Waterproof and heat-insulating anion material and preparation method thereof

Abstract

This invention provides a waterproof and heat-insulating negative ion material and its preparation method. The waterproof and heat-insulating negative ion material includes a filler and a thermosetting resin. The filler includes modified hexagonal stone, which is modified with a fluorinated surfactant, and the modified hexagonal stone accounts for 15-30 wt% of the negative ion material. The thermosetting resin includes phenolic resin and epoxy resin, and the mass ratio of phenolic resin to epoxy resin is 1-1.5:0.1-0.2. This waterproof and heat-insulating negative ion material possesses excellent heat insulation performance, waterproof and water-resistant properties, and good bactericidal and bacteriostatic properties.

Description

Technical Field

[0001] This invention relates to the field of materials, specifically to a waterproof and heat-insulating negative ion material and its preparation method. Background Technology

[0002] Since the 19th century, humanity has obtained energy through burning fossil fuels, causing global temperatures to rise by 1.1 degrees Celsius above pre-industrial levels. This trend is expected to continue for the next two decades, reaching 1.5 degrees Celsius above pre-industrial levels. Under this inevitable trajectory, global warming and rising temperatures have made energy consumption a major global challenge. Therefore, developing thermal insulation materials that can cool the substrate under sunlight has become a mainstream trend. Traditional thermal insulation materials in my country have many drawbacks, especially those made primarily of inorganic materials such as asbestos and perlite, and organic materials such as expanded polystyrene, which suffer from poor thermal insulation and waterproofing performance.

[0003] To overcome the above shortcomings, it is necessary to seek a material with good waterproof performance and excellent heat insulation effect. Summary of the Invention

[0004] The purpose of this invention is to provide a waterproof and heat-insulating negative ion material and its preparation method. This waterproof and heat-insulating negative ion material has excellent heat insulation performance and waterproof and water-resistant properties, as well as good bactericidal and bacteriostatic properties.

[0005] According to one aspect of the present invention, a waterproof and heat-insulating negative ion material is provided, comprising a filler and a thermosetting resin; the filler includes modified hexagonal stone, which is modified by a fluorinated surfactant, and the modified hexagonal stone accounts for 15-30 wt% of the negative ion material; the thermosetting resin includes phenolic resin and epoxy resin, and the ratio of phenolic resin to epoxy resin is 1-1.5:0.1-0.2 by mass. The waterproof and heat-insulating negative ion material provided by this solution can not only generate negative ions for a long time, but also has excellent heat insulation and reflection performance and good water resistance. The modified hexagonal stone used in this solution, due to its modification by a fluorinated surfactant, exposes more active sites, allowing for a longer-lasting release of negative ions. When negative ions come into contact with bacteria, they can destroy the bacterial structure, leading to bacterial death and achieving a bactericidal effect. High-temperature heat sources such as the sun and burning materials radiate radiant energy. When an object receives this radiant energy, it converts it into heat energy, causing the object's temperature to rise. This solution modifies hexagonal stone, increasing its surface roughness. When combined with a thermosetting resin in the specified ratio, the resulting negative ion material exhibits excellent reflective heat insulation. This allows the material to reflect most of the radiation energy from a high-temperature heat source, reducing its absorption and thus minimizing heat conversion. Furthermore, compared to materials made with conventional hexagonal stone and thermosetting resin, the modified hexagonal stone and resin combination produces a material with more hydrophobic groups. After curing, these groups migrate to the surface, forming an organic hydrophobic layer that enhances the material's hydrophobic and waterproof properties, preventing water from penetrating.

[0006] Preferably, the molecular structure of the fluorosurfactant satisfies general formula I: By modifying hexagonal stone with a fluorinated surfactant that satisfies the above structural formula, negative ion materials with better heat insulation and reflective properties and easier negative ion generation can be obtained. This is because the hydrophilic groups in the fluorinated surfactant have better compatibility with the surface defects of hexagonal stone, allowing the fluorinated surfactant to be better adsorbed within the surface defects, thereby improving the modification effect and ultimately enhancing the heat insulation and hydrophobic properties of the negative ion material.

