High whiteness base material powder for decorative materials and method for producing the same

Abstract

The present invention discloses a high-whiteness base material powder for decorative materials and a preparation method thereof. The high-whiteness base material powder for decorative materials is composed of the following ingredients in parts by weight: 28-42 parts of white cement clinker, 10-30 parts of quartz stone, 12-25 parts of gypsum, 1-4 parts of rare-earth-doped alumina, 2-4 parts of epoxy-modified polyurethane dispersant, 5-10 parts of nano-titanium dioxide, 0.3-0.7 parts of an active agent, and 0.2-0.5 parts of a retarder. By adding rare-earth-doped alumina, an epoxy-modified polyurethane dispersant, an active agent, and a corrosion inhibitor to the original ingredients of white cement clinker, quartz stone, gypsum, and fly ash, the whiteness and fineness of the base material powder particles are improved, the compressive strength is enhanced, the surface is smoother, more uniform, and more beautiful, and the decorative effect is enhanced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high-whiteness base material powder, and particularly relates to high-whiteness base material powder for decorative materials and a preparation method thereof. BACKGROUND

[0002] In a conventional preparation method of high-whiteness base material powder for decorative materials, barium sulfate, barium carbonate, calcium sulfate and the like are usually used as raw materials, and the high-whiteness base material powder is prepared through high-temperature melting, ball milling, spray drying and the like. However, the base material powder prepared by the conventional method has the problems of low whiteness, many impurities and unstable performance, and thus a new preparation method is needed to solve these problems.

[0003] Patent CN 110981342 B discloses a high-strength white concrete, which comprises the following components in parts by weight: white Portland cement 1 part, coarse aggregate 1.74-4 parts, sand 1.2-2.6 parts and water reducing agent 0.025-0.03 parts; the white Portland cement has a whiteness of greater than or equal to 88 and a strength greater than or equal to 42.5. The invention uses high-whiteness high-strength white Portland cement, and adds a water reducing agent to reduce the water-binder ratio, thereby improving the strength of the concrete, improving the flowability of the mixture, reducing the bleeding segregation phenomenon, delaying the setting time of the concrete, and enhancing the appearance and strength of the finished product. However, the whiteness, dispersibility and mechanical properties of the material obtained by the invention still have room for improvement. SUMMARY

[0004] The present application aims to provide high-whiteness base material powder for decorative materials and a preparation method thereof, to solve the technical problems of poor whiteness, dispersibility and mechanical properties of the powder in the prior art.

[0005] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] The present application provides high-whiteness base material powder for decorative materials, which is composed of the following components in parts by weight: 53-60 parts of white cement clinker, 26-33 parts of quartzite, 1.5-3 parts of gypsum, 2-5 parts of fly ash, 1-2 parts of rare earth doped alumina, 0.5-1 part of epoxy modified polyurethane dispersant, 1-3 parts of nano titanium dioxide, 0.3-0.7 parts of activator and 0.2-0.5 parts of retarder.

[0007] As a preferred embodiment, the preparation method of the rare earth doped alumina comprises the following steps:

[0008] P1: ultrasonic cleaning aluminum sheet, placing it in a beaker containing isopropyl alcohol, adding potassium permanganate, heating reaction with an electric heating jacket, distilling after the reaction to obtain aluminum isopropoxide;

[0009] P2: slowly add aluminum isopropyl alcohol into the isopropyl alcohol solution containing acetylacetone, stir, age, add a mixed solution of aluminum isopropyl alcohol and distilled water, after strong stirring, add nitric acid, adjust the pH to obtain an alumina sol;

[0010] P3: after dissolving cerium nitrate in distilled water, add it to the alumina sol, stir, dry, heat, incubate, cool, and grind to obtain rare earth-doped alumina.

[0011] In the above process, the non-aqueous sol-gel process is used to prepare rare earth-doped alumina. The doped rare earth cerium element has a unique electronic structure that can affect the interaction between light and materials. When light shines on the surface of the material, the rare earth cerium-doped alumina can effectively scatter the light, making the overall scattering more uniform, effectively improving the whiteness of the material. At the same time, the rare earth cerium doping can change the crystal lattice structure of alumina, affecting the light absorption and reflection performance, further enhancing the hiding power. The cerium element has high chemical stability in alumina and is not easily chemically reacted with gases, moisture and other substances in the surrounding environment, which helps to increase the weather resistance of the alumina powder. When the cerium element is exposed to the external environment, it forms a cerium oxide film by contacting with oxygen, which can protect the substrate powder from the influence of external environment such as ultraviolet light and humidity, further improving the weather resistance. The doping of rare earth cerium element changes the crystal lattice structure of alumina, forming a more stable and ordered crystal structure, which helps to improve the mechanical strength and compression resistance. The doping of cerium element helps to form smaller grains, increases the number of material blocking dislocation movement areas, and improves the strength and compression resistance of the material.

[0012] As a preferred, in the P1, the purity of aluminum sheet is 99.99%, the molar ratio of aluminum sheet to isopropyl alcohol is 1:(2-3), the heating reaction temperature is 60-80℃, and the reaction time is 4-6h.

