Thermal insulation material as well as preparation method and application thereof

Abstract

The invention relates to a thermal insulation material and a preparation method and application thereof. The thermal insulation material comprises solid waste, an exciting agent, a foaming agent, a foam stabilizer, polyurethane, an optional dispersing agent and an optional fiber material, and based on the mass of the solid waste, the mass content of the polyurethane is 1%-10%. The polyurethane modified foam geopolymer fireproof thermal insulation material provided by the invention is simple in preparation process, and has the advantages of light weight, high strength, fire resistance, non-combustibility, low thermal conductivity and low cost.

Description

Technical Field

[0001] The present application relates to the field of solid waste resource utilization, and in particular to a thermal insulation material and a preparation method and application thereof. Background Art

[0002] The construction industry consumes a lot of resources and energy, and produces a lot of solid waste, sewage and noise pollution. At the same time, the operation and maintenance of buildings also consume a lot of energy. Building energy consumption accounts for about 30% of the total social energy consumption. Developing energy-saving buildings is one of the important ways to reduce building energy consumption and reduce carbon emissions. Developing and promoting new energy-saving and environmentally friendly thermal insulation materials for roofs and walls is an important research direction for achieving building energy conservation.

[0003] At present, the main wall insulation materials at home and abroad are hollow bricks, glass wool, vermiculite, polystyrene, polyurethane, phenolic resin, foam concrete, foam geopolymer, etc. Rigid polyurethane foam, polystyrene and phenolic resin have the lightest relative density and can achieve a lower thermal conductivity, so they are widely used. However, they are organic materials and their combustion performance is mostly Class B. Buildings using polystyrene and polyurethane foam boards have serious fire hazards.

[0004] At present, Class A non-combustible wall insulation materials include foam glass, rock wool, perlite, foam concrete, foam geopolymer, etc. Foam glass, rock wool, and perlite are generally expensive and not energy-saving and environmentally friendly. Foam concrete and geopolymer are increasingly favored by researchers and society. Foam concrete has always had the problem of low strength and is difficult to modify. Thermal power generation and steel smelting industries produce a large amount of industrial solid waste such as fly ash and slag. Geopolymer uses fly ash and slag as the main material. As an inorganic thermal insulation material, it not only has the characteristics of fireproof and non-combustible, but also can reuse industrial solid waste, low cost, environmental protection and energy saving. It is a wall insulation material with broad prospects. Therefore, research and development of lightweight, high-strength, low thermal conductivity foam geopolymer wall fireproof and thermal insulation materials is of great significance to building fire prevention, energy saving, environmental protection, solid waste recycling and reducing construction costs. Summary of the invention

[0005] In order to improve the light weight and high strength characteristics of foam geopolymer, the present application provides a polyurethane modified light weight and high strength foam geopolymer fireproof and thermal insulation material. The present application adds polyurethane during the preparation of the foam geopolymer, refines the pore structure of the geopolymer while maintaining the characteristics of low apparent density, and improves its mechanical properties, thereby obtaining a polyurethane reinforced light weight and high strength foam geopolymer fireproof and thermal insulation material.

[0006] In a first aspect, the present application provides a thermal insulation material, which includes solid waste, an activator, a foaming agent, a foam stabilizer, polyurethane, and an optional dispersant and an optional fiber material.

[0007] Wherein, based on the mass of the solid waste, the mass content of polyurethane is 1%-10%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or any value therebetween.

[0008] In some embodiments, the mass content of polyurethane is 2%-6%.

[0009] Within a certain dosage range, as the amount of polyurethane increases, the viscosity of the slurry used to prepare the thermal insulation material increases, reducing the risk of mold collapse during the foaming process. At the same time, it can also significantly adjust the bubble size of the foamed geopolymer, increase the strength of the prepared thermal insulation material, and reduce the thermal conductivity. However, the polyurethane dosage should not be too high, otherwise it will increase the apparent density and thermal conductivity.

[0010] In some embodiments, the raw materials for preparing the polyurethane include polyols and isocyanates.

[0011] In some embodiments, the polyols are selected from one or more of polyether polyols, polyester polyols and aromatic polyester polyols. In some embodiments, the polyols are selected from polyether polyols.

[0012] In some embodiments, the polyether polyol is prepared by polymerization of propylene oxide and an initiator.

[0013] In some embodiments, the isocyanate is selected from one or more of polymethylene polyphenyl polyisocyanate, toluene diisocyanate (TDI) and 4,4'-diphenylmethane diisocyanate (MDI).

[0014] In some embodiments, the solid waste is selected from fly ash and / or slag.