[0007] Preferably, in the general formula I of the fluorosurfactant, n is 3-6 and m is 6-12. In general formula I, the values ​​of n and m affect the ratio of hydrophilic to lipophilic groups in the fluorosurfactant. When the fluorosurfactant satisfies the condition of n being 3-6 and m being 6-12 in general formula I, it can ensure that the hydrophilic-lipophilic balance value of the fluorosurfactant is greater than 10, while also ensuring that the carbon chain length of the fluorosurfactant is moderate and the molecular steric hindrance is small, which is beneficial for modifying hexagonalite. The resulting hexagonalite has a low solid thermal conductivity and excellent thermal insulation properties. When hexagonalite is modified using a fluorosurfactant that meets the above conditions, the modified hexagonalite has good compatibility with thermosetting resins and can form anionic materials with high crosslinking density, good hydrophobicity, and excellent thermal insulation properties.

[0008] Optionally, the fluorinated surfactant is a product manufactured by Shanghai Fluorine Technology Co., Ltd., with the brand name FEO-300. The molecular structure of this FEO-300 product satisfies General Formula I, where n = 3–6 and m = 6–8.

[0009] Optionally, the fluorinated surfactant is a product manufactured by Shanghai Fluorine Technology Co., Ltd., with the brand name FEO-500. The molecular structure of this FEO-500 product satisfies General Formula I, where n = 3 to 6 and m = 10 to 12.

[0010] Preferably, the preparation method of modified hexagonalite includes the following steps: Hexagonalite is mixed with a strong acid solution at a temperature of 25–35°C and stirred for 0.5–1 hour; then, the hexagonalite is calcined at a temperature of 300–400°C for 1–2 hours to obtain acidified hexagonalite; the acidified hexagonalite is then mixed uniformly with a fluorinated surfactant at a temperature of 60–70°C and stirred for 0.5–1 hour to obtain modified hexagonalite. Before modifying the hexagonalite with the fluorinated surfactant, the hexagonalite is first acidified to generate more surface defects and expose more active sites, thereby enhancing its ability to generate negative ions over a long period. Then, the fluorinated surfactant is mixed uniformly with the acidified hexagonalite. The fluorinated surfactant can be adsorbed onto the surface defects of the acidified hexagonalite, thus introducing fluorine into the hexagonalite and improving the bactericidal, hydrophobic, and heat-insulating properties of the negative ion materials using this modified hexagonalite.

[0011] Preferably, the concentration of the strong acid solution is 0.85–1.25 mol / L. Using a strong acid solution of the above concentration to acidify and calcine hexagonalite can promote the exposure of active sites and the generation of more surface defects in hexagonalite while ensuring the stability of its crystal structure, thereby reducing the difficulty of modifying hexagonalite.

[0012] Preferably, the strong acid solution is a hydrochloric acid solution.

[0013] Preferably, the amount of fluorinated surfactant used is 3-5 mol / 50g of acidified hexagonalite.

[0014] Preferably, the average particle size of the modified hexagonal stone is 5–15 μm. Smaller particle size modified hexagonal stone enhances the thermal insulation performance of waterproof and heat-insulating negative ion materials. Smaller particle size zirconium silicate results in a stronger heat-reflecting ability in the prepared negative ion material; however, excessively small zirconium silicate particles are prone to aggregation during curing. Therefore, after preparing the modified hexagonal stone, grinding and sieving it to ensure the average particle size meets the aforementioned requirements allows the negative ion material using this modified hexagonal stone to exhibit excellent reflective thermal insulation properties.

[0015] Preferably, the filler also includes molybdenum disulfide. Molybdenum disulfide has a special layered structure that can extend the heat transfer path of solids, and its loose layered structure can inhibit heat transfer between gas molecules, resulting in excellent thermal insulation performance. When the negative ion material includes both molybdenum disulfide and modified hexagonalite, there is a synergistic effect between the modified hexagonalite and molybdenum disulfide, which enables the negative ion material to have a better heat insulation and reflection effect, thus promoting the cooling of building walls.

