Sand-in-water decorative coating based on waste ceramic sand as well as preparation method and application of sand-in-water decorative coating

Abstract

The invention relates to the field of coating materials, in particular to a sand-in-water decorative coating based on waste ceramic sand and a preparation method and application thereof.The sand-in-water decorative coating is prepared from, by weight, ferrotitanium oxide coated ceramic sand, silica sol, urea-formaldehyde resin, urea, nonylphenol polyoxyethylene ether, sodium pyrophosphate, a flatting agent BYK-333 and a defoaming agent BYK-025. The coating is prepared from hydroxypropyl methyl cellulose, dodecanol ester, formaldehyde polycondensation and deionized water. The preparation method comprises the following steps: preparing raw materials, dispersing iron-titanium oxide coated ceramic sand and other solid particles in a reaction kettle, adding liquid raw materials, heating, stirring, and cooling. According to the invention, the ceramic sand is coated with the ferrotitanium oxide of nanowires and particles, so that the adhesive force, the performance and the color selection of the coating are remarkably enhanced, the hardness, the wear resistance, the scratch resistance, the compressive strength and the durability of the coating are remarkably improved, and the coating has wide application value in the application of building exterior wall decoration, indoor decoration and old building renovation.

Description

Technical Field

[0001] The invention relates to the field of coating materials, and in particular to a water-coated sand decorative coating based on waste ceramic sand, and a preparation method and application thereof. Background Art

[0002] In the modern construction industry, the importance of coatings cannot be ignored. It not only gives buildings visual beauty, but also directly displays the quality and service life of buildings. However, many coating products on the market generally face a series of challenges. The first problem is the shedding of ceramic particles in the coating, which not only seriously damages the aesthetics of the coating, but may also further cause damage to the surface of the building. For example, although the Chinese patent with publication number CN111117470A proposes a method of enhancing the coating by silicon nitride particles, nano-diamond particles, etc., due to the difference in the physicochemical properties between the ceramic particles and the coating matrix, the coating is prone to ceramic particles shedding during long-term use. Secondly, insufficient hardness of the coating is also a common phenomenon. Coatings with insufficient hardness are prone to scratches and wear, which significantly reduces the durability of the coating. For example, although the Chinese patent with publication number CN115558414A discloses an anti-fouling flash coating with organic matter as the main component, its hardness performance has certain limitations due to the lack of the main component to enhance hardness. Furthermore, poor color stability is also a problem that cannot be ignored. Paints with unstable colors will fade or change color after long-term use, causing the building appearance to gradually lose its original color charm. Given the problems of paint in terms of ceramic particle shedding, insufficient hardness and color stability, it is particularly important to develop a new type of paint that combines excellent particle adhesion, high hardness and color stability to meet the needs of high-performance paints. Summary of the invention

[0003] (1) Technical issues solved

[0004] The purpose of the present invention is to provide a water-based sand decorative paint based on waste ceramic sand, and a preparation method and application thereof, so as to solve the problems that the current paint has shortcomings such as easy shedding of ceramic particles, insufficient hardness and poor color stability.

[0005] (2) Technical solution

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] A water-coated sand decorative paint based on waste ceramic sand is prepared from the following raw materials in parts by weight: 10-30 parts of iron-titanium oxide-coated ceramic sand, 5-9 parts of silica sol, 3-9 parts of urea-formaldehyde resin, 0.5-1.5 parts of urea, 1-4 parts of nonylphenol polyoxyethylene ether, 2-4 parts of sodium pyrophosphate, 0.5-2 parts of leveling agent BYK-333, 0.5-1.5 parts of defoaming agent BYK-025, 1-4 parts of hydroxypropyl methylcellulose, 0.5-2 parts of dodecyl alcohol ester, 1-3 parts of formaldehyde condensation and 10-25 parts of deionized water.

[0008] Furthermore, the iron-titanium oxide coated ceramic sand consists of iron-titanium oxide and ceramic sand; the iron-titanium oxide is uniformly coated on the surface of the ceramic sand particles in the form of a mixture of nanowires and particles.

[0009] Furthermore, the mass percentage of the iron-titanium oxide and the ceramic sand is (15-40%): (85-60%).

[0010] Furthermore, the average particle size of the ceramic sand is 500 to 5000 nm.

[0011] Furthermore, the iron-titanium oxide is composed of iron oxide and titanium oxide; the chemical formula of the iron oxide is Fe x O; 2 / 3≤x≤3 / 4; titanium oxide is TiO 2 .

[0012] Furthermore, the mass percentage of the iron oxide and the titanium oxide is (5-50%): (95-50%).