[0015] In some embodiments, the fly ash is selected from fly ash that meets the requirements of national standard Grade I fly ash. In some embodiments, the slag is selected from slag that meets the requirements of national S95 grade slag powder.

[0016] In some embodiments, based on the mass of the solid waste, the mass content of the fly ash is 10%-50%, for example, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49% or any value therebetween. In some embodiments, the mass content of the fly ash is 20%-40%.

[0017] In some embodiments, based on the mass of the solid waste, the mass content of the slag is 50%-90%, for example, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79%, 80%, 81%, 83%, 85%, 87%, 89% or any value therebetween. In some embodiments, the mass content of the slag is 60%-80%.

[0018] In some embodiments, based on the mass of the solid waste, the mass content of the stimulant is 30%-80%, for example, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79% or any value therebetween. In some embodiments, the mass content of the stimulant is 40%-60%.

[0019] In some embodiments, the activator is selected from one or more of base activators.

[0020] In some embodiments, the activator includes water glass and at least one base selected from sodium hydroxide and potassium hydroxide.

[0021] In some embodiments, the modulus of the water glass is 1.0-2.0. In some embodiments, the mass concentration of the water glass is 40%-50%.

[0022] In some embodiments, the water glass is selected from sodium water glass and / or potassium water glass.

[0023] In some embodiments, based on the mass of the solid waste, the mass content of the foaming agent is 2%-12%, for example, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5% or any value therebetween. In some embodiments, the mass content of the foaming agent is 5%-10%.

[0024] In some embodiments, the foaming agent is selected from one or more of hydrogen peroxide, aluminum powder, silicon powder, ammonium salt and sodium bicarbonate.

[0025] In some embodiments, based on the mass of the solid waste, the mass content of the foam stabilizer is 0.1%-3%, for example, 0.3%, 0.5%, 0.7%, 0.9%, 1.0%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, 2.0%, 2.1%, 2.3%, 2.5%, 2.7%, 2.9% or any value therebetween. In some embodiments, the mass content of the foam stabilizer is 1%-2%.

[0026] In some embodiments, the foam stabilizer is selected from one or more of anionic surfactants, cationic surfactants and diionic surfactants. In some embodiments, the foam stabilizer is selected from one or more of calcium stearate, tea saponin, sodium dodecylbenzene sulfonate, hydroxypropyl degraded cellulose and cetyltrimethylammonium bromide.

[0027] In some embodiments, based on the mass of the solid waste, the mass content of the fiber material is 0.05%-1.5%, for example, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1.0%, 1.1%, 1.3% or any value therebetween. In some embodiments, the mass content of the fiber material is 0.1%-1%.

[0028] In some embodiments, the fiber material is selected from one or more of polyethylene fiber, polypropylene fiber and basalt fiber.

[0029] In some embodiments, the diameter of the fiber material is 5 μm-20 μm, for example, 7 μm, 9 μm, 10 μm, 11 μm, 13 μm, 15 μm, 17 μm or 19 μm. In some embodiments, the length of the fiber material is 6 mm-20 mm, for example, 7 mm, 9 mm, 10 mm, 11 mm, 13 mm, 15 mm, 17 mm or 19 mm. In some embodiments, the tensile strength of the fiber material is greater than or equal to 300 MPa.

[0030] In some embodiments, based on the mass of the solid waste, the mass content of the dispersant is 1%-15%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 12%, 13%, 14% or any value therebetween. In some embodiments, the mass content of the dispersant is 2%-8%.

[0031] In some embodiments, the dispersant is selected from lubricating oil. The main component of lubricating oil is hydrocarbon compound, which can remain stable in alkaline geopolymer solution. Its advantages are: 1. It reduces water consumption and improves the overall performance of geopolymer without interfering with the reaction of geopolymer; 2. In order to ensure hydrophobicity, more calcium stearate is added to increase the viscosity of the slurry. The use of lubricating oil can adjust the fluidity of the slurry and improve the casting effect; 3. Lubricating oil can assist in dispersing polyurethane without interfering with the reaction of polyurethane; 4. While assisting dispersion, it does not reduce the foaming effect.

[0032] In some embodiments, in the thermal insulation material, SiO 2 With Al 2 O 3 The molar ratio of Na 2 O and Al 2 O 3 The molar ratio is 0.5-2.

[0033] In a second aspect, the present application provides a method for preparing the thermal insulation material according to the first aspect, which comprises the following steps:

[0034] Step S1: performing a first mixing of solid waste, a foam stabilizer, an optional fiber material, and an optional dispersant to obtain a first mixture;

[0035] Step S2: sequentially mixing the first mixture with an activator and a foaming agent to obtain a second mixture;

[0036] Step S3: performing a third mixing of the second mixture and a raw material liquid for preparing polyurethane to obtain a third mixture;

[0037] Step S4: molding, demoulding and curing the third mixture to obtain the thermal insulation material.