[0016] Preferably, the mass ratio of modified hexagonalite to molybdenum disulfide is 3-4:0.8-1.1. When the mass ratio of modified hexagonalite to molybdenum disulfide is within the above range, the resulting waterproof and heat-insulating negative ion material exhibits high reflectivity for light with wavelengths in the range of 400-2000 nm, effectively reflecting most of the heat from sunlight.

[0017] According to another aspect of the present invention, a method for preparing the above-mentioned waterproof and heat-insulating negative ion material is provided, comprising the following operations: weighing the raw materials for preparing the waterproof and heat-insulating negative ion material according to the specified amount, and mixing the components evenly according to the specified ratio at 25-35°C to obtain the waterproof and heat-insulating negative ion material. Detailed Implementation

[0018] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0019] Example 1

[0020] (1) Preparation of modified hexagonalite

[0021] The raw materials for preparing modified hexagonal ore include hexagonal ore, a fluorinated surfactant, hydrochloric acid solution, and an aqueous solvent. The concentration of the hydrochloric acid solution is 1 mol / L, and the fluorinated surfactant selected has the following structural formula: Perfluoroalkyl ethanol polyoxyethylene ether with n = 3–6 and m = 6–8 is preferred. The preferred product is FEO-300 manufactured by Shanghai Fluorine Technology Co., Ltd.

[0022] The preparation method of modified hexagonal ore includes the following steps:

[0023] Weigh the raw material for preparing modified hexagonalite, mix hexagonalite with a strong acid solution at a solid-liquid ratio of 1:4 at 30°C, stir for 0.5 hours, filter, wash the hexagonalite with deionized water until neutral, and then calcine the hexagonalite at 350°C for 1.5 hours to obtain acidified hexagonalite.

[0024] At 65℃, acidified hexagonalite and a fluorinated surfactant were mixed evenly and stirred for 0.5 hours to obtain modified hexagonalite. The modified hexagonalite was then ground and sieved. The amount of fluorinated surfactant used was 4 mol / 50g acidified hexagonalite.

[0025] (2) Preparation of waterproof and heat-insulating negative ion materials

[0026] The raw materials for preparing this waterproof and heat-insulating negative ion material include 25 parts of filler and 70 parts of thermosetting resin. The thermosetting resin comprises 62.5 parts of phenolic resin and 7.5 parts of epoxy resin, with a mass ratio of phenolic resin to epoxy resin of 1.25:0.15. The filler includes 20 parts of the aforementioned modified hexagonal stone and 5 parts of molybdenum disulfide, with a mass ratio of modified hexagonal stone to molybdenum disulfide of 4:1. The average particle size of the modified hexagonal stone is 10 μm.

[0027] The preparation method of waterproof and heat-insulating negative ion materials includes the following steps:

[0028] Weigh out the raw materials used to prepare the waterproof and heat-insulating negative ion material according to the specified amount, and mix the components evenly at 30℃ according to the specified ratio to obtain the waterproof and heat-insulating negative ion material.

[0029] In other embodiments, additives may be added to the negative ion material, or the type and amount of additives may be adjusted, depending on the actual situation.

[0030] Example 2

[0031] This embodiment refers to the preparation method provided in Example 1 to prepare a waterproof and heat-insulating negative ion material. The difference between this embodiment and Example 1 is that in the preparation of modified hexagonal stone, an equal mass of surfactant product of brand name FEO-500 produced by Shanghai Fluorine Technology Co., Ltd. is used instead of the fluorinated surfactant used in Example 1. The main component of the surfactant brand name FEO-500 is a material with the structural formula […]. Perfluoroalkyl ethanol polyoxyethylene ether with n = 3–6 and m = 10–12. The proportions of other raw materials and the preparation method are strictly consistent with those in Example 1.