[0013] Furthermore, the preparation method of the iron-titanium oxide-coated ceramic sand is as follows: by weight, 60 to 120 parts of ferrocene, 25 to 45 parts of titanium tetraisopropoxide and 150 to 250 parts of ether solvent are added to a reaction container, heated to 45 to 70° C., stirred for 1 to 4 hours, and then 60 to 90 parts of ceramic sand are added and stirred for 2 to 4 hours, and then the tetrahydrofuran solvent is removed by distillation in an Ar atmosphere to obtain a dry mixture of organic matter containing iron and titanium elements and ceramic sand, and then the dry mixture is heated in an Ar and H atmosphere with a volume fraction of 50% each. 2 The temperature is raised from room temperature to 250-450° C. at a heating rate of 2-5° C. / min in a mixed atmosphere, and kept warm for 2-4 hours to obtain iron-titanium oxide-coated ceramic sand.

[0014] Furthermore, the preparation method of the ceramic sand is: washing the waste ceramics with tap water to remove impurities, crushing them with a crusher after drying, and then adding them into a high-energy ball mill for grinding to obtain ceramic sand, and then selecting ceramic sand with an average diameter of 500 to 5000 nm through screening.

[0015] Furthermore, the mass ratio of the urea-formaldehyde resin to urea is 6:1.

[0016] The present invention provides multiple significant advantages for coating enhancement by innovatively converting waste ceramics into ceramic sand. First of all, this method realizes the efficient reuse of waste ceramics, significantly reduces resource waste, and deeply practices the core concept of environmental protection and sustainable development. Secondly, the addition of ceramic sand significantly enhances the strength and durability of the coating, improves its impact resistance and wear resistance, and thus extends the service life of the coating. In addition, ceramic sand can also optimize the surface quality of the coating, and by filling small defects, reducing bubbles and spots, it brings a more uniform and beautiful appearance to the coating. At the same time, this innovative method also meets environmental protection requirements, reduces the exploitation of natural resources, and reduces the negative impact on the environment. Finally, waste ceramics are used as raw materials, and their cost is relatively low, thereby reducing the production cost of coatings, bringing tangible economic benefits to enterprises. In summary, the present invention prepares ceramic sand for coating enhancement by waste ceramics, which not only realizes the effective utilization of resources, but also improves the performance of coatings, improves the surface quality, promotes environmental protection, and brings economic benefits to enterprises, which has a far-reaching impact on the sustainable development and environmental protection of the coating industry.

[0017] The present invention uses iron oxide coated ceramic sand to achieve enhanced coating adhesion, color control, and overall improvement of coating performance. (1). By uniformly coating the surface of ceramic sand particles with iron-titanium oxide in the form of a mixture of nanowires and particles, the contact area between the ceramic sand particles and the coating is effectively increased, thereby significantly enhancing the adhesion between the ceramic sand particles and the coating, preventing the problem of the ceramic sand particles falling off the coating surface, and further optimizing the overall performance of the coating. (2). The present invention also cleverly introduces iron oxide and titanium oxide into the coating, which not only serve as colorants for the coating, but also provide a rich color selection for the coating. By adjusting the Fe x The value of x in O can control the color of iron oxide. For example, when x is 2 / 3, red Fe 2 O 3 , and when x is 3 / 4, black Fe 3 O 4, and titanium oxide usually appears white. The combination of iron oxide and titanium oxide enables the coating to meet various personalized needs and realize color customization. Iron-titanium oxide has very stable physical and chemical properties, which can improve the color stability of the coating. (3). Iron-titanium oxide can also increase the hardness of the coating, improve the wear resistance and scratch resistance of the coating, and enhance the compressive strength and durability of the coating. The improvement of these properties makes the coating more durable during use, can maintain excellent appearance and performance for a long time, and significantly extends the service life of the coating. In summary, the present invention uses iron-titanium oxide to coat ceramic sand particles in the form of a mixture of nanowires and particles, and adds iron oxide and titanium oxide to the coating, thereby achieving enhanced adhesion of the coating, color regulation and comprehensive improvement of the coating performance, and has multiple synergistic effects. This innovative technology is of great significance to the coating industry for improving the quality and performance of coating products.

[0018] The present invention also provides a method for preparing a water-based sand decorative coating based on waste ceramic sand, comprising the following steps:

[0019] S1: Prepare raw materials

[0020] Iron-titanium oxide-coated ceramic sand, silica sol, urea-formaldehyde resin, urea, nonylphenol polyoxyethylene ether, sodium pyrophosphate, leveling agent BYK-333, defoaming agent BYK-025, hydroxypropyl methylcellulose, dodecyl alcohol ester, formaldehyde condensation and deionized water are prepared according to the weight proportion of the formula.

[0021] S2: Dispersed solid particles raw materials

[0022] Add iron-titanium oxide-coated ceramic sand, silica sol, nonylphenol polyoxyethylene ether and deionized water into a reaction kettle and stir for 2 to 4 hours to ensure that all components are fully mixed.

