High-gradient tile with good drainage performance and preparation method of high-gradient tile

Abstract

The invention relates to the technical field of building materials, and particularly discloses a high-gradient tile with good drainage performance and a preparation method of the high-gradient tile. The high-gradient tile with the good drainage performance is prepared from raw materials as follows: polyvinyl chloride, modified glass beads, a stabilizer, titanium dioxide, an antioxidant, an ultraviolet light absorber, chlorinated polyethylene, ASA (acrylonitrile styrene acrylate) resin powder and toner. The compatibility between the glass beads and the matrix resin is effectively improved, so that the high-gradient tile has good mechanical properties, and the use requirements of the high-gradient tile under extreme weather conditions are met.

Description

Technical Field

[0001] This application relates to the technical field of building materials, and particularly relates to a high-ladder tile with good drainage performance and a preparation method thereof. Background Art

[0002] High-ladder tiles are a type of plastic building material product that has been widely promoted and used in recent years. They are usually made by co-extruding ASA and PVC resins. This type of resin tile has the advantages of bright colors, simple and feasible construction, and reasonable prices. The wave peaks of high-ladder tiles are high and the wave distances are moderate. The drainage slope of the tiles is larger, which can quickly drain rainwater and is suitable for various building types. In addition, the resin tile also has good heat insulation and waterproof properties, which can effectively protect buildings.

[0003] However, the existing PVC resin tiles are difficult to balance light weight and high strength, resulting in mechanical properties such as wind resistance and impact resistance that are difficult to meet the usage requirements under extreme weather conditions. Moreover, when PVC resin tiles are exposed to the outdoor environment for a long time, they are easily affected by environmental factors such as ultraviolet rays, high temperature, and rain, resulting in aging phenomena such as embrittlement, fading, and affecting the service life. Summary of the Invention

[0004] In order to improve the mechanical properties of high-ladder tiles and extend the service life of high-ladder tiles, this application provides a high-ladder tile with good drainage performance and a preparation method thereof.

[0005] In the first aspect, a high-ladder tile with good drainage performance provided by this application adopts the following technical solution: A high-ladder tile with good drainage performance is prepared from the following raw materials by weight: 60 - 70 parts of polyvinyl chloride, 8 - 10 parts of modified glass microspheres, 3 - 5 parts of stabilizer, 2 - 3 parts of titanium dioxide, 0.3 - 0.5 parts of antioxidant, 0.3 - 0.5 parts of ultraviolet absorber, 3 - 5 parts of chlorinated polyethylene, 1 - 3 parts of ASA resin powder, 0.2 - 0.4 parts of color powder; The preparation raw materials of the modified glass microspheres include hollow glass microspheres, acrylate monomers, maleic anhydride, and 4-vinylpyridine. The weight ratio of the hollow glass microspheres, acrylate monomers, maleic anhydride, and 4-vinylpyridine is 10:(0.8 - 1.2):(0.5 - 0.7):(0.08 - 0.12).

[0006] By adopting the above technical solutions, the ASA resin powder has good compatibility with polyvinyl chloride, and the polymer alloy formed by mixing the two is used to prepare high-tile tiles with excellent aging resistance. Chlorinated polyethylene has good toughness and impact resistance, and adding chlorinated polyethylene can effectively improve the impact resistance of the tiles. By synthesizing a ternary copolymer macromolecular coupling agent from acrylate monomers, maleic anhydride and 4-vinylpyridine and using it to modify the surface of hollow glass microspheres, an organic coating layer is formed on the surface of the hollow glass microspheres, which can greatly improve the compatibility between the glass microspheres and the matrix resin. Among them, the macromolecular coupling agent not only modifies the hollow glass microspheres in the form of physical coating, but also modifies the glass microspheres in the form of chemical bonding, that is, through the chemical bonding of the anhydride group of the macromolecular coupling agent and the hydroxyl group on the surface of the glass microspheres. The acrylate monomer can adjust the flexibility of the molecular chain, and the pyridine ring causes the dechlorination of PVC. The conjugated olefins formed after dechlorination are prone to cross-linking between chains to form a stable cross-linked structure, thereby improving the overall mechanical properties of the high-tile tiles. In addition, due to the hollow structure of the hollow glass microspheres and the presence of a certain amount of gas inside the sphere, the high-tile tiles have the characteristics of light weight and high strength, and at the same time have good heat insulation performance.

