A weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material

Abstract

The present invention relates to the technical field of polyurethane mortar, and particularly relates to a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material comprises: modified silica powder, waterborne polyurethane emulsion, dispersant, curing agent, portland cement, light resin colored sand, defoamer and leveling agent. The modified silica is modified by PS microspheres and block copolymer P123 to have a high-porosity structure. At the same time, bimetallic MOFs materials are used and compounded with a light stabilizer on the silica with high porosity, and then a fluorine-containing polymer with self-healing properties is grafted to obtain it. A weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material of the present invention has excellent weather resistance, good mechanical properties and certain self-healing properties, expanding the application field of waterborne polyurethane mortar floor materials.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane mortar, and in particular to a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material. Background Art

[0002] In the field of architectural decoration, waterborne polyurethane mortar floor materials are widely used due to their good decorative properties and convenient construction. However, there are still many deficiencies in existing materials, which limit their further development and application.

[0003] On the one hand, when traditional waterborne polyurethane mortar floor materials face complex usage environments, their comprehensive performance is difficult to meet the requirements. For example, in outdoor or indoor spaces with high humidity and high light, the floor is prone to aging, which not only affects the appearance but also reduces the service life and increases the maintenance cost, hindering its application in special environments. On the other hand, with the increasing attention to multifunctional materials, waterborne polyurethane mortar floor materials with multiple functions have become a research hotspot. However, existing products perform poorly in terms of performance, such as strength, wear resistance, chemical resistance, and self-healing performance, and are difficult to meet the market's demand for high-performance floor materials.

[0004] Therefore, it is urgent to develop a waterborne polyurethane mortar colored sand self-leveling floor material that has excellent weather resistance, decorative properties, good mechanical properties, and self-healing performance, which is of great significance for promoting the development of the architectural decoration material industry. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material to solve the problems of poor weather resistance, single function, and small application range in existing waterborne polyurethane mortar floor materials.

[0006] Based on the above purpose, the present invention provides a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material, which comprises the following raw materials in parts by weight: modified silica powder: 30 - 40 parts, waterborne polyurethane emulsion: 40 - 60 parts, dispersant: 0.5 - 1 part, curing agent: 6 - 8 parts, portland cement: 20 - 30 parts, light resin colored sand: 30 - 40 parts, defoaming agent: 0.1 - 0.3 part, and leveling agent: 0.1 - 0.3 part;

[0007] The specific preparation method of the modified silica powder is as follows:

[0008] (1) Mix copper chloride, cobalt acetate, terephthalic acid, ethylene glycol, and N,N-dimethylformamide, put them into a high-temperature hydrothermal autoclave, heat up to 150 - 170 °C with stirring, react for 12 - 18 h, cool to room temperature, filter, wash, and dry to obtain copper / cobalt bimetallic MOFs;

[0009] (2) Add PS microspheres into ethanol, ultrasonicate for 30 - 50 min, then add tetraethyl orthosilicate, heat up to 50 - 70 °C, react for 18 - 24 h, after cooling to room temperature, filter, wash, and dry to obtain mixture A;

[0010] (3) Add the mixture A obtained in (2) and block copolymer P123 into ethanol, ultrasonicate for 20 - 40 min, then add tetraethyl orthosilicate, heat up to 40 - 50 °C, react for 8 - 12 h, filter, wash, and heat in a muffle furnace at a heating rate of 1 - 5 °C to 500 - 600 °C, keep warm for 3 - 5 h, after cooling to room temperature, obtain silica with high porosity;

[0011] (4) Add the silica with high porosity obtained in (3) into ethanol, ultrasonicate for 20 - 40 min, add the copper / cobalt bimetallic MOFs obtained in (1) and a light stabilizer, heat up to 25 - 35 °C, react for 6 - 8 h, filter, wash, and dry to obtain mixture B;

[0012] (5)Under nitrogen protection, add perfluoropropyl vinyl ether, chlorotrifluoroethylene, 3 - methacrylamidophenylboronic acid, dimethyl cystine ester, and sodium dodecyl sulfate into deionized water, stir for 20 - 40 min, then add 2 - cyanopropyl - 2 - yl benzodithio and potassium persulfate, heat up to 60 - 80 °C, react for 8 - 12 h, cool to room temperature, add hydroquinone, stir for 30 - 40 min, centrifuge, wash, and dry to obtain a fluoropolymer containing disulfide bonds and borate ester bonds;

[0013] (6)Mix the mixture B obtained in (4), the fluoropolymer containing disulfide bonds and borate ester bonds obtained in (5), and N,N - dimethylformamide, heat up to 80 - 100 °C, react for 8 - 12 h, cool to room temperature, centrifuge, wash, and dry, and pass through a 300 - 400 mesh sieve to obtain modified silica powder.

[0014] Preferably, the dispersant refers to DX - 915 or DX - 407 produced by Metachemie.

[0015] Preferably, the curing agent refers to toluene diisocyanate or isophorone diisocyanate.

[0016] Preferably, the defoamer refers to BYK - 052 or BYK - 053 produced by BYK.

[0017] Preferably, the leveling agent refers to EFKA - 3777 produced by Efka or BYK - 333 produced by BYK.

[0018] Preferably, in (1), the weight ratio of copper chloride, cobalt acetate, terephthalic acid, ethylene glycol, and N,N-dimethylformamide is 3-6:1-2:0.6-1:3-5:15-25. The prepared copper / cobalt bimetallic MOFs can effectively shield the degradation of ultraviolet light due to their unique structure, enhancing the stability of the material.

[0019] Preferably, in (2), the weight ratio of PS microspheres, tetraethyl orthosilicate, and ethanol is 0.8-1:0.9-1.5:10-14.

[0020] Preferably, in (2), the particle size of the PS microspheres is 50-100 nm. The size of the PS microspheres affects the macropore pore size of the modified silica. Appropriate pores can provide a larger surface area and also provide certain structural support, preventing the pore structure of the silica from collapsing easily.