[0013] As a preferred, in the P2, the molar ratio of aluminum isopropyl alcohol to acetylacetone is 1:(2-2.5), the stirring time is 1-2h, the aging time is 1-2h, the molar ratio of aluminum isopropyl alcohol to distilled water is 1:(0.8-0.9), the strong stirring temperature is 28-32℃, the stirring time is 3-5h, and the pH is adjusted to 3.0.

[0014] As a preferred, in the P3, the molar ratio of cerium nitrate, distilled water and alumina sol is (0.001-0.05):(0.2-0.4):1, the stirring time is 14-16h, the drying temperature is 100-110℃, the drying time is 8-10h, the heating rate is 4℃ / min, the heating temperature is 800-1000℃, and the incubation time is 1-2h.

[0015] As a preferred, the preparation method of the epoxy-modified polyurethane dispersant comprises the following steps:

[0016] S1: Diphenyl methane diisocyanate is added to a three-necked flask containing tetrahydrofuran, then polyethylene glycol is added, and the reaction is heated;

[0017] S2: 2,2-dimethylol propionic acid is added to a three-necked flask, and the chain extension reaction is heated, during which dibutyl tin dilaurate is added, and 1,3-propanediol is dissolved in tetrahydrofuran and then added dropwise to the three-necked flask to perform the branching reaction;

[0018] S3: After the branching reaction is completed, the three-necked flask is cooled, 1-(3- aminopropyl) morpholine is added, and the reaction is performed, then epoxy propanol is added to perform the reaction, and an epoxy-modified polyurethane dispersant is obtained.

[0019] In the above process, an epoxy-modified polyurethane dispersant is synthesized by using diphenyl methane diisocyanate, polyethylene glycol, and 2,2-dimethylol propionic acid as raw materials, and the synthesis process is as follows:

[0020]

[0021] The synthesized epoxy-modified polyurethane dispersant has excellent dispersibility and stability, can effectively prevent the aggregation or sedimentation of the substrate powder during the processing, improve the dispersibility and stability, and introduce 1-(3- aminopropyl) morpholine as an anchoring group during the reaction, so that the dispersant has strong bonding force with the substrate powder, enhances the bonding performance between the materials, improves the adhesion of the powder coating, and maintains stable adhesion performance; at the same time, the dispersant can react with the active functional groups in the substrate powder to form a three-dimensional network structure, enhance the mechanical properties of the materials, improve the hardness and wear resistance of the powder coating, and thus improve the durability and service life of the decorative material.

[0022] As a preferred, in the S1, the relative molecular mass of the polyethylene glycol is 600, the molar ratio of the diphenyl methane diisocyanate to the polyethylene glycol is 3:(0.8-1.2), the heating temperature is 70-80℃, and the reaction time is 2-3h; in the S2, the molar ratio of the 2,2-dimethylol propionic acid to the 1,3-propanediol is (2-3):(4-6), the chain extension reaction temperature is 80-90℃, the reaction time is 2-3h, and the branching reaction time is 4-5h; in the S3, the temperature is cooled to 55-60℃, the reaction time is 1-2h, the temperature for adding the epoxy propanol to perform the reaction is 60-65℃, and the reaction time is 2-3h.

[0023] As a preferred, the preparation method of the high-whiteness substrate powder for decorative materials comprises the following steps:

[0024] Step (1): dissolving the epoxy modified polyurethane dispersant in distilled water, stirring uniformly to obtain a dispersant emulsion, then adding white cement clinker, quartzite, gypsum, fly ash and nano titanium dioxide into the dispersant emulsion for stirring to obtain a base material system;

[0025] Step (2): adding rare earth doped alumina, activator and retarder into the base material system in sequence, adding zirconium beads, high-speed ball milling, drying to obtain a high-whiteness base material powder for decorative materials.

[0026] Preferably, in the step (1), the stirring speed is 1000-1200 rpm, and the stirring time is 2-3 h.

[0027] Preferably, in the step (2), the particle size of the zirconium beads is 0.8-1.0 mm, the ball milling speed is 4000-5000 rpm, the ball milling time is 6-10 h, the drying temperature is 80-100℃, and the drying time is 3-5 h.

[0028] In summary, due to the adoption of the above technical solutions, the present application has the following advantages:

[0029] 1. In the present application, rare earth doped alumina is first prepared and added into the base material powder, which can improve the mechanical properties, stability and whiteness of the base material powder, then the epoxy modified polyurethane dispersant with excellent dispersibility and stability is prepared and added into the base material powder, which can effectively improve the stability thereof, and the obtained high-whiteness base material powder can be used in decorative materials, which can effectively improve the hiding power and service life thereof.