[0023] S3: Add liquid raw materials

[0024] Add urea-formaldehyde resin, urea, sodium pyrophosphate, leveling agent BYK-333, defoaming agent BYK-025, hydroxypropyl methylcellulose and dodecyl alcohol ester to the mixed solution of S2, then heat to 70-90°C, continue stirring for 2-4 hours, and cool.

[0025] The present invention also provides an application of water-based sand decorative paint based on waste ceramic sand in building exterior wall decoration, interior decoration and renovation of old buildings. Coating method: First, the water-based sand decorative paint is evenly applied on the exterior wall or interior wall of the building by brush, roller or other suitable coating tools. After the coating is completed, the surface of the paint is finely smoothed with a scraper or spatula to eliminate possible unevenness, ensure that the wall surface is flat and smooth, and achieve the desired effect and texture. Next, wait for the paint to dry and solidify naturally.

[0026] (3) Beneficial technical effects

[0027] The present invention uses iron-titanium oxide to coat ceramic sand, and through the mixed form of nanowires and particles, significantly enhances the adhesion between the coating and the ceramic sand, prevents falling off, and optimizes the coating performance. At the same time, the technology also introduces iron oxide and titanium oxide, providing a rich color selection for the coating and realizing precise color control. These oxides not only enhance the color stability of the coating, but also improve its hardness, wear resistance, scratch resistance, compressive strength and durability, significantly extending the service life of the coating. Silica sol, as a thickener, can effectively adjust the viscosity and fluidity of the coating to ensure smoothness during construction. Urea-formaldehyde resin, as an adhesive, not only enhances the adhesion of the coating, but also greatly improves its durability. Urea, as a reaction aid, reacts with urea-formaldehyde resin to promote the curing of the resin, thereby enhancing the stability and strength of the coating. The addition of nonylphenol polyoxyethylene ether, as a dispersant, ensures the uniform dispersion of pigments and other solid particles in the coating, further improving the quality of the coating. The addition of sodium pyrophosphate provides flame retardant properties for the coating and enhances its safety. In addition, the leveling agent BYK-333 improves the surface flatness and glossiness of the coating, reduces the foaming and fluidity problems; the defoamer BYK-025 effectively controls the formation of bubbles and foam in the coating, further improving the quality of the coating. Hydroxypropyl methylcellulose, as a thickener and rheological agent, also finely adjusts the viscosity and fluidity of the coating. Dodecyl alcohol ester, as a solvent and thickener, helps adjust the viscosity and drying speed of the coating, making the coating easier to apply and dry. Finally, formaldehyde polycondensation, as a cross-linking agent, further promotes the curing of urea-formaldehyde resin and the durability of the coating. Deionized water, as a solvent and diluent, not only adjusts the concentration and fluidity of the coating, but also ensures the stability and ease of operation of the coating during the construction process. In summary, the present invention can improve the performance of the coating, enhance durability and solvent resistance, achieve a matte effect, and has broad application prospects by optimizing the boron source, catalyst and coating formula. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the SEM morphology of the iron-titanium oxide-coated ceramic sand prepared in Example 1 of the present invention.

[0029] Figure 2 This is the macroscopic morphology of the ceramic sand powder prepared in Example 1 of the present invention.

[0030] Figure 3 This is the macroscopic morphology of the iron-titanium oxide-coated ceramic sand powder prepared in Example 1 of the present invention.

[0031] Figure 4 This is the XRD phase analysis diagram of the ceramic sand prepared in Example 1 of the present invention.

[0032] Figure 5 XRD phase analysis diagram of ceramic sand and iron-titanium oxide coated ceramic sand prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0033] To make the purpose, technical solution and advantages of the embodiments of the present invention more clear, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0034] In the case of not specifying specific conditions, the operation in the embodiment is carried out according to conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used, if the manufacturer is not indicated, are all common products on the market. The parts not mentioned in the technical content of the present invention will be processed with reference to the prior art. Unless otherwise specified, the following examples and comparative examples will be tested in parallel and use the same processing steps and parameters. Table 1 shows the reagents required for the examples and comparative examples and the corresponding purchasing companies.