[0032] Example 3

[0033] This embodiment refers to the preparation method provided in Example 1 to prepare a waterproof and heat-insulating negative ion material. The difference between this embodiment and Example 1 is that in the preparation of modified hexagonal stone, an equal mass of surfactant product of brand name YM-313 produced by Shanghai Yumu Chemical Co., Ltd. is used instead of the fluorinated surfactant used in Example 1. The main component of the surfactant brand name YM-313 is perfluoroalkyl polyoxyethylene ether, and its fluorocarbon segment is perfluorooctyl. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0034] Example 4

[0035] This embodiment refers to the preparation method provided in Example 1 to prepare a waterproof and heat-insulating negative ion material. The difference between this embodiment and Example 1 is that, in the preparation of modified hexagonal stone, an equal mass of sodium perfluorooctanoate is used instead of the fluorinated surfactant used in Example 1. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0036] Example 5

[0037] This embodiment refers to the preparation method provided in Example 1 to prepare a waterproof and heat-insulating negative ion material. The difference between this embodiment and Example 1 is that the acidification and calcination steps of hexagonal stone are omitted in the preparation of modified hexagonal stone, and the fluorinated surfactant is directly reacted with hexagonal stone for modification. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0038] Example 6

[0039] This embodiment refers to the preparation method provided in Example 1 to prepare a waterproof and heat-insulating negative ion material. The difference between this embodiment and Example 1 is that the calcination step of hexagonal stone is omitted in the preparation of the modified hexagonal stone. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0040] Example 7

[0041] This embodiment refers to the preparation method provided in Example 1 to prepare a waterproof and heat-insulating negative ion material. The difference between this embodiment and Example 1 is that, in the process of preparing the waterproof and heat-insulating negative ion material, an equal mass of modified hexagonal ore is used instead of molybdenum disulfide in Example 1. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0042] Example 8

[0043] This embodiment refers to the preparation method provided in Example 1 to prepare a waterproof and heat-insulating negative ion material. The difference between this embodiment and Example 1 is that the amount of molybdenum disulfide added is 8 parts in the preparation process, so that the mass ratio of modified hexagonalite to molybdenum disulfide in this embodiment is 4:1.5. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0044] Comparative Example 1

[0045] This comparative example uses the preparation method provided in Example 1 to prepare a material. The difference between this comparative example and Example 1 is that, in the process of preparing the waterproof and heat-insulating negative ion material, an equal mass of phenolic resin is used instead of the epoxy resin in Example 1. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0046] Comparative Example 2

[0047] This comparative example uses the preparation method provided in Example 1 to prepare a material. The difference between this comparative example and Example 1 is that, in the process of preparing the waterproof and heat-insulating negative ion material, an equal mass of unmodified hexagonal ore is used instead of the modified hexagonal ore in Example 1. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0048] Comparative Example 3

[0049] This comparative example uses the preparation method provided in Example 1 to prepare a material. The difference between this comparative example and Example 1 is that, in the process of preparing the waterproof and heat-insulating negative ion material, an equal mass of acidified hexagonalite is used instead of the modified hexagonalite in Example 1. The remaining raw material ratios and preparation methods are strictly consistent with those in Example 1.

[0050] Test Example 1

[0051] Test subjects: The waterproof and heat-insulating negative ion materials provided in Examples 1 to 8 and the materials provided in Comparative Examples 1 to 3 were respectively coated onto an insulating substrate (the substrate was required to be a square with a cut edge length of 100mm), and the substrate was heated in a forced-air drying oven to crosslink and cure. The cured materials were used as test subjects.

[0052] (1) Water resistance: The water resistance of the test object was tested in accordance with GB / T 1733-1993 Test Method for Water Resistance of Coating Film.

[0053] (2) Thermal insulation performance: The coating of the test object is uniformly coated on the glass plate and cured to obtain the test plate. A blank plate without coating is set up. The test plate and the blank plate are uniformly irradiated with infrared lamps. After the specified time, the average temperature of the test plate and the blank plate is measured by infrared thermal imager, and the thermal insulation temperature difference is calculated.

[0054] (3) Antibacterial rate: The antibacterial rate was tested in accordance with GB / T21866-2008 Antibacterial Coatings (Films) Antibacterial Properties Test Method and Antibacterial Effect. The test species was Staphylococcus aureus, and the stain resistance of the test object was tested.

[0055] Test results: The test results are shown in Table 1.