[0038] In the preparation method of the present application, the polyurethane used is a mixed liquid formed by stirring and mixing polyether polyol and isocyanate. In the traditional method of adding polyurethane to geopolymer insulation materials, polyurethane is only made into particles and used as filler. Although it can reduce the thermal conductivity, it will reduce the continuity of the matrix and is not good for strength. The present application has the following advantages: the polyurethane mixed liquid is directly mixed with the geopolymer slurry, and preferably a dispersant such as lubricating oil is used to assist in dispersion, which can make the geopolymer and polyurethane evenly mixed, and form a tighter organic-inorganic combination through intermolecular hydrogen bonds, which can simultaneously increase the matrix strength and reduce the thermal conductivity.

[0039] In some embodiments, in step S1, the temperature of the first mixing is 5° C.-40° C., for example, 10° C., 15° C., 20° C., 25° C., 30° C. or 35° C. In some embodiments, the temperature of the first mixing is room temperature.

[0040] In some embodiments, in step S1, the first mixing time is 3 min-30 min, for example, 5 min, 10 min, 15 min, 20 min or 25 min.

[0041] In some embodiments, in step S2, the temperature of the second mixing is 5° C.-40° C., for example, 10° C., 15° C., 20° C., 25° C., 30° C. or 35° C. In some embodiments, the temperature of the second mixing is room temperature.

[0042] In some embodiments, in step S2, the second mixing time is 3s-30s, for example, 5s, 10s, 15s, 20s or 25s.

[0043] In some embodiments, in step S3, the temperature of the third mixing is 5° C.-40° C., for example, 10° C., 15° C., 20° C., 25° C., 30° C. or 35° C. In some embodiments, the temperature of the third mixing is room temperature.

[0044] In some embodiments, in step S3, the third mixing time is 3s-30s, for example, 5s, 10s, 15s, 20s or 25s.

[0045] In some embodiments, in step S3, the raw material liquid for preparing the polyurethane is selected from a mixed liquid including polyether polyol and isocyanate.

[0046] In some embodiments, in step S4, the curing is selected from steam curing.

[0047] In some embodiments, in step S4, the curing temperature is 40°C-70°C, for example, 45°C, 50°C, 55°C, 60°C or 65°C.

[0048] In some embodiments, in step S4, the curing humidity is 70%-99%, for example, 75%, 80%, 85%, 90% or 95%.

[0049] In some embodiments, in step S4, the curing time is 5 h to 48 h, for example, 10 h, 18 h, 20 h, 24 h, 30 h, 36 h, 40 h, 42 h or 46 h.

[0050] In some embodiments, the method for preparing the thermal insulation material comprises the following specific steps:

[0051] a. Weigh the solid waste powder, foam stabilizer, and fiber material (toughened fiber), pour them into the slurry stirring pot, and stir them evenly in the stirring pot.

[0052] b. Then pour in the alkali activator and lubricant, stir with an electric stirrer at low speed (500r / min) for 5 minutes until the slurry is uniform, then pour in the foaming agent and stir at high speed (1100r / min) for 15 seconds. While stirring the slurry, mix the black and white polyurethane materials, the black polyurethane material is isocyanate, and the white material is polyether polyol, and stir quickly for 15 seconds. Preferably, after the foaming agent is added to the geopolymer slurry and stirred for 15 seconds, the liquid polyurethane mixture is quickly poured into the geopolymer slurry, and then stirred at high speed (1100r / min) for 15 seconds to mix the polyurethane liquid foam and the slurry evenly.

[0053] c. Pour the stirred slurry into the mold. The slurry height should be 1 / 3 to 1 / 2 of the mold height. Then put the mold into a sealed bag, foam it at room temperature of 20±2℃ for 30 minutes, and then put it into a 60℃ steam curing box for curing for 24 hours. After the curing time is over, demould it, saw off the excess part with a cutting machine, blow off the powder and get the polyurethane modified geopolymer foam fireproof and thermal insulation material.

[0054] In a third aspect, the present application provides application of the thermal insulation material described in the first aspect or the thermal insulation material prepared by the preparation method described in the second aspect in the field of building materials.

[0055] The polyurethane modified foam geopolymer fireproof and heat-insulating material provided in the present application has a simple preparation process and has the advantages of light weight, high strength, fireproof and non-combustible, low thermal conductivity and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] In order to more clearly illustrate the embodiments of the present application or the solutions in the prior art, a brief introduction will be given below to the drawings required for use in the embodiments. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0057] Figure 1 A comparison of the macroscopic images of the pore cross-sections of the thermal insulation materials of Comparative Example 6 (1A) and Example 1 (1B) of the present application is shown, and the pore structure is greatly optimized after the addition of polyurethane.