[0035] Table 1 Reagents required for the examples and comparative examples and the corresponding purchasing companies

[0036] Reagents company Silica Sol Suzhou Qihang Biotechnology Co., Ltd. Urea-formaldehyde resin Shandong West Asia Chemical Co., Ltd. Urea Shanghai MacLean Biochemical Technology Co., Ltd. Nonylphenol polyoxyethylene ether Jinan Jinhao Chemical Co., Ltd. Sodium pyrophosphate Shanghai MacLean Biochemical Technology Co., Ltd. Leveling agent BYK-333 Shandong Mantanghong New Materials Co., Ltd. Defoamer BYK-025 Shanghai MacLean Biochemical Technology Co., Ltd. Hydroxypropyl methylcellulose Shandong West Asia Chemical Co., Ltd. Dodecyl alcohol ester Himaclin Biochemical Technology Co., Ltd. Formaldehyde polycondensation Shanghai MacLean Biochemical Technology Co., Ltd. Ferrocene Shanghai MacLean Biochemical Technology Co., Ltd. Titanium Tetraisopropoxide Shandong West Asia Chemical Co., Ltd. Ether solvent Zhejiang Hangyu Pharmaceutical Technology Co., Ltd. Tetrahydrofuran solvent Shandong Mantanghong New Materials Co., Ltd. Ar gas Air Liquide (Shanghai) Co., Ltd. <![CDATA[H 2 Gas]]> Air Liquide (Shanghai) Co., Ltd.

[0037] Example 1

[0038] A water-coated sand decorative paint based on waste ceramic sand is prepared from the following raw materials in parts by weight: 10 parts of iron-titanium oxide-coated ceramic sand, 5 parts of silica sol, 3 parts of urea-formaldehyde resin, 0.5 parts of urea, 1 part of nonylphenol polyoxyethylene ether, 2 parts of sodium pyrophosphate, 0.5 parts of leveling agent BYK-333, 0.5 parts of defoaming agent BYK-025, 1 part of hydroxypropyl methylcellulose, 0.5 parts of dodecyl alcohol ester, 1 part of formaldehyde condensation, and 10 parts of deionized water.

[0039] The iron-titanium oxide coated ceramic sand is composed of iron-titanium oxide and ceramic sand; the iron-titanium oxide is uniformly coated on the surface of the ceramic sand particles in the form of a mixture of nanowires and particles.

[0040] The mass percentage of the above-mentioned iron-titanium oxide and ceramic sand is 15%:85%.

[0041] The average particle size of the ceramic sand is 500.

[0042] The above-mentioned iron-titanium oxide is composed of iron oxide and titanium oxide; the chemical formula of iron oxide is Fe x O; x is 2 / 3; titanium oxide is TiO 2 .

[0043] The mass percentage of the iron oxide and the titanium oxide is 5%:95%.

[0044] The preparation method of the iron-titanium oxide-coated ceramic sand is as follows: 60 parts of ferrocene, 25 parts of titanium tetraisopropoxide and 150 parts of ether solvent are added to a reaction container by weight, heated to 45° C., stirred for 1 hour, then 60 parts of ceramic sand are added and stirred for 2 hours, then the tetrahydrofuran solvent is distilled off in an Ar atmosphere to obtain a dry mixture of organic matter containing iron and titanium elements and ceramic sand, and then the dry mixture is heated in an Ar and H atmosphere with a volume fraction of 50%. 2 The temperature was raised from room temperature to 250°C in a mixed atmosphere at a heating rate of 2°C / min and kept for 2h to obtain iron-titanium oxide-coated ceramic sand.

[0045] The preparation method of the above-mentioned ceramic sand is: wash the waste ceramics with tap water to remove impurities, crush them with a crusher after drying, and then add them into a high-energy ball mill for grinding to obtain ceramic sand, and then select ceramic sand with an average diameter of 500 through screening.

[0046] The present invention also provides a method for preparing a water-based sand decorative coating based on waste ceramic sand, comprising the following steps:

[0047] S1: Prepare raw materials: iron-titanium oxide coated ceramic sand, silica sol, urea-formaldehyde resin, urea, nonylphenol polyoxyethylene ether, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose, dodecyl alcohol ester, formaldehyde condensation and deionized water according to the weight ratio of the formula. S2: Disperse solid particle raw materials: Add iron-titanium oxide coated ceramic sand, silica sol, nonylphenol polyoxyethylene ether and deionized water to the reactor and stir for 2 hours to ensure that all components are fully mixed. S3: Add liquid raw materials: Continue to add urea-formaldehyde resin, urea, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose and dodecyl alcohol ester to the mixed solution of S2, then heat to 70°C, continue stirring for 2 hours, and cool.

[0048] Example 2

[0049] A water-coated sand decorative paint based on waste ceramic sand is prepared from the following raw materials in parts by weight: 15 parts of iron-titanium oxide-coated ceramic sand, 6 parts of silica sol, 4.8 parts of urea-formaldehyde resin, 0.8 parts of urea, 2 parts of nonylphenol polyoxyethylene ether, 3 parts of sodium pyrophosphate, 1 part of leveling agent BYK-333, 1 part of defoaming agent BYK-025, 2 parts of hydroxypropyl methylcellulose, 1 part of dodecyl alcohol ester, 2 parts of formaldehyde condensation, and 15 parts of deionized water.

