Composite titanium dioxide material prepared by utilizing phase separation as well as preparation method and application of composite titanium dioxide material

Abstract

The invention relates to a composite titanium dioxide material prepared by phase separation, and a preparation method and application thereof. The composite titanium dioxide material comprises a polymer monomer, a cosolvent, a metal oxide, a surfactant, water and an initiator. Mixing a polymer monomer with a cosolvent to obtain a polymer monomer solution; mixing and diluting a metal oxide and water to obtain a metal oxide solution; mixing the polymer monomer solution and the metal oxide solution to obtain a blended phase separation solution; adding an initiator into the blended phase separation solution to obtain a precursor solution; the precursor solution is sprayed on the surface of glass, phase separation occurs in the evaporation process of the cosolvent, ultraviolet light is used for illumination curing to obtain a hybrid material, ball milling is carried out, and the composite titanium dioxide material is obtained. The defect that the structure of the material is broken due to strong shearing force in the high-speed dispersion process of the coating is overcome. The preparation method is simple in process, environment-friendly and easy to operate, and the dosage of titanium dioxide in the coating is remarkably reduced.

Description

Technical Field

[0001] The present invention belongs to the field of chemical engineering, and particularly relates to a composite titanium white material prepared by phase separation, a preparation method thereof, and an application thereof. Background Art

[0002] The hiding power of coatings has always been a basic requirement and main performance of coatings. Optically, both the reflection and absorption of light by pigments can cause hiding and decoloring effects. White pigments can reflect almost all visible light wavelengths with equal intensity within the entire range of visible light, so they have a large scattering ability and little absorption ability. According to the Fresnel formula n1sinθ1 = n2sinθ2, when the refractive index of the pigment is equal to that of the base material, it is transparent, and when the refractive index of the pigment is greater than that of the base material, hiding occurs. The greater the difference between the two, the stronger the hiding power.

[0003] Titanium dioxide has the highest refractive index among white pigments. Theoretically, its hiding power should also be the highest, but the particle size, particle structure, and dispersion degree of titanium dioxide also affect its hiding power. As an efficient light-scattering pigment, titanium dioxide provides excellent whiteness and hiding power for the coating film. With the rapid rise of the automotive industry, construction industry, and waterborne coating market, the overall demand for titanium dioxide has increased rapidly, and the resulting resource, energy consumption, and environmental constraints have become increasingly prominent. It is urgent to improve the sustainable development ability of the titanium dioxide industry.

[0004] Composite titanium white materials are a new type of material used to replace titanium dioxide. They are used in combination with titanium dioxide and other inorganic fillers to reduce the use of titanium dioxide, which is a very promising development area. However, the current production processes mainly include chemical deposition coating method, solid-phase mechanochemical grinding method, mechanical mixing method, and liquid-phase mechanochemical grinding method. Each of the above methods has its own defects. For example, the chemical deposition coating method produces wastewater during the preparation process, causing environmental pollution; the solid-phase mechanochemical particle coating method is prone to particle agglomeration and poor dispersion; the liquid-phase mechanochemical grinding method has the disadvantages of high energy consumption and long time consumption.

[0005] Phase separation technology is a simple and effective method for preparing polymer microporous membranes, which has potential application prospects in the fields of healthcare, cosmetics, food, and energy. Currently, the forefront research is limited to a few immiscible liquids, and the batch production and manufacturing efficiency are low, unable to meet the needs of industrial production.

[0006] Patent publication document CN115247006B discloses a light composite titanium dioxide and a preparation method thereof. The composite titanium dioxide is composed of at least one of calcined kaolin, heavy calcium powder, and barium sulfate, has a porous microsphere structure, a tapped density of 0.5 - 1.2 g / cm3, and a specific surface area of 1 - 6 m 2 / g, whiteness > 80, average particle size 40 - 50 μm.