[0058] Figure 2 The microscopic images comparing the changes in the pore walls of the thermal insulation materials in Comparative Example 6 (2A) and Example 1 (2B) of the present application are shown. It can be observed that after the addition of polyurethane, the pore walls are optimized and the defects are reduced.

[0059] Figure 3The pore size distribution, average pore size and porosity of the thermal insulation materials prepared in Comparative Example 6 and Examples 11-15 of the present application are plotted as a function of the polyurethane dosage. Within the dosage range of 0-10wt.%, the average pore size decreases as the polyurethane dosage increases, and the planar porosity also decreases accordingly. The pore size is concentrated in the range of 0.5 to 2.0 mm, the pore structure is optimized, the strength is increased, and the thermal conductivity is reduced to a lower level at a polyurethane dosage of 2-4%.

[0060] Figure 4 This is a cross-sectional view of the thermal insulation material prepared in Example 8 of the present application. DETAILED DESCRIPTION

[0061] In order to make the purpose, technical solution and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. The specific embodiments described here are only used to explain the present application and are not intended to constitute any limitation to the present application.

[0062] In some embodiments, the preparation method of the polyurethane modified foam geopolymer fireproof and thermal insulation material provided in the present application is as follows:

[0063] (1) Preparation of alkaline activator: Sodium water glass and sodium hydroxide are selected as raw materials, sodium hydroxide is dissolved in water, and mixed with water glass, stirred evenly, and the alkaline activator modulus is adjusted to 1.0-2.0.

[0064] (2) Raw material mixing

[0065] Mix the active solid waste powder, foam stabilizer and fiber for 30 seconds, then add the alkali activator and stir for 5 minutes. Then add the foaming agent and stir at high speed for 15 seconds, then add the polyurethane that has just been mixed and stirred for 15 seconds and stir at high speed for another 15 seconds.

[0066] (3) Molding

[0067] The stirred slurry was introduced into the mold, foamed at room temperature for 30 minutes, and then transferred to the steam curing box at a steam curing temperature of 60°C for 24 hours.

[0068] (4) Cutting and demoulding

[0069] Use a cutting machine to cut off the excess material, then remove the regular test block from the mold, and clean up the debris to obtain the finished product.

[0070] In some embodiments, the expected performance parameters of the polyurethane modified foam geopolymer fireproof and thermal insulation material of the present application are shown in Table 1 below:

[0071] Table 1

[0072]

[0073] In the following examples and comparative examples, the apparent density test is carried out according to GB / T5486. The flexural strength and compressive strength are tested according to GBT 17671-2021 Cement mortar strength test method (ISO method). The thermal conductivity is tested according to ISO 22007-22022 Plastics. Determination of thermal conductivity and thermal diffusivity. Part 2: Transient plane heat source (hot disk) method, and the instrument is a Hotdisk thermal conductivity meter.

[0074] The present application is further described below in conjunction with specific embodiments and comparative examples.

[0075] Example 1

[0076] Use sodium hydroxide and deionized water to prepare an alkali activator with a water glass modulus of 1.2 and a solid content of 40% for later use.

[0077] Weigh 120g of primary fly ash, 180g of S 95 mineral powder, 1.2g of polypropylene toughened fiber, and 6g of calcium stearate, use an electric stirrer to stir the dry material at low speed for 30s; add an alkali activator and lubricating oil, stir at low speed for 5min, and stir the slurry evenly; add 27g of hydrogen peroxide, stir at high speed for 15s to obtain a slurry; at the same time, 2wt.% of polyurethane black and white material (the black material is polymethylene polyphenyl polyisocyanate (PAPI), and the white material is polyether polyol (provided by Dacheng County Guang'an Chemical Co., Ltd., prepared by polymerization of propylene oxide, initiator water and glycerol, CAS No. 9003-11-6)) is mixed and stirred, and then added to the slurry and stirred at high speed for 15s.

[0078] In the slurry, based on the total mass of fly ash and mineral powder, the mass content of fly ash is 40%, the mass content of mineral powder is 60%, in addition, the mass content of alkali activator (water glass + sodium hydroxide) is equivalent to 58% of the total mass of fly ash mineral powder. Similarly, the mass content of toughening fiber is 0.4%, the mass content of calcium stearate is 2%, the mass content of hydrogen peroxide is 9%, the mass content of polyurethane mixture is 2%, and the mass content of lubricating oil is 3%.