[0030] 2. In the present application, the rare earth doped alumina is synthesized by using aluminum sheet, isopropyl alcohol and cerium nitrate as raw materials through hydrolysis and chelation, the doping of cerium can not only effectively scatter light and improve the whiteness of the material, but also change the crystal lattice structure of alumina, affect the light absorption and reflection performance, and enhance the hiding power. In addition, cerium has high stability in alumina, which helps to increase the weather resistance of alumina, and when the cerium element is exposed to the external environment, a protective cerium oxide film is formed, further enhancing the weather resistance, and the doping of cerium helps to form a more stable and ordered crystal structure, improving the mechanical strength and compression resistance.

[0031] 3. In the present application, the epoxy modified polyurethane dispersant with excellent dispersibility and stability is synthesized by using diphenyl methane diisocyanate, polyethylene glycol and 2,2-dimethylol propionic acid as raw materials through amino and hydroxyl reaction, and since 1-(3-aminopropyl) morpholine is introduced as an anchoring group in the synthesis process, the bonding force between the dispersant and the base material powder is enhanced, the adhesion between materials is enhanced, the adhesion of the powder coating is improved, and the stable adhesion performance is maintained. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0033] Embodiment 1

[0034] The embodiment discloses a high-whiteness base material powder for decorative materials, which is composed of the following ingredients in parts by weight: 57 parts of white cement clinker, 32 parts of quartz stone, 2.25 parts of gypsum, 3.5 parts of fly ash, and the ingredients of other embodiments are derived from the base ingredients of the white cement clinker, the quartz stone, the gypsum and the fly ash of the present embodiment.

[0035] Embodiment 2

[0036] The embodiment discloses a preparation method of rare earth doped alumina, comprising the following steps:

[0037] P1: 1g of aluminum sheet with a purity of 99.99% is ultrasonically cleaned and then placed in a beaker containing 6.37mL of isopropyl alcohol, potassium permanganate is added, and a heating reaction is performed using an electric heating jacket, 80℃ for 4h, after the reaction is completed, distillation is performed to obtain aluminum isopropyl alcohol;

[0038] P2: 0.97mL of aluminum isopropyl alcohol is slowly added to an isopropyl alcohol solution containing 1.30mL of acetylacetone, stirred for 1.5h, aged for 1h, and then a mixed solution of 1.063mL of aluminum isopropyl alcohol and 0.11mL of distilled water is added, after being stirred strongly at 32℃ for 4h, nitric acid is added, and after adjusting the pH to 3.0, an alumina sol is obtained;

[0039] P3: 0.969g of cerium nitrate is dissolved in 3.8mL of distilled water and then added to 102g of the alumina sol, stirred for 16h, dried at 110℃ for 8h, heated to 800℃ at a heating rate of 4℃ / min, kept at 800℃ for 2h, cooled, and ground to obtain rare earth doped alumina.

[0040] The embodiment discloses a preparation method of an epoxy modified polyurethane dispersant, comprising the following steps:

[0041] S1: 1g of diphenyl methane diisocyanate is added to a three-necked flask containing tetrahydrofuran, and then 0.77g of polyethylene glycol with a relative molecular mass of 600 is added, and a heating reaction is performed at 80℃ for 2h;

[0042] S2: 1.59 g of 2,2-dimethylolpropionic acid was added to a three-necked flask and heated for chain extension reaction at 80°C for 3 h. During the reaction, dibutyltin dilaurate was added. 1.25 g of 1,3-propylene glycol was dissolved in tetrahydrofuran and added dropwise to the three-necked flask for branching reaction for 4 h.

[0043] S3: After the branching reaction is completed, the three-necked flask is cooled to 60° C., 1-(3-aminopropyl)morpholine is added, and the reaction is carried out for 2 h. Then, glycidol is added and the reaction is carried out at 65° C. for 2 h to obtain an epoxy-modified polyurethane dispersant.

[0044] This embodiment discloses a high-whiteness base material powder for decorative materials, which is composed of the following ingredients in parts by weight: 56 parts of white cement clinker, 30 parts of quartz stone, 2.3 parts of gypsum, 3.5 parts of fly ash, 1.5 parts of rare earth-doped alumina, 0.7 parts of epoxy-modified polyurethane dispersant, 2 parts of nano-titanium dioxide, 0.5 parts of active agent, and 0.35 parts of retarder.

[0045] This embodiment discloses a method for preparing a high-whiteness base material powder for decorative materials, comprising the following steps:

[0046] Step (1): dissolving an epoxy-modified polyurethane dispersant in distilled water and stirring at 1200 rpm for 3 h to obtain a dispersant emulsion, then adding white cement clinker, quartz stone, gypsum, fly ash and nano-titanium dioxide to the dispersant emulsion and stirring to obtain a substrate system;

[0047] Step (2): rare earth-doped alumina, an active agent, and a retarder are sequentially added to the substrate system, 1.0 mm zirconium beads are added, high-speed ball milling is performed at 5000 rpm for 10 hours, and drying is performed at 100° C. for 5 hours to obtain a high-whiteness substrate powder for decorative materials.