[0007] Patent publication document CN111363200A discloses a microspherized titanium dioxide particle, a preparation device, a preparation method and an application thereof. The particle size of the microspherized titanium dioxide particle is 10 - 50 μm. The titanium dioxide particle is composed of a titanium dioxide body, a dispersant and a binder. The weight ratio of the titanium dioxide body, the dispersant and the binder is 100:0.2 - 0.5:0.2 - 0.5. The titanium dioxide particle is in a microspherical shape and has good dispersibility in an aqueous system.

[0008] Patent publication document CN109135347A discloses a microspherical composite titanium dioxide for coatings and a preparation method thereof. By preparing a mixed solution A containing sodium polystyrene sulfonate and calcium chloride, and then mixing it with ammonium bicarbonate to form a mixed solution B, a composite microsphere of calcium carbonate-coated sodium polystyrene sulfonate is prepared, and then tetrabutyl titanate is alcoholyzed to obtain a sodium polystyrene sulfonate-calcium carbonate-titanium dioxide composite material, that is, the microspherical composite titanium dioxide for coatings.

[0009] Although the above method prepares a composite titanium dioxide for use in coatings, the prepared composite titanium dioxide is prone to secondary aggregation, has certain defects, the particle size of the obtained particles is relatively large, and it is easy to break during the coating preparation process, losing the functional effects brought by the composite structure.

[0010] Patent publication document CN108176255A discloses a polyvinylidene fluoride-titanium dioxide hybrid membrane, a preparation method and an application thereof. By adding a mineralization inducer containing amino groups to a polyvinylidene fluoride membrane solution to induce the in-situ hydrolysis of a titanium precursor in the polyvinylidene fluoride solution to produce nano-titanium dioxide particles, and then preparing a polyvinylidene fluoride-titanium dioxide hybrid membrane through non-solvent induced phase inversion, the hydrophilicity of the surface of the titanium dioxide particles is improved, and thus the anti-pollution ability of the membrane is enhanced.

[0011] Patent publication document CN111644079A discloses a nanofiltration membrane material with high surface roughness and a preparation method thereof. By adopting a wet non-woven technology to prepare a polymer nanofiber coating material with high surface roughness, it has the characteristics of small pore size, high uniformity and large density. And the polymer nanofiber is prepared by a melt blending phase separation method, and the dispersion liquid is prepared by a water-based solvent. The whole process is green and pollution-free, and is easy for large-scale production, thus ensuring the batch preparation of the nanofiber coating.

[0012] Patent publication CN109666343A discloses an imitation white beetle ultra-thin and ultra-white material, its preparation method and application. The ultra-thin and ultra-white material has excellent performance and can, to a certain extent, replace the widely used titanium dioxide TiO2 in ultra-white coatings with potential carcinogenicity. This invention can prepare an imitation white beetle ultra-thin and ultra-white surface material with excellent optical scattering performance by using a simple non-solvent vapor-induced phase separation method.

[0013] The above method improves the surface performance of the material through phase separation technology. The prepared material has a three-dimensional irregular network structure inside, a relatively large porosity, and excellent optical scattering performance. However, the focused fields are all in the fiber and film fields and cannot be directly used in coating production.

[0014] Optical simulation results show that when the porosity of the material is less than 20%, the solar reflectivity increases rapidly with the increase of porosity; before the porosity reaches 50 - 60%, the reflectivity almost linearly increases to the plateau value. However, the mechanical properties (such as modulus) of the random pore structure generally rapidly decay with the increase of porosity in a square or even higher-order scaling relationship.

[0015] The material disclosed in patent publication CN109666343A is a surface material with a reflectivity of only 60 - 75%, and has a three-dimensional irregular network structure inside with a porosity of 30% - 65%. Since the material is a surface material, it cannot be directly used in coating production, and its relatively high porosity will lead to poor mechanical stability of such materials and easy fragmentation, unable to meet the actual application.