[0079] The slurry was poured into the mold, sealed, and foamed at room temperature for 30 minutes. It was then placed in a 60°C steam curing box for 24 hours, and then cut and demolded to obtain a thermal insulation material test block.

[0080] The test piece was placed in a sealed bag and cured at room temperature for 28 days, then dried at 60℃ for 24 hours. The apparent density was measured to be 163kg / m 3 , flexural strength 0.23MPa, compressive strength 0.51MPa, thermal conductivity 0.068W / (m·K).

[0081] Example 2

[0082] Use sodium hydroxide and deionized water to prepare an alkali activator with a water glass modulus of 1.2 and a solid content of 40% for later use.

[0083] Weigh 100 g of primary fly ash, 200 g of S 95 mineral powder, 3 g of polypropylene toughened fiber, and 6 g of calcium stearate, stir the dry material at low speed for 30 seconds, then add an alkali activator and lubricating oil, and use an electric stirrer to stir at low speed for 5 minutes; then add 24 g of hydrogen peroxide and stir at high speed for 15 seconds to obtain a slurry; at the same time, 8 wt.% of polyurethane black and white material (same as Example 1) is mixed and stirred, then added to the slurry and stirred at high speed for 15 seconds.

[0084] In the slurry, based on the total mass of fly ash and mineral powder, the mass content of fly ash is 33%, the mass content of mineral powder is 67%, the mass content of alkali activator (water glass + sodium hydroxide) is 60% of the total mass of fly ash and mineral powder, similarly, the mass content of toughening fiber is 1%, the mass content of calcium stearate is 2%, the mass content of hydrogen peroxide is 8%, the mass content of polyurethane mixture is 8%, and the mass content of lubricating oil is 3%.

[0085] The slurry was poured into the mold, sealed, and foamed at room temperature for 30 minutes. It was then placed in a 60°C steam curing box for 24 hours, and then cut and demolded to obtain a thermal insulation material test block.

[0086] The test piece was placed in a sealed bag and cured at room temperature for 28 days, then dried at 60℃ for 24 hours. The apparent density was measured to be 302kg / m 3 , flexural strength 0.31MPa, compressive strength 1.15MPa, thermal conductivity 0.112W / (m·K).

[0087] Example 3

[0088] Use sodium hydroxide and deionized water to prepare an alkali activator with a water glass modulus of 1.2 and a solid content of 40% for later use.

[0089] Weigh 150 g of primary fly ash, 150 g of S 95 mineral powder, 1.2 g of polypropylene toughened fiber, and 6 g of calcium stearate, use an electric stirrer to stir at low speed for 30 seconds, then add an alkali activator and lubricating oil, and stir at low speed for 5 minutes; then add 27 g of hydrogen peroxide, stir at high speed for 15 seconds to obtain a slurry; at the same time, 1 wt.% of polyurethane black and white material (same as Example 1) is mixed and stirred, then added to the slurry and stirred at high speed for 15 seconds.

[0090] In the slurry, based on the total mass of fly ash and mineral powder, the mass content of fly ash is 50%, the mass content of mineral powder is 50%, the mass content of alkali activator (water glass + sodium hydroxide) is equivalent to 64% of the total mass of fly ash and mineral powder, the mass content of toughening fiber is 0.4%, the mass content of calcium stearate is 2%, the mass content of hydrogen peroxide is 9%, the mass content of polyurethane mixture is 1%, and the mass content of lubricating oil is 3%.

[0091] The slurry was poured into the mold, sealed, and foamed at room temperature for 30 minutes. It was then placed in a 60°C steam curing box for 24 hours, and then cut and demolded to obtain a thermal insulation material test block.

[0092] The test piece was placed in a sealed bag and cured at room temperature for 28 days, then dried at 60℃ for 24 hours. The apparent density was measured to be 152kg / m 3 , flexural strength 0.22MPa, compressive strength 0.41MPa, thermal conductivity 0.059W / (m·K).

[0093] Example 4

[0094] Use sodium hydroxide and deionized water to prepare an alkali activator with a water glass modulus of 1.2 and a solid content of 40% for later use.

[0095] Weigh 30 g of primary fly ash, 270 g of S 95 mineral powder, 2.4 g of polypropylene toughened fiber, and 4 g of calcium stearate, use an electric stirrer to stir at low speed for 30 seconds, then add an alkali activator and lubricating oil, and stir at low speed for 5 minutes; add 27 g of hydrogen peroxide, stir at high speed for 15 seconds to obtain a slurry; at the same time, 4 wt.% of polyurethane black and white material (same as Example 1) is mixed and stirred, then added to the slurry and stirred at high speed for 15 seconds.

