Multilayer coated ceramic hollow microsphere and manufacturing method thereof

Abstract

The present invention discloses a multilayer coated ceramic hollow microsphere and a method for manufacturing the same, which belongs to the field of coatings and includes the following components in parts by weight: 80-100 parts of hollow ceramic microspheres, 5-10 parts of octaisobutylsilsesquioxane, 2-5 parts of polyvinylidene fluoride-hexafluoropropylene, and 26-45 parts of solvent; the multilayer coated ceramic hollow microspheres are a sandwich structure of one core and two membranes, specifically: hollow ceramic microspheres-octaisobutylsilsesquioxane-polyvinylidene fluoride-hexafluoropropylene. The outermost coating of the multilayer coated ceramic hollow microspheres of the present invention is polyvinylidene fluoride-hexafluoropropylene, which leaves a polymer film full of microcavities on the surface of the object after drying, and then adheres to the outermost surface of the hollow ceramic particles to form a coating. The coating can play a very good reflective heat insulation effect in the outermost layer of the hollow ceramic particles. At the same time, according to the material properties, it can be seen that its very good chemical stability, anti-pollution, radiation resistance, heat resistance and mechanical properties are all very excellent.

Description

Technical Field

[0001] The invention belongs to the field of coatings, and in particular relates to multi-layer coated ceramic hollow microspheres and a manufacturing method thereof. Background Art

[0002] Reflective thermal insulation coatings are made of various resins or non-resins as base materials, and are formulated with functional pigments, fillers and additives. They have high solar reflectance, near-infrared reflectance and hemispherical reflectance.

[0003] Reflective thermal insulation coatings can reflect solar infrared and visible light in the 380nm-2500nm range, preventing the sun's heat from accumulating and heating the surface. They can also automatically radiate heat and cool the surface, radiating it into the atmosphere and lowering the surface temperature. Functional pigments and fillers are a crucial component of reflective thermal insulation coatings. Numerous reflective thermal insulation pigments and fillers are available on the market, including core glass beads, ceramic balls, and modified titanium dioxide. While these pigments and fillers all offer a relatively good reflective and thermal insulation effect for sunlight in the 380nm-2500nm band, they lack this reflective and thermal insulation effect in systems without titanium dioxide.

[0004] It should be noted that the above content falls within the technical knowledge of the inventor and does not necessarily constitute prior art. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a multi-layer coated ceramic hollow microsphere and a manufacturing method thereof. The multi-layer coated ceramic hollow microsphere powder is wrapped with multiple layers of materials, so that the powder has an excellent reflective and heat-insulating effect on sunlight in the 380nm-2500nm band, and is applied to coatings to effectively enhance the reflective and heat-insulating properties of the coatings.

[0006] The purpose of the present invention can be achieved by the following technical solution: A multi-layer coated ceramic hollow microsphere, comprising the following components in parts by weight:

[0007] 80-100 parts of hollow ceramic microspheres, 5-10 parts of octaisobutylsilsesquioxane, 2-5 parts of polyvinylidene fluoride-hexafluoropropylene, and 26-45 parts of solvent.

[0008] The multi-layer coated ceramic hollow microspheres are a sandwich structure of one core and two membranes, specifically: hollow ceramic microspheres-octaisobutylsilsesquioxane-polyvinylidene fluoride-hexafluoropropylene.

[0009] Furthermore, the solvent includes 20-30 parts of isopropyl alcohol and 6-15 parts of N,N-dimethylformamide.

[0010] Further, the following components in parts by weight are included:

[0011] 100 parts of hollow ceramic microspheres, 7 parts of octaisobutylsilsesquioxane, 3 parts of polyvinylidene fluoride-hexafluoropropylene, and 35 parts of solvent.

[0012] Furthermore, the solvent includes 25 parts of isopropyl alcohol and 10 parts of N,N-dimethylformamide.

[0013] Furthermore, the outermost coating of the multi-layer coated ceramic hollow microspheres is polyvinylidene fluoride-hexafluoropropylene.

[0014] Furthermore, the inner coating of the multi-layer coated ceramic hollow microspheres is octaisobutylsilsesquioxane.

[0015] Furthermore, the main core of the multi-layer coated ceramic hollow microspheres is ceramic hollow microspheres.

[0016] A method for manufacturing multi-layer coated ceramic hollow microspheres comprises the following steps:

[0017] S1: Octaisobutylsilsesquioxane is stirred and dissolved in a reactor at room temperature with isopropyl alcohol, and then the mixture is placed in a spray device and added to the high-speed stirring hollow ceramic microbeads in the stirring tank by spraying. The spraying process takes about 8-15 minutes. After the spraying is completed, it is stirred for another 25 minutes. The above mixture is then placed in a ventilated drying oven at 90°C for 5 hours. The dried product is then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain Product 1.