[0007] Preferably, the acrylate monomer is one of methyl acrylate, ethyl acrylate, and butyl acrylate.

[0008] Preferably, the preparation method of the modified glass microspheres is as follows: (1) Dissolve acrylate monomers, maleic anhydride, and 4-vinylpyridine in acetone, introduce nitrogen, and heat to 70 - 80 °C. Then add an initiator and a chain transfer agent, and react for 2 - 3 h to obtain a copolymer solution. Then add absolute ethanol, stir, precipitate the polymer, wash 2 - 3 times, and dry to obtain a terpolymer; (2) Dissolve the terpolymer in acetone, add glass microspheres, stir and react for 3 - 4 h, filter and dry to obtain modified glass microspheres.

[0009] Preferably, the initiator in step (1) is benzoyl peroxide, and the chain transfer agent is dodecyl mercaptan.

[0010] By adopting the above technical solutions, a macromolecular coupling agent is synthesized from acrylate monomers, maleic anhydride, and 4-vinylpyridine and used to modify the surface of glass microspheres to improve the compatibility between the glass microspheres and PVC resin. Chemical bonding occurs between the modified glass microspheres and PVC resin, enabling the high-tile tiles to have good mechanical properties to meet the usage requirements of high-tile tiles under extreme weather conditions. In addition, the surface free energy of the modified glass microspheres is greatly reduced, resulting in a small contact angle when they come into contact with water, thus achieving a hydrophobic effect and enabling the tiles to have a self-cleaning function and reducing stain adhesion.

[0011] Preferably, the stabilizer is at least one of organotin stabilizers, rare earth stabilizers, and metal soap stabilizers.

[0012] By adopting the above technical solution, the stabilizer can effectively capture and inhibit the generation of free radicals, thereby delaying the process of plastic degradation.

[0013] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 626.

[0014] Preferably, the ultraviolet absorber is at least one of UV-328, UV-360, and UV-326.

[0015] By adopting the above technical solution, the antioxidant can effectively capture the free radicals generated during the processing and use of PVC resin and inhibit the occurrence of oxidation reactions. The ultraviolet absorber can absorb high-energy ultraviolet rays and convert them into harmless heat energy, thereby reducing the damage of ultraviolet rays to the PVC molecular chain. The synergistic effect of the two can more comprehensively protect the PVC resin and delay the rate of its oxidative degradation.

[0016] Preferably, the particle size of the hollow glass microspheres is 20 - 40 μm.

[0017] By adopting the above technical solution, the use of hollow glass microspheres with a particle size of 20 - 40 μm achieves the best filling effect and further improves the mechanical properties of the material.

[0018] In the second aspect, the preparation method of a high-step tile with good drainage performance provided by this application adopts the following technical solution: A preparation method of a high-step tile with good drainage performance includes the following steps: Weigh the raw materials according to the component ratio. Melt and mix polyvinyl chloride, modified glass microspheres, stabilizer, titanium dioxide, antioxidant, ultraviolet absorber, chlorinated polyethylene, ASA resin powder, and color powder at 150 - 170 °C for 20 - 30 minutes to obtain a premix. Transfer the premix to an extruder for heating and extrusion, and convey it to a shaping die for shaping to obtain a high-step tile.

[0019] Preferably, the extrusion temperature in the extruder is 170 - 180 °C, and the shaping temperature is 160 - 170 °C.

[0020] By adopting the above technical solutions, during the preparation process, by precisely controlling the temperature conditions of melt mixing and extrusion molding, the dimensional stability of high-tile during processing is ensured. Meanwhile, the synergistic effect of polyvinyl chloride, chlorinated polyethylene and ASA resin powder further improves the heat resistance of the material, enabling it to maintain stable physical properties within a relatively wide temperature range. The addition of titanium dioxide not only imparts good appearance color to high-tile, but also enhances the weather resistance and ultraviolet resistance of the material.

