0.5-0.8 parts of polycaprolactone diol, and 60-80 parts of dimethyl sulfoxide.
7. The thermal insulation wall material based on industrial waste fly ash according to claim 1, characterized in that: The silicon-modified lignocellulose is prepared by the following method: Adding rice husk ash to a sodium hydroxide solution, heating and stirring, centrifuging, separating insoluble matter, and obtaining a silicon solution; wherein the mass ratio of rice husk ash to sodium hydroxide solution is 1-3:8-12, and the concentration of the sodium hydroxide solution is 1-3 mol / L; Add lignocellulose to silicon solution, adjust pH to 5-6, heat and stir, filter, wash and dry to obtain silicon-modified lignocellulose; wherein, lignocellulose is 8-15 parts and silicon solution is 50-60 parts.
8. The thermal insulation wall material based on industrial waste fly ash according to claim 1, characterized in that: The aggregate is obtained by grinding fly ash and then grading and screening, as follows: Fly ash with a particle size of 5-10 μm accounts for 20-30%, fly ash with a particle size of 15-25 μm accounts for 40-50%, fly ash with a particle size of 40-60 μm accounts for 10-15%, and fly ash with a particle size of 80-100 μm accounts for 5-15%.
9. A method for preparing a thermal insulation wall material based on industrial waste fly ash according to any one of claims 1 to 8, characterized in that: The following steps are involved: Aggregate, silicate cement, functional additives and deionized water are mixed and stirred; modified copolymer, silicon-modified wood cellulose, water reducer and foam stabilizer are added and stirred to obtain thermal insulation wall material.
10. Use of the thermal insulation wall material based on industrial waste fly ash according to any one of claims 1 to 8 in greenhouse technology.