[0050] The iron-titanium oxide coated ceramic sand is composed of iron-titanium oxide and ceramic sand; the iron-titanium oxide is uniformly coated on the surface of the ceramic sand particles in the form of a mixture of nanowires and particles.

[0051] The mass percentage of the above-mentioned iron-titanium oxide and ceramic sand is 20%:80%.

[0052] The average particle size of the ceramic sand is 1000 nm.

[0053] The above-mentioned iron-titanium oxide is composed of iron oxide and titanium oxide; the chemical formula of iron oxide is Fe x O; wherein x = 0.7; titanium oxide is TiO 2 .

[0054] The mass percentage of the iron oxide and the titanium oxide is 20%:80%.

[0055] The preparation method of the iron-titanium oxide-coated ceramic sand is as follows: 80 parts of ferrocene, 30 parts of titanium tetraisopropoxide and 180 parts of ether solvent are added to a reaction container by weight, heated to 50° C., stirred for 2 hours, then 70 parts of ceramic sand are added and stirred for 3 hours, then the tetrahydrofuran solvent is distilled off in an Ar atmosphere to obtain a dry mixture of organic matter containing iron and titanium elements and ceramic sand, and then the dry mixture is heated in an Ar and H atmosphere with a volume fraction of 50%. 2 The temperature was raised from room temperature to 300°C at a heating rate of 3°C / min in a mixed atmosphere and kept for 3 h to obtain iron-titanium oxide-coated ceramic sand.

[0056] The preparation method of the above-mentioned ceramic sand is: wash the waste ceramics with tap water to remove impurities, crush them with a crusher after drying, and then add them into a high-energy ball mill for grinding to obtain ceramic sand, and then select ceramic sand with an average diameter of 1000nm through screening.

[0057] The present invention also provides a method for preparing a water-based sand decorative coating based on waste ceramic sand, comprising the following steps:

[0058] S1: Prepare raw materials: iron-titanium oxide coated ceramic sand, silica sol, urea-formaldehyde resin, urea, nonylphenol polyoxyethylene ether, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose, dodecyl alcohol ester, formaldehyde condensation and deionized water according to the weight ratio of the formula. S2: Disperse solid particle raw materials: Add iron-titanium oxide coated ceramic sand, silica sol, nonylphenol polyoxyethylene ether and deionized water to the reactor and stir for 3 hours to ensure that all components are fully mixed. S3: Add liquid raw materials: Continue to add urea-formaldehyde resin, urea, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose and dodecyl alcohol ester to the mixed solution of S2, then heat to 80°C, continue stirring for 3 hours, and cool.

[0059] Example 3

[0060] A water-coated sand decorative paint based on waste ceramic sand is prepared from the following raw materials in parts by weight: 25 parts of iron-titanium oxide-coated ceramic sand, 8 parts of silica sol, 6 parts of urea-formaldehyde resin, 1 part of urea, 3 parts of nonylphenol polyoxyethylene ether, 3 parts of sodium pyrophosphate, 1.5 parts of leveling agent BYK-333, 1 part of defoaming agent BYK-025, 3 parts of hydroxypropyl methylcellulose, 1.5 parts of dodecyl alcohol ester, 2 parts of formaldehyde condensation, and 20 parts of deionized water.

[0061] The iron-titanium oxide coated ceramic sand is composed of iron-titanium oxide and ceramic sand; the iron-titanium oxide is uniformly coated on the surface of the ceramic sand particles in the form of a mixture of nanowires and particles.

[0062] The mass percentage of the above-mentioned iron-titanium oxide and ceramic sand is 30%:7%.

[0063] The average particle size of the ceramic sand is 3000 nm.

[0064] The above-mentioned iron-titanium oxide is composed of iron oxide and titanium oxide; the chemical formula of iron oxide is Fe x O; x is 0.72; titanium oxide is TiO 2 .

[0065] The mass percentage of the iron oxide and the titanium oxide is 40%:60%.

[0066] The preparation method of the iron-titanium oxide-coated ceramic sand is as follows: 110 parts of ferrocene, 40 parts of titanium tetraisopropoxide and 220 parts of ether solvent are added to a reaction container by weight, heated to 60° C., stirred for 3 hours, then 80 parts of ceramic sand are added and stirred for 3 hours, then the tetrahydrofuran solvent is distilled off in an Ar atmosphere to obtain a dry mixture of organic matter containing iron and titanium elements and ceramic sand, and then the dry mixture is heated in an Ar and H atmosphere with a volume fraction of 50% each. 2 The temperature was raised from room temperature to 400°C in a mixed atmosphere at a heating rate of 4°C / min and kept for 3 hours to obtain iron-titanium oxide-coated ceramic sand.