[0048] Example 3

[0049] This embodiment discloses a method for preparing rare earth-doped aluminum oxide, comprising the following steps:

[0050] P1: After ultrasonic cleaning, 1 g of 99.99% pure aluminum sheet was placed in a beaker containing 7.07 mL of isopropyl alcohol. Potassium permanganate was added and heated using a heating mantle at 80°C for 4 h. After the reaction, aluminum isopropylate was obtained by distillation.

[0051] P2: 0.97 mL of aluminum isopropoxide was slowly added to an isopropanol solution containing 1.12 mL of acetylacetone, stirred for 1.5 h, aged for 1 h, and a mixed solution of 1.063 mL of aluminum isopropoxide and 0.112 mL of distilled water was added. After vigorous stirring at 32°C for 4 h, nitric acid was added and the pH was adjusted to 3.0 to obtain an alumina sol;

[0052] P3: 0.458 g cerium nitrate was dissolved in 4.0 mL distilled water and added to 102 g alumina sol, stirred for 16 h, dried at 110°C for 8 h, heated to 800°C at a heating rate of 4°C / min, kept for 2 h, cooled, ground, to obtain rare earth doped alumina.

[0053] The present embodiment discloses a preparation method of an epoxy modified polyurethane dispersant, comprising the following steps:

[0054] S1: 1 g of diphenylmethane diisocyanate was added to a three-necked flask containing tetrahydrofuran, followed by adding 0.65 g of polyethylene glycol with a relative molecular mass of 600, and heated at 80°C for 2 h;

[0055] S2: 1.3 g of 2,2-dimethylol propionic acid was added to a three-necked flask, heated for chain extension reaction, reacted at 80°C for 3 h, and dibutyltin dilaurate was added during the reaction, 1 g of 1,3-propanediol was dissolved in tetrahydrofuran and added dropwise to the three-necked flask, and branched reaction was carried out for 4 h;

[0056] S3: After the branched reaction was completed, the three-necked flask was cooled to 60°C, 1-(3-aminopropyl) morpholine was added, and reacted for 2 h, followed by adding epoxy propanol and reacting at 65°C for 2 h, to obtain an epoxy modified polyurethane dispersant.

[0057] The present embodiment discloses a high-whiteness base material powder for decorative materials, which is composed of the following ingredients by weight: 58 parts of white cement clinker, 32 parts of quartz stone, 1.8 parts of gypsum, 2 parts of fly ash, 1 part of rare earth doped alumina, 0.5 part of epoxy modified polyurethane dispersant, 1 part of nano titanium dioxide, 0.45 part of activator, and 0.2 part of retarder.

[0058] The present embodiment discloses a preparation method of a high-whiteness base material powder for decorative materials, comprising the following steps:

[0059] Step (1): The epoxy modified polyurethane dispersant was dissolved in distilled water, and an emulsion of the dispersant was obtained after stirring at 1200 rpm for 3 h, and then the white cement clinker, quartz stone, gypsum, fly ash, and nano titanium dioxide were added to the dispersant emulsion for stirring, to obtain a base material system;

[0060] Step (2): The rare earth doped alumina, activator, and retarder were sequentially added to the base material system, 1.0 mm zirconium beads were added, and high-speed ball milling was carried out at 5000 rpm for 10 h, and then dried at 100°C for 5 h, to obtain a high-whiteness base material powder for decorative materials.

[0061] Example 4

[0062] The present embodiment discloses a preparation method of rare earth doped alumina, comprising the following steps:

[0063] P1: 1g of aluminum sheet with a purity of 99.99% is ultrasonically cleaned and placed in a beaker containing 6.22mL of isopropyl alcohol, potassium permanganate is added, and a heating reaction is performed using an electric heating mantle, 80°C for 4h, after the reaction is completed, distillation is performed to obtain aluminum isopropoxide;

[0064] P2: 0.97mL of aluminum isopropoxide is slowly added to a solution of 1.36mL of acetylacetone in isopropyl alcohol, stirred for 1.5h, aged for 1h, a mixed solution of 1.063mL of aluminum isopropoxide and 0.105mL of distilled water is added, stirred vigorously at 32°C for 4h, then nitric acid is added, and after adjusting the pH to 3.0, an alumina sol is obtained;

[0065] P3: 1.237g of cerium nitrate is dissolved in 6.5mL of distilled water and added to 102g of alumina sol, stirred for 16h, dried at 110°C for 8h, heated to 800°C at a heating rate of 4°C / min, held for 2h, cooled, and ground to obtain rare earth-doped alumina.

[0066] The embodiment discloses a preparation method of an epoxy-modified polyurethane dispersant, comprising the following steps:

[0067] S1: 1g of diphenylmethane diisocyanate is added to a three-necked flask containing tetrahydrofuran, then 0.90g of polyethylene glycol with a relative molecular mass of 600 is added, and a heating reaction is performed at 80°C for 2h;

[0068] S2: 1.8g of 2,2-dimethylol propionic acid is added to a three-necked flask, and a chain extension reaction is performed by heating, 80°C for 3h, during the reaction, dibutyltin dilaurate is added, 1.5g of 1,3-propanediol is dissolved in tetrahydrofuran and added dropwise to the three-necked flask, and a branching reaction is performed for 4h;

[0069] S3: after the branching reaction is completed, the three-necked flask is cooled to 60°C, 1-(3-aminopropyl) morpholine is added, and a reaction is performed for 2h, then epoxypropanol is added, and a reaction is performed at 65°C for 2h to obtain an epoxy-modified polyurethane dispersant.