[0021] Preferably, in (3), the weight ratio of mixture A, block copolymer P123, tetraethyl orthosilicate, and ethanol is 1:0.1-0.2:1-1.2:10-14. The addition of block copolymer P123 enables the silica to obtain a more abundant mesoporous structure on the basis of the macroporous structure, further enhancing the porosity of the silica.

[0022] Preferably, in (4), the weight ratio of highly porous silica, copper / cobalt bimetallic MOFs, light stabilizer, and ethanol is 1:0.2-0.4:0.3-0.5:10-14.

[0023] Preferably, in (4), the light stabilizer is prepared by mixing nano-zinc oxide and nano-cerium oxide in a weight ratio of 2:1. Nano-zinc oxide and nano-cerium oxide can absorb ultraviolet light and inhibit photo-oxidative degradation.

[0024] Preferably, in (5), the weight ratio of perfluoropropyl vinyl ether, chlorotrifluoroethylene, 3-methacrylamidophenylboronic acid, cystine dimethyl ester, sodium dodecyl sulfate, 2-cyanopropyl-2-yl benzodithio, potassium persulfate, hydroquinone, and deionized water is 1:0.5-1:0.2-0.5:0.2-0.5:0.01-0.05:0.005-0.015:0.002-0.01:0.01-0.03:15-25.

[0025] Preferably, in (6), the weight ratio of mixture B, fluoropolymer containing disulfide bonds and borate bonds, and N,N-dimethylformamide is 1:0.2-0.4:10-14. The disulfide bonds provide a certain self-healing ability for the material, and the isocyanate bonds can provide a more stable chemical bond when the fluoropolymer binds to the silica.

[0026] Preferably, the weight ratio of the aqueous polyurethane emulsion, dispersant, modified silica powder, curing agent, portland cement, light resin colored sand, defoamer and leveling agent in (7) is 40 - 60: 0.5 - 1: 30 - 40: 6 - 8: 20 - 30: 30 - 40: 0.1 - 0.3: 0.1 - 0.3.

[0027] Furthermore, the present invention also provides a preparation method of the above weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material, including the following process: adding a dispersant to the aqueous polyurethane emulsion, stirring for 10 - 20 min, adding the modified silica powder, stirring for 20 - 30 min, then adding the curing agent, portland cement, light resin colored sand, defoamer and leveling agent, mixing and stirring for 1 - 3 h, then scraping and coating on the coated surface with a toothed trowel, and after curing, obtaining the weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material.

[0028] The beneficial effects of the present invention:

[0029] 1. Excellent weather resistance: The floor material of the present invention constructs a multi-level weather resistance protection system through copper / cobalt bimetallic MOFs, light stabilizers and fluorine-containing polymers with self-healing functions. Due to its unique structure, copper / cobalt bimetallic MOFs effectively shield the degradation of ultraviolet light and enhance the stability of the material; light stabilizers effectively absorb ultraviolet light and inhibit photo-oxidative degradation; fluorine-containing polymers endow the material with good chemical resistance and weather resistance. These components work synergistically to significantly reduce the influence of light, temperature and humidity changes on the material, keeping the color of the floor stable during long-term use, not easily showing phenomena such as aging and fading, and greatly extending the service life.

[0030] 2. Good mechanical properties: The silica with high porosity in the material effectively improves the structural stability and hardness of the material. At the same time, the curing agent, portland cement, etc. cooperate with other components to enhance the bonding force between the coating and the substrate. This makes the floor material not only have excellent wear resistance, and can keep the surface smooth and the structure intact when under external forces such as friction and heavy pressure, but also has strong adhesion and is not easily prone to problems such as coating peeling and delamination, ensuring the reliability and stability of the floor in various use scenarios.

[0031] 3. Self-healing function: The light stabilizers and fluorine-containing polymers with self-healing ability contained in the floor material of the present invention endow the material with self-healing ability. When scratches or minor damages appear on the material surface, the components in the light stabilizer can absorb energy and inhibit the further expansion of the damage; at the same time, the disulfide bonds in the fluorine-containing polymer with self-healing ability undergo a reversible reaction under certain conditions, promoting the rearrangement of the internal structure of the material, automatically filling the scratches and damaged parts, restoring the integrity and performance of the material, reducing the daily maintenance cost, and improving the use value of the floor. Detailed implementation manners

[0032] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with specific embodiments.

[0033] The sources of the reagents used in the embodiments of the present invention are as follows:

[0034] Copper chloride was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the product number C106774 and a purity of 99%; cobalt acetate was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number C805752 and a purity of 98%; terephthalic acid was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the product number P420255 and a purity of 99%; ethylene glycol was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the product number E103319 and a purity of 98%; PS microspheres were purchased from Suzhou NanoMicro Technologies Co., Ltd., with a particle size of 50 - 100 nm; tetraethyl orthosilicate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the product number T110593 and a purity of 98%; block polymer P123 was purchased from Tianjin Xiensi Biochemical Technology Co., Ltd., with the product number P-10691 and an industrial-grade purity; nano zinc oxide was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number Z820774 and a purity of 99.8%; nano cerium oxide was purchased from Shanghai Easychem Technology Co., Ltd., with the product number R008052 and a purity of 99.5%; perfluoropropyl vinyl ether was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number P857062 and a purity of 98%; chlorotrifluoroethylene was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number C889791 and a purity of 99.9%; 3-methacrylamidophenylboronic acid was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number M856878 and a purity of 98%; cystine dimethyl ester was purchased from Guangzhou Jiantu Technology Co., Ltd., with a purity of 98%; sodium dodecyl sulfate was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number S850167 and a purity of 97%; 2-cyanopropyl-2-yl benzodithiole was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number C885875 and a purity of 97%; potassium persulfate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the product number P112193 and a purity of 99%; hydroquinone was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number H811112 and a purity of 99%; p-toluenesulfonic acid was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number T823839 and a purity of 99%; aqueous polyurethane emulsion was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number A909856 and a solid content of 40%; portland cement was purchased from Tangshan Hongye Special Cement Co., Ltd., with the model P·I; toluene diisocyanate was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number T823849 and a purity of 98%; isophorone diisocyanate was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., with the product number I811865 and a purity of 99%; light resin colored sand was purchased from Dongguan Shili Surface Treatment Materials Co., Ltd., with a specification of 7 - 320 mesh; Cu-MOFs were purchased from Changsha Yimo Biotechnology Co., Ltd., with a purity of 98%; silicon dioxide was purchased from Tianjin Xiensi Biochemical Technology Co., Ltd., with a purity of 99%.