[0021] In summary, this application includes at least one of the following beneficial technical effects: In this application, ASA resin has good compatibility with polyvinyl chloride, and the polymer alloy formed by mixing the two is used to prepare high-tile with excellent aging resistance. Chlorinated polyethylene has good toughness and impact resistance, and adding chlorinated polyethylene can effectively improve the impact resistance of the tile. By synthesizing a ternary copolymer macromolecular coupling agent from acrylate monomer, maleic anhydride and 4-vinylpyridine and using it to modify the surface of hollow glass microspheres, an organic coating layer is formed on the surface of the hollow glass microspheres, which can greatly improve the compatibility between the glass microspheres and the matrix resin. Among them, the macromolecular coupling agent not only modifies the hollow glass microspheres in the form of physical coating, but also modifies the glass microspheres in the form of chemical bonding, that is, through the chemical bonding of the anhydride group of the macromolecular coupling agent and the hydroxyl group on the surface of the glass microspheres. The acrylate monomer can adjust the flexibility of the molecular chain, and the pyridine ring causes PVC dechlorination. The conjugated olefins formed after dechlorination are prone to cross-linking between chains to form a stable cross-linked structure, thereby improving the overall mechanical properties of high-tile. In addition, due to the characteristics of the hollow glass microspheres with a certain amount of gas wrapped inside the hollow sphere, high-tile has the characteristics of being lightweight and high-strength, and at the same time has good heat insulation performance. Specific embodiments

[0022] The following further elaborates on this application with reference to examples.

[0023] Preparation examples Preparation example 1 Preparation of modified glass microspheres: (1) Dissolve 8 g of methyl acrylate, 5 g of maleic anhydride and 0.8 g of 4-vinylpyridine in 100 mL of acetone, introduce nitrogen, and heat to 70 °C. Then add 0.1 g of benzoyl peroxide and 0.1 g of dodecyl mercaptan, and react for 2 h to obtain a copolymer solution. Then add anhydrous ethanol, stir, precipitate the polymer, wash 2 times, and dry to obtain a terpolymer; (2) Dissolve the terpolymer in 150 mL of acetone, add 100 g of glass microspheres (particle size 20 μm), stir and react for 3 h, filter by suction and dry to obtain modified glass microspheres.

[0024] Preparation example 2 Preparation of modified glass microspheres: (1) Dissolve 10 g of butyl acrylate, 6 g of maleic anhydride, and 1 g of 4-vinylpyridine in 100 mL of acetone. Pass in nitrogen and heat to 75 °C. Then add 0.12 g of benzoyl peroxide and 0.12 g of dodecyl mercaptan, and react for 2.5 h to obtain a copolymer solution. Then add anhydrous ethanol, stir, precipitate the polymer, wash it 3 times, and dry it to obtain a terpolymer; (2) Dissolve the terpolymer in 150 mL of acetone, add 100 g of glass microspheres (particle size 30 μm), stir and react for 3.5 h, filter by suction and dry to obtain modified glass microspheres.

[0025] Preparation Example 3 Preparation of modified glass microspheres: (1) Dissolve 12 g of ethyl acrylate, 7 g of maleic anhydride, and 1.2 g of 4-vinylpyridine in 100 mL of acetone. Pass in nitrogen and heat to 80 °C. Then add 0.14 g of benzoyl peroxide and 0.14 g of dodecyl mercaptan, and react for 3 h to obtain a copolymer solution. Then add anhydrous ethanol, stir, precipitate the polymer, wash it 3 times, and dry it to obtain a terpolymer; (2) Dissolve the terpolymer in 150 mL of acetone, add 100 g of glass microspheres (particle size 40 μm), stir and react for 4 h, filter by suction and dry to obtain modified glass microspheres.

[0026] Preparation Example 4 The difference between this preparation example and Preparation Example 2 is that an equal amount of octyl acrylate is used instead of butyl acrylate.

[0027] Preparation Example 5 The difference between this preparation example and Preparation Example 2 is that maleic anhydride is not added. That is, the preparation method of modified glass microspheres is as follows: (1) Dissolve 10 g of butyl acrylate and 6 g of maleic anhydride in 100 mL of acetone. Pass in nitrogen and heat to 75 °C. Then add 0.12 g of benzoyl peroxide and 0.12 g of dodecyl mercaptan, and react for 2.5 h to obtain a copolymer solution. Then add anhydrous ethanol, stir, precipitate the polymer, wash it 3 times, and dry it to obtain a binary copolymer; (2) Dissolve the binary copolymer in 150 mL of acetone, add 100 g of glass microspheres, stir and react for 3.5 h, filter by suction and dry to obtain modified glass microspheres.