[0016] Therefore, finding a suitable phase separation preparation technology to prepare composite materials with good mechanical properties and optical properties, and at the same time being a functional powder material suitable for use in the coating industry is a problem that needs to be solved currently. Summary of the Invention

[0017] In view of the above-mentioned technical problems, the present invention provides a composite titanium white material prepared by phase separation, its preparation method and application. The composite titanium white material prepared by the present invention is a powder material, which not only has excellent optical properties, far higher than the similar materials reported in the current literature, but also has excellent mechanical stability, and solves the drawback that the structure of such materials is broken due to strong shear force during the high-speed dispersion of coatings. The preparation method of the present invention has the advantages of simple process, environmental protection, easy operation, suitable for large-scale production, significantly reducing the dosage of titanium dioxide in coatings, and having high economic value.

[0018] To solve the above problems, the present invention is achieved through the following technical solutions:

[0019] The first object of the present invention is:

[0020] A preparation method of a composite titanium white material prepared by phase separation, characterized in that:

[0021] It comprises the following components in parts by weight:

[0022] 10 - 40 parts of polymer monomer, 20 - 60 parts of co - solvent, 5 - 20 parts of metal oxide, 1 - 2 parts of surfactant, 10 - 40 parts of water, 0.03 - 0.6 part of initiator;

[0023] The polymer monomer is one or a combination of tripropylene glycol diacrylate, 1,6 - hexanediol diacrylate, and 1,4 - butanediol diacrylate;

[0024] The metal oxide is one or a combination of silicon dioxide and titanium dioxide;

[0025] It comprises the following preparation steps:

[0026] S1. Mix the polymer monomer and the co - solvent, seal and let stand at room temperature for 2 h to obtain a polymer monomer solution;

[0027] S2. Mix and dilute the metal oxide and water, slowly add the surfactant, and stir magnetically until the surfactant is completely dissolved. After dissolution, let stand at room temperature for 2 h to obtain a metal oxide solution;

[0028] S3. Mix the polymer monomer solution described in step S1 and the metal oxide solution described in step S2 to obtain a co - blended phase - separation solution;

[0029] S4. Add the initiator to the co - blended phase - separation solution described in step S3 to obtain a precursor solution;

[0030] S5. Spray the precursor solution described in step S4 on the surface of glass with a size of 210 mm × 297 mm, and dry at room temperature for 30 min to wait for the co - solvent to evaporate and induce phase separation;

[0031] S6. Place the glass containing the sample in step S5 under an ultraviolet lamp for irradiation to obtain a hybrid material;

[0032] S7. Grind the hybrid material described in step S6 with a ball mill for 30 min to obtain a composite titanium white material.

[0033] A further optimization of the preparation method of the composite titanium white material prepared by phase separation according to the present invention is:

[0034] The co - solvent is one or a combination of methanol, acetone, and ethanol.

[0035] A further optimization of the preparation method of the composite titanium white material prepared by phase separation according to the present invention is:

[0036] The mass percentage concentration of the polymer monomer solution is 40-60%.

[0037] The further optimization of the preparation method of the composite titanium white material prepared by phase separation of the present invention is as follows:

[0038] The surfactant is a cationic surfactant, and its mass is 7.5-18% of the mass of the metal oxide.

[0039] The further optimization of the preparation method of the composite titanium white material prepared by phase separation of the present invention is as follows:

[0040] The mass percentage concentration of the metal oxide solution is 20-50%.

[0041] The further optimization of the preparation method of the composite titanium white material prepared by phase separation of the present invention is as follows:

[0042] The initiator is a photoinitiator, and its mass is 0.1-2% of the mass of the polymer monomer.

[0043] The further optimization of the preparation method of the composite titanium white material prepared by phase separation of the present invention is as follows:

[0044] The irradiation under the ultraviolet lamp in step S6 has an ultraviolet light curing light intensity of 1400 mw / cm 2 , and the irradiation time is 5 min.

[0045] The second invention object of the present invention is:

[0046] To provide a composite titanium white material prepared by phase separation, which is prepared according to the preparation method of the composite titanium white material prepared by phase separation described above (including the preferred method).

[0047] The further optimization of the composite titanium white material prepared by phase separation of the present invention is as follows:

[0048] The composite titanium white material is a powder material, and its median particle size is 10-50 μm, preferably 20-40 μm.