[0067] The preparation method of the above-mentioned ceramic sand is: wash the waste ceramics with tap water to remove impurities, crush them with a crusher after drying, and then add them into a high-energy ball mill for grinding to obtain ceramic sand, and then select ceramic sand with an average diameter of 3000nm through screening.

[0068] The present invention also provides a method for preparing a water-based sand decorative coating based on waste ceramic sand, comprising the following steps:

[0069] S1: Prepare raw materials: iron-titanium oxide coated ceramic sand, silica sol, urea-formaldehyde resin, urea, nonylphenol polyoxyethylene ether, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose, dodecyl alcohol ester, formaldehyde condensation and deionized water according to the weight ratio of the formula. S2: Disperse solid particle raw materials: Add iron-titanium oxide coated ceramic sand, silica sol, nonylphenol polyoxyethylene ether and deionized water to the reactor and stir for 3 hours to ensure that all components are fully mixed. S3: Add liquid raw materials: Continue to add urea-formaldehyde resin, urea, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose and dodecyl alcohol ester to the mixed solution of S2, then heat to 80°C, continue stirring for 3 hours, and cool.

[0070] Example 4

[0071] A water-coated sand decorative paint based on waste ceramic sand is prepared from the following raw materials in parts by weight: 30 parts of iron-titanium oxide-coated ceramic sand, 9 parts of silica sol, 9 parts of urea-formaldehyde resin, 1.5 parts of urea, 4 parts of nonylphenol polyoxyethylene ether, 4 parts of sodium pyrophosphate, 2 parts of leveling agent BYK-333, 1.5 parts of defoaming agent BYK-025, 4 parts of hydroxypropyl methylcellulose, 2 parts of dodecyl alcohol ester, 3 parts of formaldehyde condensation, and 25 parts of deionized water.

[0072] The iron-titanium oxide coated ceramic sand is composed of iron-titanium oxide and ceramic sand; the iron-titanium oxide is uniformly coated on the surface of the ceramic sand particles in the form of a mixture of nanowires and particles.

[0073] The mass percentage of the above-mentioned iron-titanium oxide and ceramic sand is 40%:60%.

[0074] The average particle size of the ceramic sand is 5000 nm.

[0075] The above-mentioned iron-titanium oxide is composed of iron oxide and titanium oxide; the chemical formula of iron oxide is Fe x O; x is 3 / 4; titanium oxide is TiO 2 .

[0076] The mass percentage of the iron oxide and the titanium oxide is 50%:50%.

[0077] The preparation method of the iron-titanium oxide-coated ceramic sand is as follows: 120 parts of ferrocene, 45 parts of titanium tetraisopropoxide and 250 parts of ether solvent are added to a reaction container by weight, heated to 70°C, stirred for 4 hours, then 90 parts of ceramic sand are added and stirred for 4 hours, then the tetrahydrofuran solvent is distilled off in an Ar atmosphere to obtain a dry mixture of organic matter containing iron and titanium elements and ceramic sand, and then the dry mixture is heated in an Ar and H atmosphere with a volume fraction of 50% each. 2The temperature was raised from room temperature to 450°C in a mixed atmosphere at a heating rate of 5°C / min and kept for 4 hours to obtain iron-titanium oxide-coated ceramic sand.

[0078] The preparation method of the above-mentioned ceramic sand is: wash the waste ceramics with tap water to remove impurities, crush them with a crusher after drying, and then add them into a high-energy ball mill for grinding to obtain ceramic sand, and then select ceramic sand with an average diameter of 5000nm through screening.

[0079] The present invention also provides a method for preparing a water-based sand decorative coating based on waste ceramic sand, comprising the following steps:

[0080] S1: Prepare raw materials: iron-titanium oxide coated ceramic sand, silica sol, urea-formaldehyde resin, urea, nonylphenol polyoxyethylene ether, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose, dodecyl alcohol ester, formaldehyde condensation and deionized water according to the weight ratio of the formula. S2: Disperse solid particle raw materials: Add iron-titanium oxide coated ceramic sand, silica sol, nonylphenol polyoxyethylene ether and deionized water to the reactor and stir for 4 hours to ensure that all components are fully mixed. S3: Add liquid raw materials: Continue to add urea-formaldehyde resin, urea, sodium pyrophosphate, leveling agent BYK-333, defoamer BYK-025, hydroxypropyl methylcellulose and dodecyl alcohol ester to the mixed solution of S2, then heat to 90°C, continue stirring for 4 hours, and cool.

[0081] Example 5

[0082] It is basically the same as Example 1, except that 30 parts of iron-titanium oxide-coated ceramic sand are added to prepare the coating.

[0083] Comparative Example 1

[0084] The method is basically the same as Example 1, except that ferrocene is not added in the preparation of iron-titanium oxide-coated ceramic sand.