[0035] Example 1: A specific preparation scheme of a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material, including the following steps:

[0036] (1) Mix 80 g of copper chloride, 30 g of cobalt acetate, 16 g of terephthalic acid, 80 g of ethylene glycol, and 400 g of N,N-dimethylformamide, put them into a high-temperature hydrothermal autoclave, heat up to 150 °C with stirring, react for 12 h, cool to room temperature, filter, wash, and dry to obtain copper / cobalt bimetallic MOFs;

[0037] (2) Add 320 g of PS microspheres with a particle size of 50 nm to 3.2 Kg of ethanol, ultrasonicate for 30 min, then add 350 g of tetraethyl orthosilicate, heat up to 50 °C, react for 18 h, cool to room temperature, filter, wash, and dry to obtain mixture A;

[0038] (3) Add 400 g of mixture A obtained in (2) and 40 g of block copolymer P123 to 4 Kg of ethanol, ultrasonicate for 20 min, then add 400 g of tetraethyl orthosilicate, heat up to 40 °C, react for 8 h, filter, wash, and heat in a muffle furnace at a heating rate of 1 °C to 500 °C, hold for 3 h, cool to room temperature to obtain silica with high porosity, and the pore volume is 0.53 cm 3 / g;

[0039] (4) Add 450 g of silica with high porosity obtained in (3) to 4.5 Kg of ethanol, ultrasonicate for 20 min, add 90 g of copper / cobalt bimetallic MOFs obtained in (1) and 135 g of light stabilizer (nano zinc oxide: nano cerium oxide = 2:1), heat up to 25 - 35 °C, react for 6 - 8 h, filter, wash, and dry to obtain mixture B;

[0040] (5) Under nitrogen protection, add 80 g of perfluoroalkyl vinyl ether, 40 g of chlorotrifluoroethylene, 16 g of 3-methacrylamidophenylboronic acid, 16 g of cystine dimethyl ester, and 0.8 g of sodium dodecyl sulfate to 1.2 Kg of deionized water, stir for 20 min, then add 0.4 g of 2-cyanopropyl-2-yl benzodithio and 0.16 g of potassium persulfate, heat up to 60 °C, react for 8 h, cool to room temperature, add 2.4 g of hydroquinone, stir for 30 min, centrifuge, wash, and dry to obtain a fluoropolymer containing disulfide bonds and borate ester bonds;

[0041] (6) Mix 400 g of mixture B obtained in (4), 80 g of fluoropolymer containing disulfide bonds and borate ester bonds obtained in (5), and 4 Kg of N,N-dimethylformamide, heat up to 80 °C, react for 8 h, cool to room temperature, centrifuge, wash, dry, and pass through a 300-mesh sieve to obtain modified silica powder;

[0042] (7) Add 5 g of dispersant DX-915 to 400 g of aqueous polyurethane emulsion, stir for 10 min, add 300 g of modified silica powder obtained in (6), stir for 20 min, then add 60 g of isophorone diisocyanate, 200 g of portland cement, 300 g of light resin colored sand, 1 g of defoamer BYK-052 and 1 g of leveling agent EFKA-3777. After mixing and stirring for 1 h, scrape and coat it on the surface to be coated with a toothed trowel. After curing, a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material is obtained.

[0043] Example 2: A specific preparation scheme of a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material, comprising the following steps:

[0044] (1) Mix 120 g of copper chloride, 45 g of cobalt acetate, 24 g of terephthalic acid, 120 g of ethylene glycol and 600 g of N,N-dimethylformamide, put them into a high-temperature hydrothermal autoclave, heat up to 160 °C with stirring, react for 15 h, cool to room temperature, filter, wash and dry to obtain copper / cobalt bimetallic MOFs;

[0045] (2) Add 360 g of PS microspheres with a particle size of 80 nm to 4.8 Kg of ethanol, ultrasonicate for 40 min, then add 480 g of tetraethyl orthosilicate, heat up to 60 °C, react for 21 h, cool to room temperature, filter, wash and dry to obtain mixture A;

[0046] (3) Add 400 g of mixture A obtained in (2) and 60 g of block copolymer P123 to 4.8 Kg of ethanol, ultrasonicate for 30 min, then add 440 g of tetraethyl orthosilicate, heat up to 45 °C, react for 10 h, filter, wash and heat up to 550 °C in a muffle furnace at a heating rate of 3 °C, keep warm for 4 h, and cool to room temperature to obtain silica with high porosity, and the pore volume is 0.59 cm 3 / g;

[0047] (4) Add 450 g of silica with high porosity obtained in (3) to ethanol, ultrasonicate for 30 min, add 135 g of copper / cobalt bimetallic MOFs obtained in (1) and 180 g of light stabilizer (nano zinc oxide: nano cerium oxide = 2:1), heat up to 30 °C, react for 7 h, filter, wash and dry to obtain mixture B;