[0049] The third invention object of the present invention is:

[0050] To provide the application of the composite titanium white material prepared by phase separation of the present invention, and the composite titanium white material prepared by phase separation is used as a white pigment in the fields of coatings, inks, plastics, papermaking, rubber, cosmetics, ceramics, and building materials.

[0051] The composite titanium white material prepared by the present invention is a powder material with excellent optical properties. Its reflectance in the visible light range (380nm - 780nm) reaches 80% - 100%, mainly in the range of 85 - 95%, which is much higher than the similar materials reported in the current literature. It solves the problem of the low reflectance of the materials prepared by this method. The composite titanium white material prepared by the present invention has excellent covering properties, can partially replace the titanium dioxide commonly used in coatings, and has a simple preparation technology and is easy to be scaled up for industrial production. It can be directly used in coating production. Its excellent mechanical stability also solves the drawback that the structure of such materials is broken due to strong shear force during the high-speed dispersion process of coatings.

[0052] The present invention also provides a preparation method of a composite titanium white material prepared by phase separation, which has the advantages of simple process, environmental protection, easy operation, being suitable for large-scale production, significantly reducing the dosage of titanium dioxide in coatings, and having high economic value.

[0053] The following are the explanations of the relevant terms involved in the present invention:

[0054] Phase separation technology: A binary or multi-component mixture will separate into different phases under certain conditions.

[0055] Covering power: It refers to the ability to cover the base background color. The size of the covering power depends on the difference between the refractive index of the pigment and the refractive index of the matrix resin. The larger the difference, the stronger the covering power. Description of the Drawings

[0056] Figure 1 It is a schematic diagram of the preparation process of the composite titanium white material in the present invention;

[0057] Figure 2 It is a display diagram of the composite titanium white material in the present invention;

[0058] Figure 3 It is a microscopic morphology diagram of the composite titanium white material in the present invention. Detailed Embodiments

[0059] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the content of the present invention will be described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not limited to the present invention. Any simple improvement to the preparation method of the present invention under the premise of the inventive concept of the present invention falls within the protection scope of the present invention.

[0060] Instruments and Reagents:

[0061] Tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, purchased from Aladdin Reagents;

[0062] Silica (30% concentration, pH = 3), titanium dioxide (20% concentration, average particle size 30 nm);

[0063] Co-solvents (methanol, ethanol, acetone), analytical grade, purchased from Aladdin Reagents;

[0064] The characterization instruments are ultraviolet spectrophotometer (HITACHI U-4100) and scanning electron microscope (HITACHI S-3400).

[0065] Example 1a

[0066] Step S1. Mix the polymer monomer tripropylene glycol diacrylate with the co-solvent ethanol, seal and let stand at room temperature for 2 h to obtain a tripropylene glycol diacrylate solution;

[0067] Step S2. Mix and dilute silica with water, slowly add cetyltrimethylammonium bromide, and stir with a magnetic stirrer until cetyltrimethylammonium bromide is completely dissolved. After dissolution, let stand at room temperature for 2 h to obtain a silica solution;

[0068] Step S3. Mix the tripropylene glycol diacrylate solution described in Step S1 and the silica solution described in Step S2 to obtain a blend phase separation solution;

[0069] Step S4. Add 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone to the blend phase separation solution described in Step S3 to obtain a precursor solution;

[0070] Step S5. Spray the precursor solution described in Step S4 on the surface of a glass with a size of 210 mm × 297 mm, and dry at room temperature for 30 min to wait for ethanol evaporation-induced phase separation;

[0071] Step S6. Place the glass containing the sample in Step S5 under an ultraviolet lamp with 1400 mw / cm 2 and irradiate for 5 min to obtain a hybrid material;

[0072] Step S7. Grind the hybrid material described in Step S6 with a ball mill for 30 min to obtain a composite titanium white material.

[0073] Preferably, the mass percentage concentration of the polymer monomer solution described in Step S1 is 45-55%.