[0018] S2: Dissolve polyvinylidene fluoride-hexafluoropropylene in N,N-dimethylformamide, and then add it to the product 1 stirred in S1 by spraying to obtain a mixture. The spraying process is about 6-10 minutes, and then stirred for 25 minutes. The mixture is then dried at 160°C for 3 hours. The dried mixture is then placed in a reactor and fully dispersed using a jet mill to obtain the final product.

[0019] Beneficial effects of the present invention:

[0020] 1. The outermost coating of the multi-layer coated ceramic hollow microspheres of the present invention is polyvinylidene fluoride-hexafluoropropylene. After drying, this raw material will leave a polymer film full of microcavities on the surface of the object, and then adhere to the outermost surface of the hollow ceramic particles to form a coating. When sunlight irradiates the surface, since the coating is a microporous structure with a sufficiently large specific surface area, the heat generated by the sunlight will be dispersed and isolated on the microporous surface of the coating. At the same time, these tiny cavities, ranging from a few hundred nanometers to a few microns, can reflect most of the incident sunlight. Therefore, the coating can play a very good reflective and heat-insulating effect on the outermost layer of the hollow ceramic particles. At the same time, according to the characteristics of the material, it can be seen that it has very good chemical stability, anti-pollution, radiation resistance, heat resistance and mechanical properties.

[0021] 2. The inner coating of the multi-layer coated ceramic hollow microspheres of the present invention is octaisobutylsilsesquioxane, which has a cage-like structure with an inorganic framework core formed by Si-O and surrounded by isobutyl groups. Therefore, the coating material is very stable. At the same time, this compound has excellent porosity and nano-size effect. At the same time, due to its low density, it has very good hardness after drying. Due to its porous properties, this material has an excellent reflective and heat-insulating effect against sunlight. At the same time, it has high hardness and good stability. When used in coatings, it does not react with the coating, improving the coating stability and hardness.

[0022] 3. The core of the multi-layer coated ceramic hollow microspheres of the present invention is a ceramic hollow microsphere. This material is generally composed of composite inorganic particles of silicon trioxide, aluminum trioxide, iron trioxide, and titanium dioxide. These microspheres have a porous, hollow structure and are inert, stable, heat-resistant, and have excellent sunlight reflection properties. Using this material as the core and then coating it with the two coatings above further enhances the reflective and heat-insulating properties. DETAILED DESCRIPTION

[0023] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0024] Example 1

[0025] A multi-layer coated ceramic hollow microsphere comprises the following components in parts by weight:

[0026] 100 parts of hollow ceramic microspheres, 7 parts of octaisobutylsilsesquioxane, 3 parts of polyvinylidene fluoride-hexafluoropropylene, and 35 parts of a solvent, wherein the solvent includes 25 parts of isopropyl alcohol and 10 parts of N,N-dimethylformamide.

[0027] A method for manufacturing multi-layer coated ceramic hollow microspheres comprises the following steps:

[0028] S1: Octaisobutylsilsesquioxane was stirred and dissolved in a reactor at room temperature using isopropyl alcohol, and then the mixture was placed in a spray device and added to the high-speed stirring hollow ceramic microbeads in a stirring reactor by spraying. The spraying process took about 12 minutes. After the spraying was completed, the mixture was stirred for another 25 minutes. The mixture was then dried in a ventilated drying oven at 90°C for 5 hours. The dried product was then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain Product 1.

[0029] S2: Dissolve polyvinylidene fluoride-hexafluoropropylene in N,N-dimethylformamide, and then add it to the product 1 stirred in S1 by spraying to obtain a mixture. The spraying process is about 8 minutes, and then stirred for 25 minutes. The mixture is then dried at 160°C for 3 hours. The dried mixture is then placed in a reactor and fully dispersed using a jet mill to obtain the final product.

[0030] S3. Disperse the final product at 12% in a water-based paint formula without titanium dioxide, then adjust the paint to a dark yellow. Finally, test the product lightness L to 54, and then test the performance according to GB / T251261.

[0031] Example 2

[0032] A multi-layer coated ceramic hollow microsphere comprises the following components in parts by weight:

[0033] 90 parts of hollow ceramic microspheres, 10 parts of octaisobutylsilsesquioxane, 5 parts of polyvinylidene fluoride-hexafluoropropylene, and 45 parts of a solvent, wherein the solvent includes 30 parts of isopropyl alcohol and 15 parts of N,N-dimethylformamide.