[0048] (5) Under nitrogen protection, 120 g of perfluoroalkyl vinyl ether, 90 g of chlorotrifluoroethylene, 42 g of 3 - methacrylamidophenylboronic acid, 42 g of dimethyl cystine and 4.2 g of sodium dodecyl sulfate were added to 2.4 Kg of deionized water, stirred for 30 min, then 1.2 g of 2 - cyanopropyl - 2 - yl benzodithiole and 0.72 g of potassium persulfate were added, the temperature was raised to 70 °C, reacted for 10 h, cooled to room temperature, 2.4 g of hydroquinone was added, stirred for 35 min, and after centrifugation, washing and drying, a fluoropolymer containing disulfide bonds and borate ester bonds was obtained;

[0049] (6) 400 g of mixture B obtained in (4), 120 g of the fluoropolymer containing disulfide bonds and borate ester bonds obtained in (5) and N,N - dimethylformamide were mixed, the temperature was raised to 90 °C, reacted for 10 h, cooled to room temperature, centrifuged, washed, dried, and passed through a 350 - mesh sieve to obtain modified silica powder;

[0050] (7) 7.5 g of dispersant DX - 915 was added to 500 g of aqueous polyurethane emulsion, stirred for 15 min, 350 g of the modified silica powder obtained in (6) was added, stirred for 25 min, then 70 g of isophorone diisocyanate, 250 g of portland cement, 350 g of light resin colored sand, 2 g of defoamer BYK - 052 and 2 g of leveling agent EFKA - 3777 were added, after mixing and stirring for 2 h, it was scraped onto the coated surface with a toothed trowel, and after curing, a weather - resistant decorative aqueous polyurethane mortar colored sand self - leveling floor material was obtained.

[0051] Example 3: A specific preparation scheme of a weather - resistant decorative aqueous polyurethane mortar colored sand self - leveling floor material, including the following steps:

[0052] (1) 180 g of copper chloride, 60 g of cobalt acetate, 30 g of terephthalic acid, 150 g of ethylene glycol and 750 g of N,N - dimethylformamide were mixed, put into a high - temperature hydrothermal autoclave, stirred and heated to 170 °C, reacted for 18 h, cooled to room temperature, filtered, washed and dried to obtain copper / cobalt bimetallic MOFs;

[0053] (2) 300 g of PS microspheres with a particle size of 100 nm were added to 5.2 Kg of ethanol, ultrasonicated for 50 min, then 450 g of tetraethyl orthosilicate was added, the temperature was raised to 70 °C, reacted for 24 h, after cooling to room temperature, filtered, washed and dried to obtain mixture A;

[0054] (3) Add 500 g of compound A and 100 g of block copolymer P123 obtained in (2) into ethanol, ultrasonicate for 40 min, then add 600 g of tetraethyl orthosilicate, heat up to 50 °C, react for 12 h, filter and wash, and heat up to 600 °C in a muffle furnace at a heating rate of 5 °C, hold for 5 h, and after cooling to room temperature, obtain silica with high porosity, and the pore volume is 0.56 cm 3 / g;

[0055] (4) Add 500 g of silica with high porosity obtained in (3) into 7 Kg of ethanol, ultrasonicate for 40 min, add 200 g of copper / cobalt bimetallic MOFs obtained in (1) and 250 g of light stabilizer (nano zinc oxide: nano cerium oxide = 2:1), heat up to 35 °C, react for 8 h, filter, wash and dry to obtain mixture B;

[0056] (5) Under nitrogen protection, add 100 g of perfluoropropyl vinyl ether, 100 g of chlorotrifluoroethylene, 50 g of 3-methacrylamidophenylboronic acid, 50 g of cystine dimethyl ester and 5 g of sodium dodecyl sulfate into 2.5 Kg of deionized water, stir for 40 min, then add 1.5 g of 2-cyanopropyl-2-yl benzodithio and 1 g of potassium persulfate, heat up to 80 °C, react for 12 h, cool to room temperature, add 3 g of hydroquinone, stir for 40 min, centrifuge, wash and dry to obtain a fluorinated polymer containing disulfide bonds and borate ester bonds;

[0057] (6) Mix 500 g of mixture B obtained in (4), 100 g of fluorinated polymer containing disulfide bonds and borate ester bonds obtained in (5) and 7 Kg of N,N-dimethylformamide, heat up to 100 °C, react for 12 h, cool to room temperature, centrifuge, wash and dry, and pass through a 400-mesh sieve to obtain modified silica powder;

[0058] (7) Add 10 g of dispersant DX-915 to 600 g of aqueous polyurethane emulsion, stir for 20 min, add 400 g of modified silica powder obtained in (6), stir for 30 min, then add 80 g of isophorone diisocyanate, 300 g of portland cement, 400 g of light resin colored sand, 3 g of defoamer BYK-052 and 3 g of leveling agent EFKA-3777, mix and stir for 3 h, then scrape with a toothed trowel on the surface to be coated, and after curing, obtain a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material.

[0059] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that: replace the copper / cobalt bimetallic MOF with a common single-metal MOF. The specific preparation process is as follows: A specific preparation scheme for a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material includes the following steps:

[0060] (1) Add 360 g of PS microspheres with a particle size of 80 nm to 4.8 Kg of ethanol, ultrasonicate for 40 min, then add 480 g of tetraethyl orthosilicate, heat up to 60 °C, react for 21 h, cool to room temperature, filter, wash, and dry to obtain mixture A;

[0061] (2) Add 400 g of the mixture A obtained in (1) and 60 g of block copolymer P123 to 4.8 Kg of ethanol, ultrasonicate for 30 min, then add 440 g of tetraethyl orthosilicate, heat up to 45 °C, react for 10 h, filter, wash, and heat in a muffle furnace at a heating rate of 3 °C to 550 °C, hold for 4 h, and cool to room temperature to obtain silica with high porosity, and the pore volume is 0.54 cm 3 / g;