[0074] Preferably, the mass of the surfactant cetyltrimethylammonium bromide described in Step S2 is 7.5-18% of the mass of the metal oxide.

[0075] Preferably, the mass percentage concentration of the metal oxide solution described in Step S2 is 20-30%.

[0076] Preferably, the mass of the initiator 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone described in step S4 is 0.2-1.8% of the mass of the polymer monomer.

[0077] For the specific dosages of each raw material, see Table 1.

[0078] Example 1b

[0079] Step S1. Mix the polymer monomer dipropylene glycol diacrylate with the co-solvent ethanol, seal and let stand at room temperature for 2 h to obtain a dipropylene glycol diacrylate solution.

[0080] Step S2. Mix and dilute titanium dioxide with water, slowly add cetyltrimethylammonium bromide, and stir magnetically until cetyltrimethylammonium bromide is completely dissolved. After dissolution, let stand at room temperature for 2 h to obtain a titanium dioxide solution.

[0081] Step S3. Mix the dipropylene glycol diacrylate solution described in step S1 and the titanium dioxide solution described in step S2 to obtain a co-blended phase separation solution.

[0082] Step S4. Add 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone to the co-blended phase separation solution described in step S3 to obtain a precursor solution.

[0083] Step S5. Spray the precursor solution described in step S4 onto the surface of glass with a size of 210 mm × 297 mm, and dry at room temperature for 30 min to wait for ethanol evaporation to induce phase separation.

[0084] Step S6. Place the glass containing the sample in step S5 under an ultraviolet lamp with an intensity of 1400 mw / cm 2 and irradiate for 5 min to obtain a hybrid material.

[0085] Step S7. Grind the hybrid material described in step S6 with a ball mill for 30 min to obtain a composite titanium white material.

[0086] Preferably, the mass percentage concentration of the polymer monomer solution described in step S1 is 45-55%.

[0087] Preferably, the mass of the surfactant cetyltrimethylammonium bromide described in step S2 is 7.5-18% of the mass of the metal oxide.

[0088] Preferably, the mass percentage concentration of the metal oxide solution described in step S2 is 20-30%.

[0089] Preferably, the mass of the initiator 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone described in step S4 is 0.2-1.8% of the mass of the polymer monomer.

[0090] The specific dosages of each raw material are shown in Table 1 in detail.

[0091] Example 2a

[0092] Step S1. Mix the polymer monomer 1,6 - hexanediol diacrylate with the co - solvent ethanol, seal and let stand at room temperature for 2 h to obtain a 1,6 - hexanediol diacrylate solution.

[0093] Step S2. Mix and dilute silica with water, slowly add cetyltrimethylammonium bromide while stirring magnetically until cetyltrimethylammonium bromide is completely dissolved. After dissolution, let stand at room temperature for 2 h to obtain a silica solution.

[0094] Step S3. Mix the 1,6 - hexanediol diacrylate solution described in Step S1 and the silica solution described in Step S2 to obtain a blend phase - separation solution.

[0095] Step S4. Add 2 - hydroxy - 4-(2 - hydroxyethoxy)-2 - methylpropiophenone to the blend phase - separation solution described in Step S3 to obtain a precursor solution.

[0096] Step S5. Spray the precursor solution described in Step S4 on the surface of a glass with a size of 210 mm×297 mm, and dry at room temperature for 30 min to wait for ethanol evaporation - induced phase separation.

[0097] Step S6. Place the glass containing the sample obtained in Step S5 under an ultraviolet lamp with an intensity of 1400 mw / cm 2 and irradiate for 5 min to obtain a hybrid material.

[0098] Step S7. Grind the hybrid material described in Step S6 with a ball mill for 30 min to obtain a composite titanium white material.

[0099] Preferably, the mass percentage concentration of the polymer monomer solution described in Step S1 is 45 - 55%.

[0100] Preferably, the mass of the surfactant cetyltrimethylammonium bromide described in Step S2 is 7.5 - 18% of the mass of the metal oxide.