[0034] A method for manufacturing multi-layer coated ceramic hollow microspheres comprises the following steps:

[0035] S1: Octaisobutylsilsesquioxane was stirred and dissolved in a reactor at room temperature using isopropyl alcohol, and then the mixture was placed in a spray device and added to the high-speed stirring hollow ceramic microbeads in a stirring reactor by spraying. The spraying process took about 15 minutes. After the spraying was completed, the mixture was stirred for another 25 minutes. The mixture was then dried in a ventilated drying oven at 90°C for 5 hours. The dried product was then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain Product 1.

[0036] S2: Dissolve polyvinylidene fluoride-hexafluoropropylene in N,N-dimethylformamide, and then add it to the product 1 stirred in S1 by spraying to obtain a mixture. The spraying process is about 10 minutes, and then stirred for 25 minutes. The mixture is then dried at 160°C for 3 hours. The dried mixture is then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain the final product.

[0037] S3. Disperse the final product at 12% in a water-based paint formula without titanium dioxide, then adjust the paint to a dark yellow. Finally, test the product lightness L to 51, and then test the performance according to GB / T251261.

[0038] Example 3

[0039] A multi-layer coated ceramic hollow microsphere comprises the following components in parts by weight:

[0040] 80 parts of hollow ceramic microspheres, 5 parts of octaisobutylsilsesquioxane, 2 parts of polyvinylidene fluoride-hexafluoropropylene, and 45 parts of a solvent, wherein the solvent includes 20 parts of isopropyl alcohol and 6 parts of N,N-dimethylformamide.

[0041] A method for manufacturing multi-layer coated ceramic hollow microspheres comprises the following steps:

[0042] S1: Octaisobutylsilsesquioxane was stirred and dissolved in a reactor at room temperature using isopropyl alcohol, and then the mixture was placed in a spray device and added to the high-speed stirring hollow ceramic microbeads in a stirring reactor by spraying. The spraying process took about 8 minutes. After the spraying was completed, the mixture was stirred for another 25 minutes. The mixture was then dried in a ventilated drying oven at 90°C for 5 hours. The dried product was then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain Product 1.

[0043] S2: Dissolve polyvinylidene fluoride-hexafluoropropylene in N,N-dimethylformamide, and then add it to the product 1 stirred in S1 by spraying to obtain a mixture. The spraying process is about 6 minutes, and then stirred for 25 minutes. The mixture is then dried at 160°C for 3 hours. The dried mixture is then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain the final product.

[0044] S3. Disperse the final product at 12% in a water-based paint formula without titanium dioxide, then adjust the paint to a dark yellow. Finally, test the product lightness L to 58, and then test the performance according to GB / T251261.

[0045] Comparison sample 1

[0046] In the same formula, 12% 800 mesh heavy calcium carbonate was used to replace the product of the present invention and dispersed in the formula. The paint was then adjusted to a dark yellow color. Finally, the lightness L of the product was tested to be 53. The performance was then tested according to GB / T251261.

[0047] Comparison sample 2

[0048] In the same formula, 12% hollow ceramic microspheres were used to replace the product of the present invention and dispersed in the formula. The paint was then adjusted to a dark yellow. Finally, the product lightness L was tested to be 52, and the performance was tested according to GB / T251261.

[0049] Comparison sample 3

[0050] In the same formula, 12% precipitated barium sulfate was used instead of the product of the present invention and dispersed in the formula. The paint was then adjusted to a dark yellow. Finally, the lightness L of the product was tested to be 59. The performance was then tested in accordance with GB / T251261.

[0051] The performance comparison of Examples 1-3 and Comparative Samples 1-3 is shown in the following table:

[0052]

[0053] According to the above table: the addition of the final product of the present invention to a general titanium dioxide-free water-based paint complies with GB / T251261, while the same formula using the same proportion of materials instead of the final product of the present invention does not comply with GB / T251261.

[0054] The multi-layer coated ceramic hollow microspheres of the present invention are a sandwich structure of one core and two membranes, specifically: hollow ceramic microspheres-octaisobutylsilsesquioxane-polyvinylidene fluoride-hexafluoropropylene.

[0055] The outermost coating of the multi-layer coated ceramic hollow microspheres of the present invention is polyvinylidene fluoride-hexafluoropropylene. After drying, the raw material will leave a polymer film full of microcavities on the surface of the object, and then adhere to the outermost surface of the hollow ceramic particles to form a coating. When sunlight irradiates the surface, since the coating is a microporous structure with a sufficiently large specific surface area, the heat generated by the sunlight will be dispersed and isolated on the microporous surface of the coating. At the same time, these tiny cavities, ranging from hundreds of nanometers to several microns, can reflect most of the incident sunlight. Therefore, the coating can play a very good reflective heat-insulating effect in the outermost layer of the hollow ceramic particles. At the same time, according to the characteristics of the material, it can be seen that its very good chemical stability, anti-pollution, radiation resistance, heat resistance and mechanical properties are all very excellent.