[0062] (3) Add 450 g of the silica with high porosity obtained in (2) to ethanol, ultrasonicate for 30 min, add 135 g of Cu-MOFs and 180 g of light stabilizer (nano zinc oxide: nano cerium oxide = 2:1), heat up to 30 °C, react for 7 h, filter, wash, and dry to obtain mixture B;

[0063] (5) Under nitrogen protection, add 120 g of perfluoroalkyl vinyl ether, 90 g of chlorotrifluoroethylene, 42 g of 3-methacrylamidophenylboronic acid, 42 g of cystine dimethyl ester, and 4.2 g of sodium dodecyl sulfate to 2.4 Kg of deionized water, stir for 30 min, then add 1.2 g of 2-cyanopropyl-2-yl benzodithio and 0.72 g of potassium persulfate, heat up to 70 °C, react for 10 h, cool to room temperature, add 2.4 g of hydroquinone, stir for 35 min, centrifuge, wash, and dry to obtain a fluorinated polymer containing disulfide bonds and borate ester bonds;

[0064] (6) Mix 400 g of the mixture B obtained in (4), 120 g of the fluorinated polymer containing disulfide bonds and borate ester bonds obtained in (5), and N,N-dimethylformamide, heat up to 90 °C, react for 10 h, cool to room temperature, centrifuge, wash, dry, and pass through a 350-mesh sieve to obtain modified silica powder;

[0065] (7) Add 7.5 g of dispersant DX-915 to 500 g of aqueous polyurethane emulsion, stir for 15 min, add 350 g of the modified silica powder obtained in (6), stir for 25 min, then add 70 g of isophorone diisocyanate, 250 g of Portland cement, 350 g of light resin colored sand, 2 g of defoamer BYK-052, and 2 g of leveling agent EFKA-3777, mix and stir for 2 h, then scrape with a toothed trowel onto the surface to be coated, and after curing, obtain a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material.

[0066] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that the modified silica does not pass through PS microspheres to prepare macropores. The specific preparation process is as follows: A specific preparation scheme for a weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material includes the following steps:

[0067] (1) Mix 120 g of copper chloride, 45 g of cobalt acetate, 24 g of terephthalic acid, 120 g of ethylene glycol, and 600 g of N,N-dimethylformamide, put them into a high-temperature hydrothermal autoclave, heat up to 160 °C with stirring, react for 15 h, cool to room temperature, filter, wash, and dry to obtain copper / cobalt bimetallic MOFs;

[0068] (2) Add 90 g of block copolymer P123 to 4.8 Kg of ethanol, ultrasonicate for 30 min, then add 660 g of tetraethyl orthosilicate, heat up to 45 °C, react for 10 h, filter, wash, and heat in a muffle furnace at a heating rate of 3 °C to 550 °C, keep warm for 4 h, and after cooling to room temperature, obtain porous silica with a pore volume of 0.36 cm 3 / g;

[0069] (3) Add 450 g of the porous silica obtained in (2) to ethanol, ultrasonicate for 30 min, add 135 g of the copper / cobalt bimetallic MOFs obtained in (1) and 180 g of a light stabilizer (nano zinc oxide: nano cerium oxide = 2:1), heat up to 30 °C, react for 7 h, filter, wash, and dry to obtain mixture A;

[0070] (4) Under nitrogen protection, add 120 g of perfluoroalkyl vinyl ether, 90 g of chlorotrifluoroethylene, 42 g of 3-methacrylamidophenylboronic acid, 42 g of cystine dimethyl ester, and 4.2 g of sodium dodecyl sulfate to 2.4 Kg of deionized water, stir for 30 min, then add 1.2 g of 2-cyanopropyl-2-yl benzodithio and 0.72 g of potassium persulfate, heat up to 70 °C, react for 10 h, cool to room temperature, add 2.4 g of hydroquinone, stir for 35 min, centrifuge, wash, and dry to obtain a fluorinated polymer containing disulfide bonds and borate ester bonds;

[0071] (5) Mix 400 g of mixture A obtained in (3), 120 g of the fluorinated polymer containing disulfide bonds and borate ester bonds obtained in (5), and N,N-dimethylformamide, heat up to 90 °C, react for 10 h, cool to room temperature, centrifuge, wash, dry, and pass through a 350-mesh sieve to obtain modified silica powder;

[0072] (6) Add 7.5 g of dispersant DX-915 to 500 g of aqueous polyurethane emulsion, stir for 15 min, add 350 g of modified silica powder obtained in (5), stir for 25 min, then add 70 g of isophorone diisocyanate, 250 g of portland cement, 350 g of light resin colored sand, 2 g of defoamer BYK-052 and 2 g of leveling agent EFKA-3777. After mixing and stirring for 2 h, scrape and coat it on the surface to be coated with a serrated trowel. After curing, a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material is obtained.

[0073] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that the modified silica does not pass through the preparation of mesopores by block copolymer P123. The specific preparation process is as follows: A specific preparation scheme for a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material includes the following steps:

[0074] (1) Mix 120 g of copper chloride, 45 g of cobalt acetate, 24 g of terephthalic acid, 120 g of ethylene glycol and 600 g of N,N-dimethylformamide, put them into a high-temperature hydrothermal kettle, heat up to 160 °C with stirring, react for 15 h, cool to room temperature, filter, wash and dry to obtain copper / cobalt bimetallic MOFs;

[0075] (2) Add 360 g of PS microspheres with a particle size of 80 nm to 4.8 Kg of ethanol, ultrasonicate for 40 min, then add 480 g of tetraethyl orthosilicate, heat up to 60 °C, react for 21 h, cool to room temperature, filter, wash, and heat up to 550 °C in a muffle furnace at a heating rate of 3 °C, hold for 4 h, and cool to room temperature to obtain porous silica with a pore volume of 0.27 cm 3 / g;