[0056] Table 1. Test performance of each test subject

[0057] Group Water resistance Thermal insulation temperature difference (°C) Antibacterial rate Example 1 1440h 28.7 99.8％ Example 2 1440h 28.4 99.8％ Example 3 1200h 24.3 98.8％ Example 4 1080h 21.9 99.5％ Example 5 1200h 22.7 98.8％ Example 6 1200h 20.5 99.8％ Example 7 1440h 22.1 99.8％ Example 8 1440h 26.6 99.8％ Comparative Example 1 1080h 16.4 ＜85％ Comparative Example 2 960h 12.5 ＜90％ Comparative Example 3 960h 10.6 ＜95％

[0058] Results analysis:

[0059] Comparing the test performance of Examples 1-8 with Comparative Examples 1-3 in Table 1, it can be found that, compared with the materials prepared in Comparative Examples 1-3, the waterproof and heat-insulating negative ion materials provided in Examples 1-8 not only possess excellent heat insulation performance and waterproof and water-resistant properties, but also have strong bactericidal and bacteriostatic properties. Among them, the waterproof and heat-insulating composite materials provided in Examples 1-2 have the best comprehensive performance, with good water resistance and waterproofing, strong heat insulation and heat preservation capabilities, and strong bacteriostatic and bacteriostatic capabilities.

[0060] Comparing the test performance of Examples 1-8 with that of Comparative Example 1 in Table 1, it can be found that, compared with the negative ion material made only by phenolic resin, the negative ion material prepared by combining phenolic resin and epoxy resin with modified hexagonal stone can generate negative ions for a longer period of time, and has stronger bactericidal and bacteriostatic ability, better heat insulation performance, and water resistance.

[0061] Comparing the test performance of Examples 1-8 with that of Comparative Examples 2-3 in Table 1, it can be found that the negative ion materials of Examples 1-8 exhibit better thermal insulation, waterproofing, and antibacterial effects than the materials of Comparative Examples 2-3. This indicates that modified hexagonal stone modified with fluorinated surfactants can improve the thermal insulation, antibacterial, and waterproofing properties of negative ion materials.

[0062] Furthermore, comparing the negative ion materials provided in Examples 1-4, it can be found that the heat insulation and waterproof performance of Examples 1-3 are superior to those of Example 4. This demonstrates that modifying hexagonal stone with a fluorosurfactant containing polyoxyethylene ether groups can give the negative ion materials better hydrophobic and heat insulation effects.

[0063] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A waterproof and heat-insulating negative ion material, characterized in that, Including fillers and thermosetting resins, The filler comprises modified hexagonalite and molybdenum disulfide, and the mass ratio of modified hexagonalite to molybdenum disulfide is 3~4:0.8~1.

1. The modified hexagonalite is modified with a fluorinated surfactant, and the modified hexagonalite accounts for 15-30 wt% of the negative ion material; the molecular structure of the fluorinated surfactant satisfies general formula I: n is 3~6, ​​m is 6~12; The preparation method of the modified hexagonalite includes the following operations: at a temperature of 25~35℃, hexagonalite is mixed with a strong acid solution, the concentration of the strong acid solution being 0.85~1.25mol / L, and stirred for 0.5~1 hour; then the hexagonalite is calcined at a temperature of 300~400℃ for 1~2 hours to obtain acidified hexagonalite; at a temperature of 60~70℃, the acidified hexagonalite is mixed evenly with a fluorinated surfactant and stirred for 0.5~1 hour to obtain modified hexagonalite; The thermosetting resin includes phenolic resin and epoxy resin, and the ratio of phenolic resin to epoxy resin is 1~1.5:0.1~0.2 by mass.

2. The waterproof and heat-insulating negative ion material as described in claim 1, characterized in that, The amount of the fluorinated surfactant used is 3~5 mol / 50 g of acidified hexagonalite.

3. The waterproof and heat-insulating negative ion material as described in claim 1, characterized in that, The modified hexagonal stone has an average particle size of 5~15μm.

4. A method for preparing a waterproof and heat-insulating negative ion material as described in any one of claims 1 to 3, characterized in that, Includes the following operations: Weigh out the raw materials used to prepare the waterproof and heat-insulating negative ion material according to the specified amount, and mix the components evenly at 25~35℃ according to the specified ratio to obtain the waterproof and heat-insulating negative ion material.

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