[0101] Preferably, the mass percentage concentration of the metal oxide solution described in Step S2 is 20 - 30%.

[0102] Preferably, the mass of the initiator 2 - hydroxy - 4-(2 - hydroxyethoxy)-2 - methylpropiophenone described in Step S4 is 0.2 - 1.8% of the mass of the polymer monomer.

[0103] The specific dosages of each raw material are shown in Table 1 in detail.

[0104] Example 2b

[0105] Step S1. Mix the polymer monomer 1,6 - hexanediol diacrylate with the co - solvent ethanol, seal and let stand at room temperature for 2 h to obtain a 1,6 - hexanediol diacrylate solution;

[0106] Step S2. Mix and dilute titanium dioxide with water, slowly add cetyltrimethylammonium bromide while stirring magnetically until cetyltrimethylammonium bromide is completely dissolved. After dissolution, let stand at room temperature for 2 h to obtain a titanium dioxide solution;

[0107] Step S3. Mix the 1,6 - hexanediol diacrylate solution described in Step S1 and the titanium dioxide solution described in Step S2 to obtain a blend phase - separation solution;

[0108] Step S4. Add 2 - hydroxy - 4-(2 - hydroxyethoxy)-2 - methylpropiophenone to the blend phase - separation solution described in Step S3 to obtain a precursor solution;

[0109] Step S5. Spray the precursor solution described in Step S4 onto the surface of a glass with a size of 210 mm×297 mm, and dry at room temperature for 30 min to wait for ethanol evaporation - induced phase separation;

[0110] Step S6. Place the glass containing the sample obtained in Step S5 under an ultraviolet lamp with an intensity of 1400 mw / cm 2 and irradiate for 5 min to obtain a hybrid material;

[0111] Step S7. Grind the hybrid material described in Step S6 using a ball mill for 30 min to obtain a composite titanium white material.

[0112] Preferably, the mass percentage concentration of the polymer monomer solution described in Step S1 is 45 - 55%;

[0113] Preferably, the mass of the surfactant cetyltrimethylammonium bromide described in Step S2 is 7.5 - 18% of the mass of the metal oxide;

[0114] Preferably, the mass percentage concentration of the metal oxide solution described in Step S2 is 20 - 30%;

[0115] Preferably, the mass of the initiator 2 - hydroxy - 4-(2 - hydroxyethoxy)-2 - methylpropiophenone described in Step S4 is 0.2 - 1.8% of the mass of the polymer monomer.

[0116] The specific dosages of each raw material are shown in Table 1.

[0117] Example 3a

[0118] Step S1. Mix the polymer monomer 1,4 - butanediol diacrylate with the co - solvent ethanol, seal and let stand at room temperature for 2 h to obtain a 1,4 - butanediol diacrylate solution;

[0119] Step S2. Mix and dilute silica with water, slowly add cetyltrimethylammonium bromide, and stir magnetically at the same time until cetyltrimethylammonium bromide is completely dissolved. After dissolution is completed, let it stand at room temperature for 2 h to obtain a silica solution;

[0120] Step S3. Mix the 1,4-butanediol diacrylate solution described in Step S1 and the silica solution described in Step S2 to obtain a blend phase separation solution;

[0121] Step S4. Add 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone to the blend phase separation solution described in Step S3 to obtain a precursor solution;

[0122] Step S5. Spray the precursor solution described in Step S4 on the surface of a glass with a size of 210 mm × 297 mm, and dry it at room temperature for 30 min to wait for ethanol evaporation-induced phase separation;

[0123] Step S6. Place the glass containing the sample obtained in Step S5 under an ultraviolet lamp with an intensity of 1400 mw / cm 2 and irradiate it for 5 min to obtain a hybrid material;

[0124] Step S7. Grind the hybrid material described in Step S6 with a ball mill for 30 min to obtain a composite titanium white material.

[0125] Preferably, the mass percentage concentration of the polymer monomer solution described in Step S1 is 45-55%.

[0126] Preferably, the mass of the surfactant cetyltrimethylammonium bromide described in Step S2 is 7.5-18% of the mass of the metal oxide.