[0070] The embodiment discloses a high-whiteness base material powder for decorative materials, which is composed of the following components in parts by weight: 54 parts of white cement clinker, 28 parts of quartz stone, 2.7 parts of gypsum, 4 parts of fly ash, 2 parts of rare earth-doped alumina, 0.6 parts of epoxy-modified polyurethane dispersant, 3 parts of nano titanium dioxide, 0.55 parts of activator, and 0.5 parts of retarder.

[0071] The embodiment discloses a preparation method of a high-whiteness base material powder for decorative materials, comprising the following steps:

[0072] Step (1): Dissolve the epoxy-modified polyurethane dispersant in distilled water, stir at 1200 rpm for 3 h to obtain a dispersant emulsion, then add white cement clinker, quartzite, gypsum, fly ash and nano-titanium dioxide into the dispersant emulsion for stirring to obtain a substrate system;

[0073] Step (2): Add rare earth-doped alumina, activator and retarder into the substrate system in sequence, add 1.0 mm zirconium beads, high-speed ball mill at 5000 rpm for 10 h, dry at 100℃ for 5 h to obtain a high-whiteness substrate powder for decorative materials.

[0074] Example 5

[0075] This example discloses a preparation method of rare earth-doped alumina, comprising the following steps:

[0076] P1: After ultrasonic cleaning, 1 g of aluminum sheet with a purity of 99.99% is placed in a beaker containing 7.80 mL of isopropyl alcohol, potassium permanganate is added, and heating reaction is carried out using an electric heating mantle, 80℃ for 4 h, after the reaction is completed, distillation is carried out to obtain aluminum isopropoxide;

[0077] P2: 0.97 mL of aluminum isopropoxide is slowly added to an isopropyl alcohol solution containing 1.28 mL of acetylacetone, stirred for 1.5 h, aged for 1 h, and then a mixed solution of 1.063 mL of aluminum isopropoxide and 0.108 mL of distilled water is added, after stirring at 32℃ for 4 h, nitric acid is added, and the pH is adjusted to 3.0 to obtain an alumina sol;

[0078] P3: After 1.595 g of cerium nitrate is dissolved in 5.4 mL of distilled water, it is added to 102 g of alumina sol, stirred for 16 h, dried at 110℃ for 8 h, heated to 800℃ at a heating rate of 4℃ / min, and kept for 2 h, cooled, and ground to obtain rare earth-doped alumina.

[0079] This example discloses a preparation method of an epoxy-modified polyurethane dispersant, comprising the following steps:

[0080] S1: 1 g of diphenyl methane diisocyanate is added to a three-necked flask containing tetrahydrofuran, then 0.85 g of polyethylene glycol with a relative molecular mass of 600 is added, and heating reaction is carried out at 80℃ for 2 h;

[0081] S2: 1.9 g of 2,2-dimethylol propionic acid is added to the three-necked flask, chain extension reaction is carried out by heating, 80℃ for 3 h, and during the reaction, dibutyltin dilaurate is added, 1.3 g of 1,3-propanediol is dissolved in tetrahydrofuran and added dropwise to the three-necked flask, and branching reaction is carried out for 4 h;

[0082] S3: After the branching reaction is completed, the three-necked flask is cooled to 60°C, 1-(3- aminopropyl) morpholine is added, and the reaction is carried out for 2 h, then propylene oxide is added, and the reaction is carried out at 65°C for 2 h to obtain an epoxy-modified polyurethane dispersant.

[0083] The embodiment discloses a high-whiteness base material powder for decorative materials, which is composed of the following ingredients in parts by weight: 59 parts of white cement clinker, 27 parts of quartz stone, 2.5 parts of gypsum, 5 parts of fly ash, 1.8 parts of rare earth-doped alumina, 0.8 parts of an epoxy-modified polyurethane dispersant, 1.5 parts of nano titanium dioxide, 0.3 parts of an activator, and 0.3 parts of a retarder.

[0084] The embodiment discloses a preparation method of a high-whiteness base material powder for decorative materials, which comprises the following steps:

[0085] Step (1): The epoxy-modified polyurethane dispersant is dissolved in distilled water, and an emulsion of the dispersant is obtained after stirring at 1200 rpm for 3 h; then the white cement clinker, the quartz stone, the gypsum, the fly ash, and the nano titanium dioxide are added to the emulsion of the dispersant and stirred to obtain a base material system;

[0086] Step (2): The rare earth-doped alumina, the activator, and the retarder are sequentially added to the base material system, 1.0 mm zirconium beads are added, and high-speed ball milling is carried out at 5000 rpm for 10 h; and the high-whiteness base material powder for decorative materials is obtained by drying at 100°C for 5 h.