[0096] In the slurry, based on the total mass of fly ash and mineral powder, the mass content of fly ash is 10%, the mass content of mineral powder is 90%, the mass content of alkali activator (water glass + sodium hydroxide) is equivalent to 60% of the total mass of fly ash mineral powder, similarly, the mass content of toughening fiber is 0.8%, the mass content of calcium stearate is 1.3%, the mass content of hydrogen peroxide is 9%, the mass content of polyurethane mixture is 4%, and the mass content of lubricating oil is 3%.

[0097] The slurry was poured into the mold, sealed, and foamed at room temperature for 30 minutes. It was then placed in a 60°C steam curing box for 24 hours, and then cut and demolded to obtain a thermal insulation material test block.

[0098] The test piece was placed in a sealed bag and cured at room temperature for 28 days, then dried at 60℃ for 24 hours. The apparent density was measured to be 191kg / m 3 , flexural strength 0.34MPa, compressive strength 0.55MPa, thermal conductivity 0.079W / (m·K).

[0099] Example 5

[0100] Use sodium hydroxide and deionized water to prepare an alkali activator with a water glass modulus of 1.2 and a solid content of 40% for later use.

[0101] Weigh 81 g of primary fly ash, 189 g of S 95 mineral powder, 30 g of HL 38 hollow glass microspheres, 1.2 g of polypropylene toughened fiber, and 6 g of calcium stearate, use an electric stirrer to stir at low speed for 30 seconds, then add an alkali activator and lubricating oil and stir at low speed for 5 minutes; add 27 g of hydrogen peroxide and stir at high speed for 15 seconds to obtain a slurry; at the same time, 1 wt.% of polyurethane black and white material (same as in Example 1) is mixed and stirred, then added to the slurry and stirred at high speed for 15 seconds.

[0102] The slurry was poured into the mold, sealed, and foamed at room temperature for 30 minutes. It was then placed in a 60°C steam curing box for 24 hours, and then cut and demolded to obtain a thermal insulation material test block.

[0103] In the slurry, based on the total mass of fly ash and mineral powder, the mass content of fly ash is 27%, the mass content of mineral powder is 73%, the mass content of alkali activator (water glass + sodium hydroxide) is 77% of the total mass of fly ash and mineral powder, similarly, the mass content of glass microbeads is 10%, the mass content of toughening fiber is 0.4%, the mass content of calcium stearate is 2%, the mass content of hydrogen peroxide is 9%, the mass content of polyurethane mixture is 1%, and the mass content of lubricating oil is 3%.

[0104] After the test piece was cured at room temperature for 28 days, it was dried at 60℃ for 24 hours. The apparent density after drying was 141kg / m 3 , flexural strength 0.28MPa, compressive strength 0.47MPa, thermal conductivity 0.052W / (m·K).

[0105] Embodiments 6 to 10

[0106] The difference between Examples 6 to 10 and Example 1 is that the dosage of solid waste powder (fly ash and / or mineral powder), hydrogen peroxide and polyurethane is different, as shown in Table 2. The other components and operations are the same, and the performance test data are shown in Table 3.

[0107] Examples 11 to 15

[0108] The difference between Examples 11 to 15 and Example 2 is that the dosage of solid waste powder (fly ash and / or mineral powder), activator, foaming agent hydrogen peroxide and polyurethane is different, see Table 2 for details. The other components and operations are the same, and the performance test data are shown in Table 3.

[0109] Example 16

[0110] The difference between Example 16 and Example 1 is that the types of polyurethane black and white materials are different, wherein the white material of Example 16 is polyester polyol (polybutylene adipate-1,4-diol, PBA1000, purchased from Liduo Chemical), and the rest are the same, see Table 2 for details. The performance test data is shown in Table 3.

[0111] As can be seen from Table 3, after polyester polyol replaces polyether polyol, the result is not favorable for strength. This is because the polyurethane formed by polyether polyol and isocyanate has better hydrolysis resistance, while the ester group of the polyurethane formed by polyester polyol and isocyanate is more easily hydrolyzed in alkaline solution; the polyether polyurethane used in this application has better water resistance and can better enhance the toughness and strength of the foamed geopolymer.

[0112] Table 2

[0113]

[0114] Table 3

[0115]

[0116]

[0117] Comparative Examples 1 to 5

[0118] Directly adding polyurethane particles with a fineness of 200 mesh will cause the hydration product C / NASH to be separated by the polyurethane particles, resulting in more defects. It is difficult for organic particles to form a sufficient connection with inorganic geopolymers, which will reduce the strength of the geopolymer matrix and is very unfavorable to the flexural strength.