[0076] (3) Add 450 g of the porous silica obtained in (2) to ethanol, ultrasonicate for 30 min, add 135 g of copper / cobalt bimetallic MOFs and 180 g of light stabilizer (nano zinc oxide: nano cerium oxide = 2:1) obtained in (1), heat up to 30 °C, react for 7 h, filter, wash and dry to obtain mixture A;

[0077] (4) Under nitrogen protection, add 120 g of perfluoroalkyl vinyl ether, 90 g of chlorotrifluoroethylene, 42 g of 3-methacrylamidophenylboronic acid, 42 g of dimethyl cystine and 4.2 g of sodium dodecyl sulfate to 2.4 Kg of deionized water, stir for 30 min, then add 1.2 g of 2-cyanopropyl-2-yl benzodithio and 0.72 g of potassium persulfate, heat up to 70 °C, react for 10 h, cool to room temperature, add 2.4 g of hydroquinone, stir for 35 min, centrifuge, wash and dry to obtain a fluoropolymer containing disulfide bonds and borate bonds;

[0078] (5) Mix 400 g of the mixture A obtained in (3), 120 g of the fluoropolymer containing disulfide bonds and borate bonds obtained in (4), and N,N-dimethylformamide, heat up to 90 °C, react for 10 h, cool to room temperature, centrifuge, wash, dry, and pass through a 350-mesh sieve to obtain modified silica powder;

[0079] (6) Add 7.5 g of dispersant DX-915 to 500 g of aqueous polyurethane emulsion, stir for 15 min, add 350 g of the modified silica powder obtained in (6), stir for 25 min, then add 70 g of isophorone diisocyanate, 250 g of portland cement, 350 g of light resin colored sand, 2 g of defoamer BYK-052 and 2 g of leveling agent EFKA-3777, mix and stir for 2 h, then scrape with a toothed trowel on the surface to be coated, and after curing, obtain a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material.

[0080] Comparative Example 4: The difference between Comparative Example 4 and Example 2 is that the modified silica is replaced with ordinary silica. The specific preparation process is as follows: A specific preparation scheme for a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material includes the following steps:

[0081] (1) Mix 120 g of copper chloride, 45 g of cobalt acetate, 24 g of terephthalic acid, 120 g of ethylene glycol, and 600 g of N,N-dimethylformamide, put them into a high-temperature hydrothermal kettle, heat up to 160 °C with stirring, react for 15 h, cool to room temperature, filter, wash, and dry to obtain copper / cobalt bimetallic MOFs;

[0082] (2) Add 450 g of silica to ethanol, ultrasonicate for 30 min, add 135 g of the copper / cobalt bimetallic MOFs obtained in (1) and 180 g of light stabilizer (nano zinc oxide: nano cerium oxide = 2:1), heat up to 30 °C, react for 7 h, filter, wash, and dry to obtain mixture A;

[0083] (3) Under nitrogen protection, add 120 g of perfluoroalkyl vinyl ether, 90 g of chlorotrifluoroethylene, 42 g of 3-methacrylamidophenylboronic acid, 42 g of dimethyl cystine, and 4.2 g of sodium dodecyl sulfate to 2.4 Kg of deionized water, stir for 30 min, then add 1.2 g of 2-cyanopropyl-2-yl benzodisulfide and 0.72 g of potassium persulfate, heat up to 70 °C, react for 10 h, cool to room temperature, add 2.4 g of hydroquinone, stir for 35 min, centrifuge, wash, and dry to obtain a fluoropolymer containing disulfide bonds and borate bonds;

[0084] (4) Mix 400 g of the mixture A obtained in (2), 120 g of the fluoropolymer containing disulfide bonds and borate ester bonds obtained in (3), and N,N-dimethylformamide, heat up to 90 °C, react for 10 h, cool to room temperature, centrifuge, wash, dry, and pass through a 350-mesh sieve to obtain modified silica powder;

[0085] (5) Add 7.5 g of dispersant DX-915 to 500 g of aqueous polyurethane emulsion, stir for 15 min, add 350 g of the modified silica powder obtained in (4), stir for 25 min, then add 70 g of isophorone diisocyanate, 250 g of portland cement, 350 g of light resin colored sand, 2 g of defoamer BYK-052 and 2 g of leveling agent EFKA-3777, mix and stir for 2 h, then scrape and coat on the coated surface with a toothed trowel. After curing, a weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor material is obtained.

[0086] Performance test:

[0087] Prepare the weather-resistant decorative aqueous polyurethane mortar colored sand self-leveling floor materials with consistent sizes from Examples 1-3 and Comparative Examples 1-4 respectively according to the preparation method as test samples.

[0088] Weather resistance test: Conduct the test according to the conditions specified in Standard GB / T 1865-2009. During the test, parameters such as the irradiance of the xenon arc lamp, blackboard temperature, relative humidity, and water spray cycle of each specimen are kept consistent to simulate the changes in light, temperature, and humidity in the natural environment. Continuously test for 2000 h, take out the specimens and use a color difference meter to measure the color change of the specimens before and after aging. The experimental data are shown in Table 1; then continue to detect the adhesion grade of the specimens after aging by the cross-cut method according to Standard GB / T 9286-2021. The rating is divided into 0-5 levels, and level 0 represents the best adhesion state. The experimental data are shown in Table 1.

[0089] Abrasion resistance test: Conduct the test according to Standard GB / T 1768-2006. Weigh the mass of the specimens before and after friction with a balance with an accuracy of 0.001 g, and calculate the mass loss rate. The experimental results are shown in Table 1.

[0090] Self-healing experiment: Use a sharp tool to scratch a 0.5-mm deep and 2-cm long scratch on the surface of the prepared floor material specimens. Place the specimens with scratches in a constant temperature and humidity chamber at a temperature of 25 °C and a relative humidity of 50% to allow the material to self-heal naturally. After seven days, observe the repair situation of the material, and the repair rate The experimental results are shown in Table 1.