[0087] Embodiment 6

[0088] The embodiment discloses a preparation method of rare earth-doped alumina, which comprises the following steps:

[0089] P1: After 1 g of aluminum sheet with a purity of 99.99% is ultrasonically cleaned, the aluminum sheet is placed in a beaker containing 6.41 mL of isopropyl alcohol, potassium permanganate is added, and heating reaction is carried out by using an electric heating mantle; the reaction is carried out at 80°C for 4 h; after the reaction is completed, distillation is carried out to obtain aluminum isopropoxide;

[0090] P2: 0.97 mL of aluminum isopropoxide is slowly added to an isopropyl alcohol solution containing 1.33 mL of acetylacetone, stirring is carried out for 1.5 h, aging is carried out for 1 h, a mixed solution of 1.063 mL of aluminum isopropoxide and 0.1 mL of distilled water is added, and after stirring at 32°C for 4 h, nitric acid is added, and after the pH is adjusted to 3.0, an alumina sol is obtained;

[0091] P3: After 0.633 g of cerium nitrate is dissolved in 7.0 mL of distilled water, the solution is added to 102 g of the alumina sol, stirring is carried out for 16 h, drying is carried out at 110°C for 8 h, the temperature is raised to 800°C at a temperature rising rate of 4°C / min, and the temperature is kept for 2 h, and after cooling and grinding, rare earth-doped alumina is obtained.

[0092] The embodiment discloses a preparation method of an epoxy-modified polyurethane dispersant, and comprises the following steps:

[0093] S1: 1g of diphenylmethane diisocyanate is added into a three-necked flask containing tetrahydrofuran, then 0.75g of polyethylene glycol with a relative molecular mass of 600 is added, and the reaction is heated at 80℃ for 2h;

[0094] S2: 1.4g of 2,2-dimethylol propionic acid is added into a three-necked flask, and the chain extension reaction is heated, the reaction is carried out at 80℃ for 3h, and during the reaction, dibutyltin dilaurate is added, 1.2g of 1,3-propanediol is dissolved in tetrahydrofuran, and then added dropwise into the three-necked flask, and the branching reaction is carried out for 4h;

[0095] S3: after the branching reaction is completed, the three-necked flask is cooled to 60℃, 1-(3-aminopropyl) morpholine is added, the reaction is carried out for 2h, then epoxypropanol is added, the reaction is carried out at 65℃ for 2h, and the epoxy-modified polyurethane dispersant is obtained.

[0096] The embodiment discloses a high-whiteness base material powder for decorative materials, which is composed of the following components in parts by weight: 60 parts of white cement clinker, 31 parts of quartz stone, 2.3 parts of gypsum, 3 parts of fly ash, 1.2 parts of rare earth doped alumina, 0.9 parts of epoxy-modified polyurethane dispersant, 2.5 parts of nano titanium dioxide, 0.7 parts of activator and 0.4 parts of retarder.

[0097] The embodiment discloses a preparation method of a high-whiteness base material powder for decorative materials, which comprises the following steps:

[0098] Step (1): the epoxy-modified polyurethane dispersant is dissolved in distilled water, and after stirring at 1200rpm for 3h, a dispersant emulsion is obtained, then the white cement clinker, the quartz stone, the gypsum, the fly ash and the nano titanium dioxide are added into the dispersant emulsion for stirring, and a base material system is obtained;

[0099] Step (2): the rare earth doped alumina, the activator and the retarder are sequentially added into the base material system, 1.0mm zirconium beads are added, high-speed ball milling is carried out at 5000rpm for 10h, and drying is carried out at 100℃ for 5h, and the high-whiteness base material powder for decorative materials is obtained.

[0100] Embodiment 7

[0101] The embodiment discloses a preparation method of rare earth doped alumina, which comprises the following steps:

[0102] P1: after 1g of aluminum sheet with a purity of 99.99% is ultrasonically cleaned, the aluminum sheet is placed in a beaker containing 7.36mL of isopropyl alcohol, potassium permanganate is added, and the reaction is heated by using an electric heating mantle, the reaction is carried out at 80℃ for 4h, and after the reaction is completed, distillation is carried out, and aluminum isopropoxide is obtained;

[0103] P2: 0.97 mL of aluminum isopropoxide was slowly added to a solution of 1.21 mL of acetylacetone in isopropyl alcohol, stirred for 1.5 h, aged for 1 h, a mixed solution of 1.063 mL of aluminum isopropoxide and 0.106 mL of distilled water was added, after stirring at 32℃ for 4 h, nitric acid was added, and an alumina sol was obtained after adjusting the pH to 3.0;

[0104] P3: 0.113 g of cerium nitrate was dissolved in 6.8 mL of distilled water and added to 102 g of alumina sol, stirred for 16 h, dried at 110℃ for 8 h, heated to 800℃ at a heating rate of 4℃ / min, held for 2 h, cooled, and ground to obtain a rare earth-doped alumina.

