High-temperature resistant ceramic tile for building and preparation method thereof

Abstract

The present invention discloses a high-temperature resistant building ceramic tile and a preparation method thereof, and relates to the field of ceramic technology. When preparing high-temperature resistant building ceramic tiles, the present invention first reacts vinyl-terminated amino silicone oil and 2-amino-4-pyridinemethyl mercaptan, and then reacts with 2-(diphenylphosphine)benzaldehyde to obtain modified polysiloxane; secondly, clay and a mixed iron salt solution are mixed, and coprecipitated under the action of sodium hydroxide to obtain modified clay; finally, modified clay, magnesium trisilicate, titanium carbide, zirconium diboride, aluminum oxide, and boron nitride are mixed and ground, pressed into a blank, dried and sintered, and then sprayed with modified polysiloxane to obtain the high-temperature resistant building ceramic tile. The high-temperature resistant building ceramic tile prepared by the present invention has good high-temperature resistance and self-cleaning performance.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramics, in particular to a high-temperature resistant ceramic tile for construction and a preparation method thereof. Background Art

[0002] Ceramic tiles are a new type of roofing material, widely used on the roofs and walls of residential buildings such as homes, villas, and apartments, as well as industrial buildings such as factories, warehouses, and workshops. However, existing ceramic tiles still have some shortcomings. For example, their high-temperature resistance may not be optimal. In rainy and dusty environments, ceramic tiles need to have self-cleaning capabilities to maintain the building's aesthetics and extend its service life. Summary of the Invention

[0003] The object of the present invention is to provide a high-temperature resistant ceramic tile for construction and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] The invention discloses a high-temperature resistant ceramic tile for construction. The high-temperature resistant ceramic tile for construction is obtained by mixing and grinding modified clay, magnesium trisilicate, titanium carbide, zirconium diboride, aluminum oxide and boron nitride, pressing them into blanks, drying and sintering them, and then spraying them with modified polysiloxane.

[0006] Preferably, the modified polysiloxane is obtained by reacting vinyl-terminated amino silicone oil with 2-amino-4-pyridylmethyl mercaptan, and then reacting with 2-(diphenylphosphine)benzaldehyde.

[0007] A method for preparing high-temperature resistant ceramic tiles for construction, comprising the following steps:

[0008] (1) Octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane are mixed in a mass ratio of 4:1, heated to 80°C, 0.02-0.03 times the mass of octamethylcyclotetrasiloxane in a 25 wt% tetramethylammonium hydroxide aqueous solution is added, the temperature is then raised to 100°C, 0.01-0.02 times the mass of octamethylcyclotetrasiloxane in 1,3-bis(aminopropyl)tetramethyldisiloxane is added, the temperature is then raised to 115°C, the reaction is continued for 6 hours, the temperature is further raised to 140°C, the reaction is continued for 40 minutes, and the temperature is then lowered to 135°C and distilled under reduced pressure to obtain vinyl-terminated amino silicone oil;

[0009] (2) vinyl-terminated amino silicone oil, 2-amino-4-pyridylmethyl mercaptan, azobisisobutyronitrile and anhydrous toluene are mixed in a mass ratio of 1: (4.1-4.2): (0.1-0.3): (10-12), and the mixture is heated to 100° C. in a sealed, anhydrous and oxygen-free environment under an argon atmosphere, and reacted for 2 h. After cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution 4-5 times the volume of anhydrous toluene is added, and extracted with ethyl acetate. The organic phase is washed 3-4 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed with pure water 3-4 times. Finally, the pre-modified polysiloxane is obtained by rotary evaporation at 80° C. for 5-10 min.

[0010] (3) Weigh pre-modified polysiloxane and 2-(diphenylphosphino)benzaldehyde in a mass ratio of 1:(3-3.5), mix the pre-modified polysiloxane, potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:(3-3.5):20, heat to 90-100°C and stir for 3-4 hours to obtain a pre-modified polysiloxane solution, and mix 2-(diphenylphosphino)benzaldehyde and N,N-dimethylformamide in a mass ratio of 1:20 to obtain 2-(diphenylphosphino)benzaldehyde. solution, adding the 2-(diphenylphosphine)benzaldehyde solution dropwise to the pre-modified polysiloxane solution at a dropping rate of 1 mL / min, continuing to react at 90-100° C. for 3-4 hours, cooling to room temperature, adding pure water 10-12 times the mass of the pre-modified polysiloxane, cooling to 0° C. and standing for 2-3 hours, adding acetone 3-4 times the mass of the pre-modified polysiloxane solution, filtering and drying at 50-60° C. for 12 hours to obtain modified polysiloxane;