[0056] The inner coating of the multi-layer coated ceramic hollow microspheres of the present invention is octaisobutylsilsesquioxane. The molecule has a cage-like structure, with an inorganic framework core formed by Si-O surrounded by isobutyl groups. This coating material is very stable. The compound also exhibits excellent porosity and nano-size effects. Due to its low density, it has very good hardness after drying. Due to its porous nature, the material has excellent reflective and thermal insulation properties against sunlight. Furthermore, its high hardness and excellent stability make it non-reactive with the coating when applied, improving both the coating's stability and hardness.

[0057] The core of the multi-layer coated ceramic hollow microspheres is a ceramic hollow microsphere. This material is generally composed of composite inorganic particles of silicon trioxide, aluminum trioxide, iron trioxide, and titanium dioxide. These microspheres have a porous, hollow structure and are inert, stable, heat-resistant, and have excellent sunlight reflection properties. Using this core material and coating it with the two coatings above further enhances its reflective and heat-insulating properties.

[0058] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0059] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A method for producing multi-layer coated ceramic hollow microspheres, characterized in that: The steps include: S1: Octaisobutylsilsesquioxane is stirred and dissolved in a reactor at room temperature using isopropyl alcohol. The mixture is then placed in a spray device and added to the high-speed stirring hollow ceramic microbeads in a stirred tank by spraying. The spraying process lasts for 8-15 minutes. After the spraying is completed, the mixture is stirred for another 25 minutes. The mixture is then dried in a ventilated drying oven at 90° C. for 5 hours. The dried product is then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain Product 1. S2: Dissolve polyvinylidene fluoride-hexafluoropropylene in N,N-dimethylformamide, and then add it to the stirred product 1 in S1 by spraying to obtain a mixture. The spraying process is 6-10 minutes, followed by stirring for 25 minutes. The mixture is then dried at 160°C for 3 hours. The dried mixture is then placed in a reactor and fully dispersed using a jet mill to obtain the final product. The multi-layer coated ceramic hollow microspheres include the following components in parts by weight: 80-100 parts of hollow ceramic microspheres, 5-10 parts of octaisobutylsilsesquioxane, 2-5 parts of polyvinylidene fluoride-hexafluoropropylene, and 26-45 parts of solvent; The multilayer coated ceramic hollow microspheres are a sandwich structure of one core and two membranes, specifically: hollow ceramic microspheres-octaisobutylsilsesquioxane-polyvinylidene fluoride-hexafluoropropylene; The solvent includes 20-30 parts of isopropyl alcohol and 6-15 parts of N,N-dimethylformamide.

2. The method for manufacturing multi-layer coated ceramic hollow microspheres according to claim 1, characterized in that: Comprise the following components in parts by weight: 100 parts of hollow ceramic microspheres, 7 parts of octaisobutylsilsesquioxane, 3 parts of polyvinylidene fluoride-hexafluoropropylene, and 35 parts of solvent.

3. The method for manufacturing multi-layer coated ceramic hollow microspheres according to claim 2, characterized in that: The solvent includes 25 parts of isopropyl alcohol and 10 parts of N,N-dimethylformamide.

4. The method for manufacturing multi-layer coated ceramic hollow microspheres according to claim 1, characterized in that: The outermost coating of the multi-layer coated ceramic hollow microspheres is polyvinylidene fluoride-hexafluoropropylene.

5. The method for manufacturing multi-layer coated ceramic hollow microspheres according to claim 1, characterized in that: The inner coating of the multi-layer coated ceramic hollow microspheres is octaisobutylsilsesquioxane.

6. The method for manufacturing multi-layer coated ceramic hollow microspheres according to claim 1, characterized in that: The main core of the multi-layer coated ceramic hollow microsphere is a ceramic hollow microsphere.

7. The method for manufacturing multi-layer coated ceramic hollow microspheres according to claim 3, characterized in that: The steps include: S1: Octaisobutylsilsesquioxane was stirred and dissolved in a reactor at room temperature using isopropyl alcohol, and the mixture was then placed in a spray device and added to the high-speed stirring hollow ceramic microbeads in a stirred tank by spraying. The spraying process lasted for 12 minutes. After the spraying was completed, the mixture was stirred for another 25 minutes. The mixture was then dried in a ventilated drying oven at 90° C. for 5 hours. The dried product was then placed in a reactor and fully dispersed using a jet mill for 15 minutes to obtain Product 1. S2: Dissolve polyvinylidene fluoride-hexafluoropropylene in N,N-dimethylformamide, and then add it to the product 1 stirred in S1 by spraying to obtain a mixture. The spraying process is 8 minutes, and then stirred for 25 minutes. The mixture is then dried at 160°C for 3 hours. The dried mixture is then placed in a reactor and fully dispersed using a jet mill to obtain the final product.

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