[0105] The present embodiment discloses a preparation method of an epoxy-modified polyurethane dispersant, comprising the following steps:

[0106] S1: 1 g of diphenylmethane diisocyanate was added to a three-necked flask containing tetrahydrofuran, followed by adding 0.82 g of polyethylene glycol with a relative molecular mass of 600, and heated to react at 80℃ for 2 h;

[0107] S2: 1.7 g of 2,2-dimethylol propionic acid was added to a three-necked flask, heated to perform chain extension reaction, reacted at 80℃ for 3 h, and dibutyltin dilaurate was added during the reaction, 1.4 g of 1,3-propanediol was dissolved in tetrahydrofuran and added dropwise to the three-necked flask to perform branching reaction for 4 h;

[0108] S3: After the branching reaction was completed, the three-necked flask was cooled to 60℃, 1-(3-aminopropyl) morpholine was added, and reacted for 2 h, followed by adding epoxypropanol to react at 65℃ for 2 h to obtain an epoxy-modified polyurethane dispersant.

[0109] The present embodiment discloses a high-whiteness base material powder for decorative materials, which is composed of the following ingredients by weight: 58 parts of white cement clinker, 30 parts of quartz stone, 2.7 parts of gypsum, 3 parts of fly ash, 1.8 parts of rare earth-doped alumina, 0.6 parts of epoxy-modified polyurethane dispersant, 3 parts of nano-titanium dioxide, 0.45 parts of activator, and 0.25 parts of retarder.

[0110] The present embodiment discloses a preparation method of a high-whiteness base material powder for decorative materials, comprising the following steps:

[0111] Step (1): The epoxy-modified polyurethane dispersant was dissolved in distilled water, and an emulsion of the dispersant was obtained after stirring at 1200 rpm for 3 h, followed by adding white cement clinker, quartz stone, gypsum, fly ash, and nano-titanium dioxide to the dispersant emulsion to perform stirring, and a base material system was obtained;

[0112] Step (2): The rare earth doped alumina, the active agent and the retarder were sequentially added into the substrate system, 1.0 mm zirconium beads were added, high-speed ball milling was carried out at 5000 rpm for 10 h, and drying was carried out at 100 DEG C for 5 h to obtain the high-whiteness substrate powder for decorative materials.

[0113] Comparative Example 1

[0114] Comparative Example 1 is compared with Example 1. In the process of preparing the rare earth doped alumina, no cerium nitrate is added in Comparative Example 1, and other conditions are unchanged.

[0115] Comparative Example 2

[0116] Comparative Example 2 is compared with Example 1. In the process of preparing the epoxy modified polyurethane dispersant, no 1,3-propanediol is added in Comparative Example 2, and other conditions are unchanged.

[0117] Experimental Example

[0118] The properties of the high-whiteness substrate powder for decorative materials prepared in Examples 2-7 and Comparative Examples 1-2 were tested.

[0119] I. Mechanical property test

[0120] After the sample was dissolved in water, a uniform particle-free paste was obtained by stirring, and the paste was uniformly brushed on a clean, dry and oil-free flat wall surface with a brush. After brushing, the substrate powder was naturally dried. The abrasion resistance of the sample was measured according to the standard ASTM D1044-18, the hardness of the sample was tested by using a Berkovich indenter, and the indentation resistance was calculated according to H = 100 / L, wherein H represents the indentation resistance, and L represents the indentation length (mm). The test results are shown in Table 1:

[0121] Table 1

[0122]

[0123]

[0124] It can be seen from the test results in Table 1 that the high-whiteness substrate powder prepared in Examples 2-7 has excellent mechanical properties, excellent abrasion resistance and hardness. It can be seen from the comparison between Comparative Example 1 and Examples 2-7 that the addition of cerium nitrate can effectively improve the abrasion resistance and hardness of the high-whiteness substrate powder.

[0125] II. Dispersion test

[0126] 100 g of the sample was accurately weighed, passed through a glass funnel with an outer diameter of 1 cm, and slowly added to a beaker containing 2 L of 40 DEG C distilled water. The time (s) for the sample to completely disperse in the water was recorded under the stirring speed of 40 rpm. The test results are shown in Table 2:

[0127] Table 2

[0128]

[0129] From the test results of Table 2, it can be seen that the high-whiteness base material powder prepared in Examples 2-7 has excellent dispersing performance. From the comparison between Comparative Example 2 and Examples 2-7, it can be seen that the addition of 1,3-propanediol can improve the dispersing performance of the high-whiteness base material powder.

[0130] The above description is merely preferred embodiments of the present application. The present application is not limited to the above-described embodiments, and any modifications and changes within the scope of the present application disclosed in the specification and the claims, and the equivalent thereof, should be encompassed in the scope of the present application.

[0131] The preferred embodiments of the present application disclosed above are only used to help explain the present application. The preferred embodiments do not describe all the details and limit the present application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present specification. The present specification selects and describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is limited only by the claims and the entire scope and equivalents thereof.