[0127] Preferably, the mass percentage concentration of the metal oxide solution described in Step S2 is 20-30%.

[0128] Preferably, the mass of the initiator 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone described in Step S4 is 0.2-1.8% of the mass of the polymer monomer.

[0129] For the specific dosages of each raw material, please refer to Table 1.

[0130] Example 3b

[0131] Step S1. Mix the polymer monomer 1,4-butanediol diacrylate with the co-solvent ethanol, and seal and let it stand at room temperature for 2 h to obtain a 1,4-butanediol diacrylate solution;

[0132] Step S2. Mix and dilute titanium dioxide with water, slowly add cetyltrimethylammonium bromide while using magnetic stirring until cetyltrimethylammonium bromide is completely dissolved. After dissolution is complete, let it stand at room temperature for 2 h to obtain a titanium dioxide solution;

[0133] Step S3. Mix the 1,4-butanediol diacrylate solution described in Step S1 and the titanium dioxide solution described in Step S2 to obtain a blend phase separation solution;

[0134] Step S4. Add 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone to the blend phase separation solution described in Step S3 to obtain a precursor solution;

[0135] Step S5. Spray the precursor solution described in Step S4 onto the surface of a glass with a size of 210 mm × 297 mm, and dry it at room temperature for 30 min to wait for ethanol evaporation to induce phase separation;

[0136] Step S6. Place the glass containing the sample obtained in Step S5 under an ultraviolet lamp with an intensity of 1400 mw / cm 2 and irradiate it for 5 min to obtain a hybrid material;

[0137] Step S7. Grind the hybrid material described in Step S6 using a ball mill for 30 min to obtain a composite titanium white material.

[0138] Preferably, the mass percentage concentration of the polymer monomer solution described in Step S1 is 45 - 55%.

[0139] Preferably, the mass of the surfactant cetyltrimethylammonium bromide described in Step S2 is 7.5 - 18% of the mass of the metal oxide.

[0140] Preferably, the mass percentage concentration of the metal oxide solution described in Step S2 is 20 - 30%.

[0141] Preferably, the mass of the initiator 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone described in Step S4 is 0.2 - 1.8% of the mass of the polymer monomer.

[0142] For the specific dosages of each raw material, please refer to Table 1.

[0143] Measure the visible light (380 nm - 780 m) reflectivity of the composite titanium white material by spectrophotometry, and measure the average particle size of the composite titanium white material using a particle size analyzer.

[0144] Table 1 Specific raw material composition table of each example (parts by weight)

[0145]

[0146] According to the 6 different embodiments in Table 1, the following experimental data parameters can be obtained, as shown in Table 2. Among them, the test result of the particle size is the average particle size, and the reflectance is tested using an ultraviolet-visible-near-infrared spectrophotometer. The test of the coating covering performance refers to the national standard GB / T 23981-2019. Specifically, the composite titanium white material prepared in the embodiment is substituted and verified in the formulation with a 10% content (10% improvement), and the difference in the contrast ratio is compared.

[0147] Experimental data table of each embodiment in Table 2

[0148]

[0149] As can be seen from Table 2, the composite material provided by the present invention still has excellent covering performance under the 10% improvement scheme of titanium white, far exceeding the first-class product index required by GB / T 23981-2019.

[0150] Comparing Example 1a and Example 1b, it can be seen that choosing silica with a lower refractive index can obtain better reflectance, thereby improving the covering performance of the coating.

[0151] Comparing Example 1a and Example 2a, it can be seen that choosing the photocurable resin 1,6-hexanediol diacrylate can further improve the reflectance of the composite titanium white material.

[0152] In summary, the above are only the preferred examples of the present invention, and there is no any formal limitation to the present invention; any equivalent changes made by those skilled in the art without departing from the technical solution of the present invention, using the disclosed technical content for some changes, modifications and evolutions, are regarded as the equivalent examples of the present invention; at the same time, any equivalent changes, modifications and evolutions made to the above embodiments according to the essential technology of the present invention still fall within the protection scope of the technical solution of the present invention.