[0028] Preparation Example 6 The difference between this preparation example and Preparation Example 2 is that 4-vinylpyridine is not added. That is, the preparation method of modified glass microspheres is as follows: (1) Dissolve 10 g of butyl acrylate and 1 g of 4-vinylpyridine in 100 mL of acetone, introduce nitrogen, and heat to 75 °C. Then add 0.12 g of benzoyl peroxide and 0.12 g of dodecyl mercaptan, and react for 2.5 h to obtain a copolymer solution. Then add anhydrous ethanol, stir, precipitate the polymer, wash it 3 times, and dry it to obtain a binary copolymer; (2) Dissolve the binary copolymer in 150 mL of acetone, add 100 g of glass microspheres, stir and react for 3.5 h, filter by suction and dry to obtain modified glass microspheres. Example

[0029] Example 1 A high-tile with good drainage performance, comprising the following raw materials: 600 g of polyvinyl chloride (Qilu Petrochemical S-700), 80 g of modified glass microspheres (prepared in Preparation Example 1), 30 g of organic tin stabilizer, 20 g of titanium dioxide, 1.5 g of antioxidant 1010, 1.5 g of antioxidant 168, 3 g of UV-328, 30 g of chlorinated polyethylene (Dow CPE135A), 10 g of ASA resin powder (Korea Kumho XC500A), 2 g of color powder.

[0030] Among them, the preparation method of the high-tile with good drainage performance in this example includes the following steps: Weigh the raw materials according to the component ratio. Melt and knead polyvinyl chloride, modified glass microspheres, organic tin stabilizer, titanium dioxide, antioxidant 1010, antioxidant 168, UV-328, chlorinated polyethylene, ASA resin powder, and color powder at 150 °C for 20 min to obtain a premix. Transfer the premix to an extruder, extrude it under the heating condition of 170 °C, and convey it to a shaping die for shaping to obtain a high-tile.

[0031] Example 2 A high-tile with good drainage performance, comprising the following raw materials: 650 g of polyvinyl chloride (Qilu Petrochemical S-700), 90 g of modified glass microspheres (prepared in Preparation Example 2), 40 g of rare earth stabilizer, 25 g of titanium dioxide, 2 g of antioxidant 1076, 2 g of antioxidant 626, 4 g of UV-326, 40 g of chlorinated polyethylene (Dow CPE135A), 20 g of ASA resin powder (Korea Kumho XC500A), 3 g of color powder.

[0032] Among them, the preparation method of the high-tile with good drainage performance in this example includes the following steps: Weigh the raw materials according to the group ratio. Mix polyvinyl chloride, modified glass microspheres, rare earth stabilizer, titanium dioxide, antioxidant 1076, antioxidant 626, UV-326, chlorinated polyethylene, ASA resin powder, and color powder by melt mixing at 160 °C for 25 minutes to obtain a premix. Transfer the premix to an extruder, extrude it under heating conditions at 175 °C, and convey it to a shaping die for shaping to obtain a high-step tile.

[0033] Example 3 A high-step tile with good drainage performance, comprising the following raw materials: 700 g of polyvinyl chloride (Qilu Petrochemical S-700), 100 g of modified glass microspheres (prepared in Preparation Example 3), 50 g of metal soap stabilizer, 30 g of titanium dioxide, 2.5 g of antioxidant 1010, 2.5 g of antioxidant 626, 5 g of UV-360, 50 g of chlorinated polyethylene (Dow CPE135A), 30 g of ASA resin powder (Korea Kumho XC500A), and 4 g of color powder.

[0034] Among them, the preparation method of the high-step tile with good drainage performance in this example includes the following steps: Weigh the raw materials according to the group ratio. Mix polyvinyl chloride, modified glass microspheres, metal soap stabilizer, titanium dioxide, antioxidant 1010, antioxidant 626, UV-360, chlorinated polyethylene, ASA resin powder, and color powder by melt mixing at 170 °C for 30 minutes to obtain a premix. Transfer the premix to an extruder, extrude it under heating conditions at 180 °C, and convey it to a shaping die for shaping to obtain a high-step tile.