[0091] Pore volume: measured by elliptical porosimetry. The results are shown in Table 1.

[0092] Table 1 Performance test results

[0093]

[0094] Data Analysis:

[0095] From the data of Examples 1-3 in Table 1, it can be seen that the weather-resistant decorative water-based polyurethane mortar colored sand self-leveling floor materials of Examples 1-3 all exhibit good weather resistance, high wear resistance and good self-repairing properties. Among them, the comprehensive performance of Example 2 is the best, and the pore volume reaches 0.59 cm 3 / g, which shows that the introduction of copper / cobalt bimetallic MOFs used in the present invention significantly improves the catalytic activity and stability of the material through the synergistic effect between metals, effectively delays the degradation caused by ultraviolet rays, and the modified silica loads light stabilizers and MOFs through high porosity to achieve precise distribution of functional components. The reasonable design of pore structure is the key to functional synergy. Finally, the fluorinated polymers with disulfide bonds and borate bonds give the material dynamic self-healing ability. This fluorinated polymer is grafted on the modified silica to obtain a larger surface area, which is easier to contact with the external environment, thereby better playing a role.

[0096] As can be seen from Table 1, the weather resistance, wear resistance and self-healing properties of Comparative Example 1 compared to Example 2 are all reduced, and the adhesion level is reduced. This may be because the copper / cobalt bimetallic MOFs can produce a synergistic effect by virtue of their unique bimetallic structure. This synergistic effect can enhance the material's ability to shield ultraviolet rays and effectively inhibit photooxidative degradation, thereby significantly improving the stability and weather resistance of the material. In terms of wear resistance, bimetallic MOFs can synergize with other ingredients to enhance the bonding force between the coating and the substrate, and help to improve the overall structural stability of the material. In terms of self-healing performance, the weather-resistant protection system constructed by bimetallic MOFs can provide a stable environment for the disulfide bonds in the fluoropolymer to exert their self-healing function. Ordinary monometallic MOFs cannot provide such favorable conditions, and the self-healing function of the fluoropolymer is affected, and the self-healing rate of the material is reduced.

[0097] It can be seen from Table 1 that the weather resistance, wear resistance and self-healing property of Comparative Example 2 are significantly decreased compared with Example 2, and the adhesion level is also reduced. This may be because the macroporous structure constructed by PS microspheres is the key link in forming high porosity. Without this key link, the pore volume is reduced to 0.36 cm 3 / g. The macropores in Example 2 provide sufficient space for subsequent loading of functional components such as light stabilizers and bimetallic MOFs, which is conducive to the uniform dispersion and efficient functioning of these components. In terms of weather resistance, the macroporous structure enables the light stabilizer to better contact with external light, enhancing the absorption and shielding effect of ultraviolet rays. At the same time, a reasonable macroporous structure helps to enhance the overall structural stability of the material, enabling the internal structure to better maintain integrity when the material is subjected to external forces such as friction. The macroporous structure also provides a larger movement space and reaction sites for the disulfide bonds in the fluoropolymer, enabling a more effective reversible reaction to occur for repair when the material is damaged. The absence of macropores in Comparative Example 2 limits the self-healing reaction of the fluoropolymer, resulting in a reduced repair rate. Finally, in terms of adhesion, the macroporous structure can increase the contact area and mechanical interlocking effect between the coating and the substrate, enhancing adhesion.

[0098] As can be seen from Table 1, Comparative Example 3 is inferior to Example 2 in terms of weather resistance, abrasion resistance, self-healing rate, and adhesion grade. This may be because in the process of Example 2, the block copolymer P123 acts as a template to precisely regulate the formation of mesoporous structures, enriching the porosity of silica. Mesopores play a crucial role in increasing porosity. Without mesopores to regulate porosity, the pore volume of the obtained silica decreases to 0.27 cm 3 / g. The appropriate pore size and high specific surface area in Example 2 greatly promote the uniform dispersion and efficient loading of functional components such as light stabilizers and copper / cobalt bimetallic MOFs. In terms of weather resistance, the mesoporous structure enables the light stabilizer to be fully exposed and more effectively absorb ultraviolet rays. At the same time, the bimetallic MOFs, with the help of the good dispersion of mesopores, better shield ultraviolet rays and inhibit the photooxidative degradation of the material. In terms of abrasion resistance, mesopores enhance the structural stability and toughness of the material. When subjected to external forces such as friction and heavy pressure, the mesoporous structure can effectively disperse stress and reduce local damage. In terms of self-healing performance, mesopores provide more reaction sites and diffusion channels for the disulfide bonds in the fluoropolymer. When the material is damaged, these chemical bonds can quickly move and react through the mesopores to achieve self-healing. In terms of adhesion, the mesoporous structure increases the contact area and interaction force between the coating and the substrate, improving adhesion.

[0099] As can be seen from Table 1, the performance of Comparative Example 4 has decreased significantly compared to Example 2. This may be because the ordinary silica used in Comparative Example 4 has poor porosity, and the pore volume is only 0.03 cm 3 / g. In Example 2, the prepared modified silica has a unique high-porosity structure. The abundant surface porosity and pore sizes of different dimensions can load key functional components such as bimetallic MOFs and light stabilizers, and provide a stable environment conducive to their functioning. The pore structure allows the light stabilizer to fully contact external light, enhancing the absorption and scattering capabilities of ultraviolet rays. At the same time, the bimetallic MOFs can effectively shield ultraviolet rays in the pores, inhibiting the photo-oxidative degradation of the material. When the material is subjected to friction, this high-porosity structure can also disperse stress and reduce surface damage. Meanwhile, without such modification, the low specific surface area also makes it difficult for the self-healing compound to reach the damaged location, restricting the performance of the self-healing function. Finally, the special structure of the modified silica increases the contact area and mechanical interlocking effect between the coating and the substrate, enabling the coating to be tightly bonded to the substrate. The structure of ordinary silica is simple and cannot provide sufficient bonding force, resulting in poor adhesion between the coating and the substrate.