[0153] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of concise description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered that it is within the scope described in this specification.

[0154] The experimental methods without specific conditions in the present invention are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer.

[0155] For various optimized technical solutions in the present invention, unless otherwise stated, various optimized technical solutions can be combined with each other.

[0156] Unless otherwise stated, the percentages and parts are weight percentages and weight parts.

[0157] For experimental methods not specified in the description and examples, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer.

[0158] In the present invention, various raw materials, reagents, and components are, unless otherwise specified, the corresponding raw materials commonly used in the art.

[0159] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to persons skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the method of the present invention.

Claims

1. A preparation method of a composite titanium white material prepared by phase separation, characterized in that: It comprises the following components in parts by weight: 10 - 40 parts of polymer monomer, 20 - 60 parts of cosolvent, 5 - 20 parts of metal oxide, 1 - 2 parts of surfactant, 10 - 40 parts of water, 0.03 - 0.6 part of initiator; The polymer monomer is one or a combination of dipropylene glycol diacrylate, 1,6 - hexanediol diacrylate, and 1,4 - butanediol diacrylate; The metal oxide is one or a combination of silicon dioxide and titanium dioxide; It comprises the following preparation steps: S1. Mix the polymer monomer and the cosolvent, seal and let stand at room temperature for 2 h to obtain a polymer monomer solution; S2. Mix and dilute the metal oxide and water, slowly add the surfactant while stirring magnetically until the surfactant is completely dissolved, and after dissolution, let stand at room temperature for 2 h to obtain a metal oxide solution; S3. Mix the polymer monomer solution obtained in step S1 and the metal oxide solution obtained in step S2 to obtain a blend phase - separation solution; S4. Add the initiator to the blend phase - separation solution obtained in step S3 to obtain a precursor solution; S5. Spray the precursor solution obtained in step S4 on the surface of glass with a size of 210 mm×297 mm, and dry at room temperature for 30 min to wait for the cosolvent to evaporate and induce phase separation; S6. Place the glass containing the sample obtained in step S5 under an ultraviolet lamp for irradiation to obtain a hybrid material; S7. Grind the hybrid material obtained in step S6 with a ball mill for 30 min to obtain a composite titanium white material.

2. The preparation method of the composite titanium white material prepared by phase separation according to claim 1, characterized in that: The cosolvent is one or a combination of methanol, acetone, and ethanol.

3. The preparation method of the composite titanium white material prepared by phase separation according to claim 1, characterized in that: The mass percentage concentration of the polymer monomer solution is 40 - 60%.

4. The preparation method of the composite titanium white material prepared by phase separation according to claim 1, characterized in that: The surfactant is a cationic surfactant, and its mass is 7.5 - 18% of the mass of the metal oxide.

5. The preparation method of the composite titanium white material prepared by phase separation according to claim 1, characterized in that: The mass percentage concentration of the metal oxide solution is 20 - 50%.

6. The preparation method of the composite titanium white material prepared by phase separation according to claim 1, characterized in that: The initiator is a photo - initiator, and its mass is 0.1 - 2% of the mass of the polymer monomer.

7. The preparation method of the composite titanium white material prepared by phase separation according to claim 1, characterized in that: The ultraviolet light irradiation described in step S6 has an ultraviolet light curing light intensity of 1400 mw / cm 2 , and the irradiation time is 5 minutes.

8. A composite titanium white material prepared by phase separation, characterized in that: It is prepared according to the preparation method of the composite titanium white material prepared by phase separation according to any one of claims 1 - 7.

9. The composite titanium white material prepared by phase separation according to claim 8, characterized in that: The composite titanium white material is a powder material with a median particle size of 10 - 50 μm.

10. An application of the composite titanium white material prepared by phase separation according to claim 8, characterized in that: The application of the composite titanium white material prepared by phase separation as a white pigment in the fields of coatings, inks, plastics, papermaking, rubbers, cosmetics, ceramics, and building materials.

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