[0119] As shown in Table 4 and Table 5. Polyurethane particles are made by reacting polyether polyol and isocyanate. The process flow is as follows:

[0120] Use sodium hydroxide and deionized water to prepare an alkali activator with a water glass modulus of 1.2 and a solid content of 40% for later use.

[0121] Weigh 77 g of primary fly ash, 179 g of S 95 mineral powder, 45 g of polyurethane particles, 1.2 g of polypropylene toughened fiber, and 6 g of calcium stearate, use an electric stirrer to stir at low speed for 30 seconds, then add alkali activator and lubricating oil, stir at low speed for 5 minutes; add 27 g of 30% mass fraction of Chinese medicine hydrogen peroxide, stir at high speed for 30 seconds to obtain a slurry.

[0122] In the slurry, based on the total mass of 300g of fly ash and mineral powder, they account for 30% and 70% respectively. 15% polyurethane particles replace 45g of powder mass (Comparative Example 4), then the fly ash mass is reduced from 90g to 77g, the mineral powder mass is reduced from 210g to 179g, and the total mass of the three is 300g (similarly, in Comparative Example 1, the fly ash is 90g, the mineral powder is 210g, and the polyurethane particles are 0g; in Comparative Example 2, the fly ash is 85.5g, the mineral powder is 199.5g, and the polyurethane particles are 15g; in Comparative Example 3, the fly ash is 81g, the mineral powder is 189g, and the polyurethane particles are 30g; in Comparative Example 4, the fly ash is 76.5g, the mineral powder is 178.5g, and the polyurethane particles are 60g; in Comparative Example 5, the fly ash output is 72g, and the mineral powder content is 168g). The mass content of the alkali activator (water glass + sodium hydroxide) is equivalent to 58% of the total mass of 300g. Similarly, the mass content of the toughened fiber is 0.4% of the total mass, the mass content of calcium stearate is 2.0%, the mass content of hydrogen peroxide is 9%, and the mass content of the lubricating oil is 3% of the total mass.

[0123] The slurry was poured into the mold, sealed, and foamed at room temperature for 30 minutes. It was then placed in a 60°C steam curing box for 24 hours, and then cut and demolded to obtain a thermal insulation material test block.

[0124] The test pieces were placed in sealed bags and cured at room temperature for 28 days, then dried at 60°C for 24 hours. The apparent density, flexural strength, compressive strength and thermal conductivity were measured as shown in Table 5.

[0125] Table 4

[0126]

[0127] Table 5

[0128] sample Flexural strength MPa Compressive strength MPa <![CDATA[28d apparent density kg / m 3 > Thermal conductivity W / (m·K) Comparative Example 1 0.22 0.44 193 0.095 Comparative Example 2 0.14 0.41 197 0.094 Comparative Example 3 0.16 0.45 206 0.096 Comparative Example 4 0.15 0.38 214 0.099 Comparative Example 5 0.17 0.37 226 0.103

[0129] Comparative Example 6

[0130] The difference between Comparative Example 6 and Example 6 is that the polyurethane mixture content is 0 and the hydrogen peroxide content is 9%. The flexural strength is 0.12MPa, the compressive strength is 0.23MPa, and the apparent density is 174kg / m 3 , the thermal conductivity is 0.085W / (m·K).

[0131] Comparison of the pore cross-section macroscopic images of the thermal insulation materials of Comparative Example 6 (1A) and Example 1 (1B) of the present application Figure 1 As shown, from Figure 1 It can be seen that the pore structure is greatly optimized after the addition of polyurethane.

[0132] The microscopic images of the changes in the pore walls of the thermal insulation materials in Comparative Example 6 (2A) and Example 1 (2B) of the present application are as follows: Figure 2 As shown, from Figure 2 It can be observed that after adding polyurethane, the pore wall is optimized and the defects are reduced.

[0133] The pore size distribution, average pore size and porosity of the thermal insulation materials prepared in Comparative Example 6 and Examples 11-15 of the present application vary with the polyurethane content as shown in the figure. Figure 3 As shown. Figure 3 It can be seen that within the range of 0-10wt.%, the average pore size decreases with the increase of polyurethane dosage, the planar porosity also decreases, the pore size is concentrated in the range of 0.5-2.0mm, the pore structure is optimized, the strength is increased, and the thermal conductivity is reduced to a lower level at 2-4% polyurethane dosage.

[0134] The polyurethane modified foam geopolymer fireproof and heat-insulating material provided in the present application is prepared with fly ash and mineral powder as main raw materials, combined with other mineral raw materials and toughening fibers, using advanced chemical foaming technology. It has simple production process, reliable performance and good stability. The product can be used as fireproof material, heat-insulating material, sound-proof material, thermal insulation material, etc.