[0100] Those of ordinary skill in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material, characterized in that It includes the following raw materials by weight fraction: modified silica powder: 30 - 40 parts, aqueous polyurethane emulsion: 40 - 60 parts, dispersant: 0.5 - 1 part, curing agent: 6 - 8 parts, portland cement: 20 - 30 parts, light resin colored sand: 30 - 40 parts, defoamer: 0.1 - 0.3 part, and leveling agent: 0.1 - 0.3 part; The specific preparation method of the modified silica powder is as follows: (1) Mix copper chloride, cobalt acetate, terephthalic acid, ethylene glycol, and N,N - dimethylformamide, put them into a high - temperature hydrothermal autoclave, heat up to 150 - 170 °C with stirring, react for 12 - 18 h, cool to room temperature, filter, wash, and dry to obtain copper / cobalt bimetallic MOFs; (2) Add PS microspheres into ethanol, ultrasonicate for 30 - 50 min, then add tetraethyl orthosilicate, heat up to 50 - 70 °C, react for 18 - 24 h, after cooling to room temperature, filter, wash, and dry to obtain mixture A; (3) Add the mixture A obtained in (2) and block copolymer P123 into ethanol, ultrasonicate for 20 - 40 min, then add tetraethyl orthosilicate, heat up to 40 - 50 °C, react for 8 - 12 h, filter, wash, and heat up in a muffle furnace at a heating rate of 1 - 5 °C to 500 - 600 °C, keep warm for 3 - 5 h, after cooling to room temperature, obtain silica with high porosity; (4) Add the silica with high porosity obtained in (3) into ethanol, ultrasonicate for 20 - 40 min, add the copper / cobalt bimetallic MOFs obtained in (1) and light stabilizer, heat up to 25 - 35 °C, react for 6 - 8 h, filter, wash, and dry to obtain mixture B; (5) Under nitrogen protection, add perfluoropropyl vinyl ether, chlorotrifluoroethylene, 3 - (methacrylamido)phenylboronic acid, cystine dimethyl ester, and sodium dodecyl sulfate into deionized water, stir for 20 - 40 min, then add 2 - cyanopropyl - 2 - yl benzodithio and potassium persulfate, heat up to 60 - 80 °C, react for 8 - 12 h, cool to room temperature, add hydroquinone, stir for 30 - 40 min, centrifuge, wash, and dry to obtain a fluorinated polymer containing disulfide bonds and borate ester bonds; (6) Mix the mixture B obtained in (4), the fluorinated polymer containing disulfide bonds and borate ester bonds obtained in (5), and N,N - dimethylformamide, heat up to 80 - 100 °C, react for 8 - 12 h, cool to room temperature, centrifuge, wash, dry, and pass through a 300 - 400 - mesh sieve to obtain modified silica powder.

2. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, characterized in that, The dispersant refers to DX - 915 or DX - 407 produced by Metachemie; the curing agent refers to toluene diisocyanate or isophorone diisocyanate; the defoamer refers to BYK - 052 or BYK - 053 produced by BYK; the leveling agent refers to EFKA - 3777 produced by Efka or BYK - 333 produced by BYK.

3. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, characterized in that, In (1), the weight ratio of copper chloride, cobalt acetate, terephthalic acid, ethylene glycol, and N,N - dimethylformamide is 3 - 6:1 - 2:0.6 - 1:3 - 5:15 - 25.

4. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, characterized in that, In the above (2), the weight ratio of PS microspheres, tetraethyl orthosilicate and ethanol is 0.8 - 1:0.9 - 1.5:10 - 14, and the particle size of the PS microspheres is 50 - 100 nm.

5. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, characterized in that, In the above (3), the weight ratio of mixture A, block copolymer P123, tetraethyl orthosilicate and ethanol is 1:0.1 - 0.2:1 - 1.2:10 - 14.

6. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, characterized in that, In the above (4), the weight ratio of silica with high porosity, copper / cobalt bimetallic MOFs, light stabilizer and ethanol is 1:0.2 - 0.4:0.3 - 0.5:10 - 14.

7. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, wherein, In the above (4), the light stabilizer is prepared by mixing nano zinc oxide and nano cerium oxide in a weight ratio of 2:

1.

8. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, characterized in that, In the above (5), the weight ratio of perfluoropropyl vinyl ether, chlorotrifluoroethylene, 3 - methacrylamidophenylboronic acid, dimethyl cystine, sodium dodecyl sulfate, 2 - cyanopropyl - 2 - yl benzodithio, potassium persulfate, hydroquinone and deionized water is 1:0.5 - 1:0.2 - 0.5:0.2 - 0.5:0.01 - 0.05:0.005 - 0.015:0.002 - 0.01:0.01 - 0.03:15 - 25.

9. The weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to claim 1, characterized in that, In the above (6), the weight ratio of mixture B, fluorine - containing polymer containing disulfide bonds and borate bonds and N,N - dimethylformamide is 1:0.2 - 0.4:10 - 14.

10. The preparation method of the weather-resistant decorative waterborne polyurethane mortar colored sand self-leveling floor material according to any one of claims 1-9, characterized in that, It includes the following process: adding a dispersant to the aqueous polyurethane emulsion, stirring for 10 - 20 min, adding modified silica powder, stirring for 20 - 30 min, then adding a curing agent, portland cement, light resin colored sand, defoaming agent and leveling agent, mixing and stirring for 1 - 3 h, then scraping and coating on the surface to be coated with a serrated trowel, and after curing, a weather - resistant decorative aqueous polyurethane mortar colored sand self - leveling floor material is obtained.

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