[0035] Example 4 The difference between this example and Example 2 is that the modified glass microspheres prepared in Preparation Example 4 are used.

[0036] Comparative Example Comparative Example 1 A high-step tile with good drainage performance, different from Example 2 in that the modified glass microspheres prepared in Preparation Example 5 are used.

[0037] Comparative Example 2 A high-step tile with good drainage performance, different from Example 2 in that the modified glass microspheres prepared in Preparation Example 6 are used.

[0038] Comparative Example 3 A high-step tile with good drainage performance, different from Example 2 in that unmodified glass microspheres of equal amount are used instead of modified glass microspheres.

[0039] Comparative Example 4 A high-step tile with good drainage performance, different from Example 2 in that glass fibers of equal amount are used instead of modified glass microspheres.

[0040] Comparative Example 5 A high-step tile with good drainage performance, which is different from Example 2 in that modified glass microspheres are not added.

[0041] Performance detection test Tensile strength test, impact strength test, flexural strength test, and aging resistance test were carried out on the high-step tiles with good drainage performance prepared in Examples 1-4 and Comparative Examples 1-5. The test results are recorded in Table 1.

[0042] 1. Tensile strength test: The tensile strength was tested with a CMT4304 type electronic universal testing machine in accordance with the provisions of GB / T 1040.2-2022.

[0043] 2. Impact strength test: The impact strength was tested with a ZBC1400-1 type impact testing machine in accordance with the provisions of GB / T 1843-2008.

[0044] 3. Flexural strength test: The flexural strength and flexural modulus were inspected in accordance with the standard of GB / T 9341-2008. The specimen type was type I, and the dimensions of the test bar (mm) were: 80 (±0.2) × 10 (±0.2) × 4.0 (±0.2), and the flexural speed was 10 mm / min.

[0045] 4. Aging resistance test: According to the provisions of GB / T 16422.2-2022 and GB / T 1843-2008, the specimen was irradiated with ultraviolet light for 1000 h, and its color difference and retention rate of impact strength were tested and calculated, with the unit of %.

[0046] Table 1 It can be seen from Example 2, Example 4 and the data in Table 1 that due to the difference in the carbon chain length in the molecule, the modification effect of octyl acrylate used to synthesize the ternary copolymer macromolecular coupling agent on glass microspheres is not as good as that of butyl acrylate. The ternary copolymer macromolecular coupling agent synthesized by using butyl acrylate, maleic anhydride and 4-vinylpyridine can modify the hollow glass microspheres, uniformly disperse the hollow glass microspheres in the resin matrix, and significantly improve the processing performance and mechanical properties of the high-step tiles.

[0047] According to the data in Example 2, Comparative Examples 1-2, and Table 1, it can be seen that in Comparative Examples 1-2, a binary copolymer was used to modify glass microspheres, and the modification effect was poor. In this application, a ternary copolymer macromolecular coupling agent was synthesized by using acrylate monomer, maleic anhydride, and 4-vinylpyridine and used to perform surface modification on hollow glass microspheres, forming an organic coating layer on the surface of the hollow glass microspheres, which can greatly improve the compatibility between the glass microspheres and the matrix resin. Among them, the anhydride group in the ternary copolymer macromolecular coupling agent undergoes chemical bonding with the hydroxyl group on the surface of the glass microspheres. The acrylate monomer can adjust the flexibility of the molecular chain, and the pyridine ring causes dechlorination of PVC. The conjugated olefins formed after dechlorination are prone to intermolecular crosslinking, forming a stable crosslinked structure, thereby improving the compatibility between the glass microspheres and the PVC resin and enabling the prepared high-tile to have good mechanical properties.