Claims

1. A high whiteness base material powder for decorative materials, characterized in that: The invention is composed of the following ingredients in parts by weight: 53-60 parts of white cement clinker, 26-33 parts of quartz stone, 1.5-3 parts of gypsum, 2-5 parts of fly ash, 1-2 parts of rare earth-doped alumina, 0.5-1 part of epoxy modified polyurethane dispersant, 1-3 parts of nano titanium dioxide, 0.3-0.7 part of active agent, and 0.2-0.5 part of retarder; The preparation method of the epoxy-modified polyurethane dispersant comprises the following steps: S1: Add diphenylmethane diisocyanate to a three-necked flask containing tetrahydrofuran, then add polyethylene glycol and heat to react; S2: 2,2-dihydroxymethylpropionic acid is added to a three-necked flask and heated to perform a chain extension reaction. During the reaction, dibutyltin dilaurate is added. 1,3-propylene glycol is dissolved in tetrahydrofuran and then added dropwise to the three-necked flask to perform a branching reaction. S3: After the branching reaction is completed, the three-necked flask is cooled, 1-(3-aminopropyl)morpholine is added and reacted, and then glycidol is added and reacted to obtain an epoxy-modified polyurethane dispersant.

2. The high-whiteness base material powder for decorative materials according to claim 1, characterized in that: The preparation method of the rare earth-doped alumina comprises the following steps: P1: After ultrasonic cleaning, place the aluminum sheet in a beaker filled with isopropyl alcohol, add potassium permanganate, and heat with an electric heating mantle. After the reaction is complete, distill to obtain aluminum isopropyl alcohol; P2: Slowly add aluminum isopropoxide to an isopropanol solution containing acetylacetone, stir, age, add a mixed solution of aluminum isopropoxide and distilled water, stir vigorously, add nitric acid, and adjust the pH to obtain an alumina sol; P3: Dissolve cerium nitrate in distilled water and add it to alumina sol, stir, dry, heat, keep warm, cool, and grind to obtain rare earth-doped alumina.

3. The high-whiteness base material powder for decorative materials according to claim 2, characterized in that: In the P1, the purity of the aluminum flakes is 99.99%, the molar ratio of the aluminum flakes to isopropyl alcohol is 1:(2-3), the heating reaction temperature is 60-80° C., and the reaction time is 4-6 hours.

4. The high-whiteness base material powder for decorative materials according to claim 2, characterized in that: In the P2, the molar ratio of aluminum isopropoxide to acetylacetone is 1:(2-2.5), the stirring time is 1-2 hours, the aging time is 1-2 hours, the molar ratio of aluminum isopropoxide to distilled water is 1:(0.8-0.9), the strong stirring temperature is 28-32°C, the stirring time is 3-5 hours, and the pH is adjusted to 3.

0.

5. The high-whiteness base material powder for decorative materials according to claim 2, characterized in that: In the P3, the molar ratio of cerium nitrate, distilled water and alumina sol is (0.001-0.05): (0.2-0.4): 1, the stirring time is 14-16 hours, the drying temperature is 100-110°C, the drying time is 8-10 hours, the heating rate is 4°C / min, the heating temperature is 800-1000°C, and the holding time is 1-2 hours.

6. The high-whiteness base material powder for decorative materials according to claim 1, characterized in that: In S1, the relative molecular mass of polyethylene glycol is 600, the molar ratio of diphenylmethane diisocyanate to polyethylene glycol is 3:(0.8-1.2), the heating temperature is 70-80°C, and the reaction time is 2-3 hours; in S2, the molar ratio of 2,2-dihydroxymethylpropionic acid to 1,3-propylene glycol is (2-3):(4-6), the chain extension reaction temperature is 80-90°C, the reaction time is 2-3 hours, and the branching reaction time is 4-5 hours; in S3, the temperature is cooled to 55-60°C, the reaction time is 1-2 hours, the temperature of adding glycidol for reaction is 60-65°C, and the reaction time is 2-3 hours.

7. The method for preparing a high-whiteness base material powder for decorative materials according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step (1): dissolving an epoxy-modified polyurethane dispersant in distilled water and stirring the mixture to obtain a dispersant emulsion; then adding white cement clinker, quartz stone, gypsum, fly ash and nano-titanium dioxide to the dispersant emulsion and stirring the mixture to obtain a substrate system; Step (2): rare earth-doped alumina, an active agent and a retarder are sequentially added to the substrate system, zirconium beads are added, high-speed ball milling is performed, and drying is performed to obtain a high-whiteness substrate powder for decorative materials.

8. The method for preparing high-whiteness base material powder for decorative materials according to claim 7, characterized in that: In the step (1), the stirring speed is 1000-1200 rpm, and the stirring time is 2-3 h.

9. The method for preparing high-whiteness base material powder for decorative materials according to claim 7, characterized in that: In the step (2), the particle size of the zirconium beads is 0.8-1.0 mm, the ball milling speed is 4000-5000 rpm, the ball milling time is 6-10 h, the drying temperature is 80-100° C., and the drying time is 3-5 h.

Images