[0085] Comparative Example 2

[0086] The method is basically the same as Example 1, except that titanium tetraisopropoxide is not added in the preparation of iron-titanium oxide-coated ceramic sand.

[0087] Comparative Example 3

[0088] The method is basically the same as Example 1, except that no iron-titanium oxide-coated ceramic sand is added to the coating.

[0089] Characterization Tests:

[0090] The present invention uses a scanning electron microscope to observe the morphology of iron-titanium oxide-coated ceramic sand. Figure 1The iron-titanium oxide is uniformly covered on the surface of the ceramic sand in the form of nanowires and particles, providing a good structural basis for increasing the adhesion of the ceramic sand in the coating.

[0091] Figure 2 This is the original macroscopic appearance of ceramic sand. It can be seen that ceramic sand appears white. When iron-titanium oxides coat ceramic sand, such as Figure 3 As mentioned above, since the surface of ceramic sand contains more ferric oxide, the ceramic sand appears light red in macroscopic view, which provides a good basis for coloring the paint.

[0092] Then X-ray Diffraction (XRD) was used to characterize the physical phases of ceramic sand and iron-titanium oxide-coated ceramic sand. Figure 4 It can be seen that the physical phase of ceramic sand is mainly silicon dioxide, while iron titanium Figure 5 Phase analysis of oxide-coated ceramic sand showed the presence of obvious iron oxide and titanium dioxide, proving the effectiveness of the phase.

[0093] Performance Testing:

[0094] Wear resistance is one of the important indicators in coating applications. The wear resistance of coatings refers to GB / T1768-2006 >>>> Determination of wear resistance of paints and varnishes. The equipment used is Taber wear tester. During the test, the coating is applied on a flat rigid surface. The sample is mounted on the turntable of the Taber wear tester and calculated by measuring the milligram loss of 1000 cycles of wear. The weight applied during the test is 1000g. The wear resistance of polyurethane coatings can be evaluated through testing, thus providing a basis for its application in coatings.

[0095] Adhesion test: ISO 2409 standard evaluation method, this method is specifically used to determine the adhesion performance of paint on the wall. This method is designed to ensure that the paint can adhere firmly to the wall, and the test substrate is selected as an ordinary glass surface for testing. According to the rating criteria in the ISO 2409 standard, the test results will be quantitatively evaluated according to the degree of coating removal. The rating is divided into 0 to 5 levels, each level corresponds to a different degree of coating removal or delamination. Specifically, level 0 means that the coating is intact and shows excellent adhesion performance; level 1 means that the coating has slight peeling at the cut intersection, but the peeling area does not exceed 5%; level 2 means that the peeling area does not exceed 15%; level 3 means that the peeling area does not exceed 30%; level 4 means that the peeling area reaches but does not exceed 50%; and level 5 means that the coating is completely peeled off at the cut intersection, and the peeling area exceeds 50%.

[0096] Artificial aging test: Refer to GB / T 9754-2007 "Determination of 20°, 60°, 85° specular gloss of paints and varnishes without metallic pigments", use PG-1M gloss meter to measure the gloss of the coating. Refer to GB11186.2-1989 "Measurement of paint film color Part 2 Color measurement", use Spctro-guide colorimeter to measure the color difference of the coating.

[0097] Hardness: The coating hardness is measured according to the provisions of Method B in GB / T 6739-1996 "Pencil Method for Determination of Coating Hardness", and the test results are evaluated according to 4.6 in GB / T 6739-1996 "Pencil Method for Determination of Coating Hardness".

[0098] The performance test results of the coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 3 are summarized in Table 2.

[0099] Table 2 Performance test results of coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 3

[0100]

[0101] The main difference between Comparative Example 1 and Example 1 is whether ferrocene is added in the preparation of iron-titanium oxide-coated ceramic sand. Therefore, there is no iron oxide on the surface of the ceramic sand particles. From Table 2, it can be seen that the addition of ferrocene can increase the wear resistance, hardness, color stability and adhesion of the coating.

[0102] The main difference between Comparative Example 2 and Example 1 is whether titanium tetraisopropoxide is added in the preparation of iron-titanium oxide-coated ceramic sand. Therefore, there is no titanium oxide on the surface of the ceramic sand particles. From Table 2, it can be seen that the addition of titanium isopropoxide can increase the wear resistance, hardness, color stability and adhesion of the coating.

[0103] The main difference between Comparative Example 3 and Example 1 is whether iron-titanium oxide-coated ceramic sand is added to the coating. Therefore, the surface of the silica particles is not grafted with octadecanol water-resistant groups. It can be seen from Table 2 that the addition of iron-titanium oxide-coated ceramic sand can increase the wear resistance, hardness, color stability and adhesion of the coating.