[0135] The technical solution of the present application is not limited to the above-mentioned specific embodiments, and all technical variations made according to the technical solution of the present application fall within the protection scope of the present application.

Claims

1. A thermal insulation material comprising solid waste, an activator, a foaming agent, a foam stabilizer, polyurethane, an optional dispersant, and an optional fiber material, in, Based on the mass of the solid waste, the mass content of polyurethane is 1%-10%, preferably 2%-6%.

2. The thermal insulation material according to claim 1, characterized in that: The raw materials for preparing the polyurethane include polyols and isocyanates. Preferably, the polyol material is selected from one or more of polyether polyols, polyester polyols and aromatic polyester polyols, preferably selected from polyether polyols; Preferably, the isocyanate is selected from one or more of polymethylene polyphenyl polyisocyanate, toluene diisocyanate and 4,4'-diphenylmethane diisocyanate (MDI).

3. The thermal insulation material according to claim 1 or 2, characterized in that: The solid waste is selected from fly ash and / or slag, Preferably, based on the mass of the solid waste, the mass content of the fly ash is 10%-50%, preferably 20%-40%; and / or the mass content of the slag is 50%-90%, preferably 60%-80%.

4. The thermal insulation material according to any one of claims 1 to 3, wherein the mass content of the activator is 30%-80%, preferably 40%-60%, based on the mass of the solid waste; and / or The activator is selected from one or more alkaline activators. Preferably, the activator includes water glass and at least one alkali selected from sodium hydroxide and potassium hydroxide. More preferably, the modulus of the water glass is 1.0-2.0 and the mass concentration is 40%-50%.

5. The thermal insulation material according to any one of claims 1 to 4, characterized in that: Based on the mass of the solid waste, the mass content of the foaming agent is 2%-12%, preferably 5%-10%; and / or Based on the mass of the solid waste, the mass content of the foam stabilizer is 0.1%-3%, preferably 1%-2%; and / or Based on the mass of the solid waste, the mass content of the fiber material is 0.05%-1.5%, preferably 0.1%-1%; and / or Based on the mass of the solid waste, the mass content of the dispersant is 1%-15%, preferably 5%-10%.

6. The thermal insulation material according to any one of claims 1 to 5, characterized in that: The foaming agent is selected from one or more of hydrogen peroxide, aluminum powder, silicon powder, ammonium salt and sodium bicarbonate; The foam stabilizer is selected from one or more of anionic surfactants, cationic surfactants and diionic surfactants, preferably one or more of calcium stearate, tea saponin, sodium dodecylbenzene sulfonate, hydroxypropyl degraded cellulose, and hexadecyltrimethylammonium bromide; and / or The fiber material is selected from one or more of polyethylene fiber, polypropylene fiber and basalt fiber; and / or The fiber material has a diameter of 5 μm-20 μm, a length of 6 mm-20 mm, and a tensile strength greater than or equal to 300 MPa; and / or The dispersant is selected from lubricating oil.

7. The thermal insulation material according to any one of claims 1 to 6, characterized in that: In the thermal insulation material, the molar ratio of SiO2 to Al2O3 is 2-4.5, and the molar ratio of Na2O to Al2O3 is 0.5-2.

8. A method for preparing a thermal insulation material according to any one of claims 1 to 7, comprising the following steps: Step S1: performing a first mixing of solid waste, a foam stabilizer, an optional fiber material, and an optional dispersant to obtain a first mixture; Step S2: sequentially mixing the first mixture with an activator and a foaming agent to obtain a second mixture; Step S3: performing a third mixing of the second mixture and a raw material liquid for preparing polyurethane to obtain a third mixture; Step S4: molding, demoulding and curing the third mixture to obtain the thermal insulation material.

9. The preparation method according to claim 8, characterized in that: In step S1, the temperature of the first mixing is 5°C-40°C, and the time of the first mixing is 3min-30min; and / or In step S2, the temperature of the second mixing is 5°C-40°C, and the time of the second mixing is 3s-30s; and / or In step S3, the temperature of the third mixing is 5°C-40°C, and the time of the third mixing is 3s-30s; and / or In step S3, the raw material liquid for preparing the polyurethane is selected from a mixed liquid including polyether polyol and isocyanate; and / or In step S4, the curing is selected from steam curing, and / or the curing temperature is 40° C.-70° C., the curing humidity is 70%-99%, and the curing time is 5h-48h.

10. Use of the thermal insulation material according to any one of claims 1 to 7 or the thermal insulation material prepared by the preparation method according to claim 8 or 9 in the field of building materials.

Images