[0048] According to the data in Example 2, Comparative Example 3, and Table 1, it can be seen that in Comparative Example 3, unmodified glass microspheres were added to the PVC resin matrix. Due to the poor compatibility between the glass microspheres and the resin matrix and the easy agglomeration of the glass microspheres, it will have an adverse effect on the PVC resin. In this application, a macromolecular coupling agent was synthesized by using acrylate monomer, maleic anhydride, and 4-vinylpyridine to perform surface modification on the glass microspheres, improving the problem of poor compatibility between the glass microspheres and the PVC resin and enabling the glass microspheres to be uniformly dispersed in the PVC resin, effectively improving the mechanical properties and aging resistance of the material.

[0049] According to the data in Example 2, Comparative Examples 4-5, and Table 1, it can be seen that the high-tile prepared by filling the PVC resin with modified glass microspheres has the characteristics of light weight and high strength. The hollow structure of the hollow glass microspheres can absorb and disperse external forces, reducing stress concentration, thereby significantly improving the impact resistance of the high-tile. In addition, its spherical structure is evenly distributed in the resin matrix, and at an appropriate filling ratio, both the tensile strength and flexural modulus of the high-tile can be significantly improved.

[0050] This specific embodiment is only an explanation of this application and does not limit this application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as they are within the scope of the claims of this application, they are protected by the patent law.

Claims

1. A high tread tile with good drainage performance, characterized in that: The invention is prepared from the following raw materials by weight: 60-70 parts of polyvinyl chloride, 8-10 parts of modified glass microspheres, 3-5 parts of stabilizer, 2-3 parts of titanium dioxide, 0.3-0.5 parts of antioxidant, 0.3-0.5 parts of ultraviolet absorber, 3-5 parts of chlorinated polyethylene, 1-3 parts of ASA resin powder, 0.2-0.4 parts of color powder; The raw materials for preparing the modified glass microspheres include hollow glass microspheres, acrylate monomers, maleic anhydride and 4-vinyl pyridine, and the weight ratio of the hollow glass microspheres, acrylate monomers, maleic anhydride and 4-vinyl pyridine is 10: (0.8-1.2): (0.5-0.7): (0.08-0.12).

2. A high tread tile with good drainage performance according to claim 1, characterized in that: The acrylic acid ester monomer is one of methyl acrylate, ethyl acrylate and butyl acrylate.

3. A high tread tile with good drainage performance according to claim 1, characterized in that: The preparation method of the modified glass microspheres is as follows: (1) dissolving acrylate monomer, maleic anhydride and 4-vinylpyridine in acetone, introducing nitrogen, and heating to 70-80°C, then adding initiator and chain transfer agent, reacting for 2-3 hours to obtain a copolymer solution, then adding anhydrous ethanol, stirring, precipitating a polymer, washing 2-3 times, and drying to obtain a terpolymer; (2) Dissolve the terpolymer in propanol, add glass microbeads, stir and react for 3-4 hours, and obtain modified glass microbeads after filtration and drying.

4. A high tread tile with good drainage performance according to claim 3, characterized in that: In the step (1), the initiator is benzoyl peroxide, and the chain transfer agent is dodecyl mercaptan.

5. A high tread tile with good drainage performance according to claim 1, characterized in that: The stabilizer is at least one of an organic tin stabilizer, a rare earth stabilizer, and a metal soap stabilizer.

6. A high tread tile with good drainage performance according to claim 1, characterized in that: The antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 626.

7. A high tread tile with good drainage performance according to claim 1, characterized in that: The ultraviolet absorber is at least one of UV-328, UV-360 and UV-326.

8. A high tread tile with good drainage performance according to claim 1, characterized in that: The particle size of the hollow glass microspheres is 20-40 μm.

9. A method for preparing a high-tee tile with good drainage performance as claimed in any one of claims 1 to 8, characterized in that: The following steps are involved: The raw materials are weighed according to the component ratio, and polyvinyl chloride, modified glass microbeads, stabilizer, titanium dioxide, antioxidant, ultraviolet absorber, chlorinated polyethylene, ASA resin powder and color powder are melt-mixed at 150-170° C. for 20-30 minutes to obtain a premix; the premix is ​​transferred to an extruder for heating and extrusion, and transported to a shaping mold for shaping to obtain a high teva.

10. The method for preparing a high-tee tile with good drainage performance according to claim 9, characterized in that: The extrusion temperature in the extruder is 170-180°C, and the setting temperature is 160-170°C.

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