[0104] In summary, the iron-titanium oxide-coated ceramic sand in the present invention can achieve a simultaneous increase in the wear resistance, hardness, color stability and adhesion of the coating, achieving a synergistic effect. This technology has important application value in the coating field and can provide excellent performance and effects in multiple fields.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that all equivalent structural changes made under the concept of the present invention and using the contents of the present invention specification and drawings should be covered within the scope of protection of the claims of the present invention.

Claims

1. A water-in-sand decorative paint based on waste ceramic sand, characterized in that: The following raw materials are prepared by weight: 10-30 parts of iron-titanium oxide coated ceramic sand, 5-9 parts of silica sol, 3-9 parts of urea-formaldehyde resin, 0.5-1.5 parts of urea, 1-4 parts of nonylphenol polyoxyethylene ether, 2-4 parts of sodium pyrophosphate, 0.5-2 parts of leveling agent BYK-333, 0.5-1.5 parts of defoaming agent BYK-025, 1-4 parts of hydroxypropyl methylcellulose, 0.5-2 parts of dodecyl alcohol ester, 1-3 parts of formaldehyde polycondensation, and 10-25 parts of deionized water; The iron-titanium oxide coated ceramic sand is composed of iron-titanium oxide and ceramic sand; the iron-titanium oxide is uniformly coated on the surface of the ceramic sand particles in the form of a mixture of nanowires and particles; The preparation method of the iron-titanium oxide coated ceramic sand is as follows: by weight, 60 to 120 parts of ferrocene, 25 to 45 parts of titanium tetraisopropoxide and 150 to 250 parts of ether solvent are added into a reaction container, heated to 45 to 70° C., stirred for 1 to 4 hours, then 60 to 90 parts of ceramic sand are added and stirred for 2 to 4 hours, then the tetrahydrofuran solvent is distilled off in an Ar atmosphere to obtain a dry mixture of organic matter containing iron and titanium elements and ceramic sand, then the dry mixture is heated from room temperature to 250 to 450° C. at a heating rate of 2 to 5° C. / min in a mixed atmosphere of Ar and H2 with a volume fraction of 50%, and kept warm for 2 to 4 hours to obtain the iron-titanium oxide coated ceramic sand.

2. A water-in-sand decorative paint based on waste ceramic sand as claimed in claim 1, characterized in that: The mass percentage of the iron-titanium oxide and the ceramic sand is (15-40%): (85-60%).

3. A water-in-sand decorative paint based on waste ceramic sand as claimed in claim 1, characterized in that: The average particle size of the ceramic sand is 500-5000nm.

4. A water-in-sand decorative paint based on waste ceramic sand as claimed in claim 1, characterized in that: The iron-titanium oxide is composed of iron oxide and titanium oxide; the chemical formula of the iron oxide is Fe x O; wherein 2 / 3≤x≤3 / 4; the titanium oxide is TiO2.

5. A water-in-sand decorative paint based on waste ceramic sand as claimed in claim 4, characterized in that: The mass percentage of the iron oxide and the titanium oxide is (5-50%): (95-50%).

6. The water-in-sand decorative paint based on waste ceramic sand according to claim 1, characterized in that: The preparation method of the ceramic sand is as follows: the waste ceramic is washed with tap water to remove impurities, dried and crushed by a crusher, then added into a high-energy ball mill for pulverization to obtain ceramic sand, and then sieved to select ceramic sand with an average diameter of 500 to 5000 nm.

7. The water-in-sand decorative paint based on waste ceramic sand according to claim 1, characterized in that: The mass ratio of the urea-formaldehyde resin to urea is 6:

1.

8. The method for preparing the water-in-sand decorative paint based on waste ceramic sand according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: Prepare raw materials Iron-titanium oxide-coated ceramic sand, silica sol, urea-formaldehyde resin, urea, nonylphenol polyoxyethylene ether, sodium pyrophosphate, leveling agent BYK-333, defoaming agent BYK-025, hydroxypropyl methylcellulose, dodecyl alcohol ester, formaldehyde polycondensation and deionized water are prepared according to the weight ratio of the formula; S2: Dispersed solid particles raw materials Add iron-titanium oxide-coated ceramic sand, silica sol, nonylphenol polyoxyethylene ether and deionized water into a reaction kettle and stir for 2 to 4 hours to ensure that all components are fully mixed; S3: Add liquid raw materials Add urea-formaldehyde resin, urea, sodium pyrophosphate, leveling agent BYK-333, defoaming agent BYK-025, hydroxypropyl methylcellulose and dodecyl alcohol ester to the mixed solution of S2, then heat to 70-90°C, continue stirring for 2-4 hours, and cool.

9. Application of a water-based sand decorative paint based on waste ceramic sand as described in any one of claims 1 to 7 in building exterior wall decoration, interior decoration and renovation of old buildings.

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