[0011] (4) Clay and pure water were mixed in a mass ratio of 3:10 to obtain a clay dispersion, the mixed iron salt solution and the clay dispersion were mixed in a mass ratio of 1:(2-3) for 5-10 minutes, 10M sodium hydroxide solution (3-4 times the mass of the mixed iron salt solution) was added, and the mixture was stirred at a speed of 100-200 r / min for 60 minutes to prepare raw material balls with a particle size of 5 mm, and the raw material balls were dried at 267 Pa and 90° C. for 12 hours to obtain modified clay;

[0012] (5) Weigh the following raw materials by mass: 28-33 parts of modified clay, 7-11 parts of magnesium trisilicate, 9-14 parts of titanium carbide, 11-15 parts of zirconium diboride, 3-5 parts of aluminum oxide, and 3-4 parts of boron nitride; mix the above raw materials and grind them in a ball mill to obtain powder. The ball mill speed is 200 rpm / min and the grinding time is 6 hours. Pour the powder into a mold and use a press to form a blank. The press pressure is 50 tons. Place the blank in a dryer at a temperature of 280°C for drying. After drying, sinter it in a high-temperature furnace to obtain a ceramic tile precursor; spray the modified polysiloxane on the surface of the ceramic tile precursor and dry it naturally to obtain a high-temperature resistant ceramic tile for construction.

[0013] Preferably, the preparation method of the mixed iron salt solution in step (1) is: stirring and mixing ferric chloride hexahydrate, ferric chloride tetrahydrate and pure water in a mass ratio of 1:0.37:10 for 10 minutes to obtain a mixed iron salt solution.

[0014] Preferably, the clay particle size in step (4) is 500-700 mesh.

[0015] Preferably, the sintering process parameters in step (5) are as follows: heating to 700-760°C at a rate of 6-10°C / min and keeping it for 3-5 hours, then heating to 1180-1210°C at a rate of 11-13°C / min and keeping it for 2-3 hours, then heating to 1740-1780°C at a rate of 6-8°C / min and keeping it for 1-3 hours, then cooling to 900-930°C and keeping it for 2-3 hours.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] When preparing high-temperature resistant ceramic tiles for construction, the present invention comprises the following steps: first, reacting vinyl-terminated amino silicone oil with 2-amino-4-pyridylmethyl mercaptan, and then reacting with 2-(diphenylphosphine)benzaldehyde to obtain modified polysiloxane; second, mixing clay and a mixed iron salt solution, and coprecipitating under the action of sodium hydroxide to obtain modified clay; finally, mixing and grinding the modified clay, magnesium trisilicate, titanium carbide, zirconium diboride, aluminum oxide, and boron nitride, pressing the mixture into a blank, drying and sintering the blank, and then spraying the blank with the modified polysiloxane to obtain the high-temperature resistant ceramic tiles for construction.

[0018] First, vinyl-terminated amino silicone oil is reacted with the thiol on 2-amino-4-pyridylmethylthiol through a click reaction between the thiol and double bond to graft aminopyridine, and aminopyridine is reacted with 2-(diphenylphosphine)benzaldehyde through a Schiff base reaction between the amino group to obtain a phosphorus-containing ligand; secondly, clay and a mixed iron salt solution are mixed and co-precipitated under the action of sodium hydroxide. In the subsequent high-temperature calcination process to prepare ceramic tiles, magnetic iron oxide particles can be generated; finally, modified clay, magnesium trisilicate, titanium carbide, zirconium diboride, aluminum oxide, and boron nitride are mixed and ground, pressed into a blank, dried and sintered, and then modified. High-temperature resistant ceramic tiles for construction obtained by spraying polysiloxane; magnesium trisilicate, titanium carbide, zirconium diboride, aluminum oxide, and boron nitride can greatly improve the high-temperature resistance of ceramic tiles. The spraying of modified polysiloxane modifies the surface of the ceramic tiles with a hydrophobic layer, which can provide the ceramic tiles with good hydrophobic and self-cleaning properties. The iron particles contained in the modified clay and other components containing metal elements in the ceramic tiles can form metal ligands with the phosphorus-containing ligands in the modified polysiloxane on the surface, thereby giving the ceramic tiles photocatalytic degradation properties, which can degrade some small molecular organic matter, thereby further improving the self-cleaning ability of the ceramic tiles. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0020] The mixed iron salt solution used in the following examples and comparative examples was prepared by stirring and mixing ferric chloride hexahydrate, ferric chloride tetrahydrate, and pure water in a mass ratio of 1:0.37:10 for 10 minutes to obtain a mixed iron salt solution; the clay particle size used was 500-700 mesh.

[0021] Example 1:

[0022] A method for preparing high-temperature resistant ceramic tiles for construction, comprising the following steps:

[0023] (1) Octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane were mixed in a mass ratio of 4:1, heated to 80°C, 0.02 times the mass of octamethylcyclotetrasiloxane was added with a 25 wt% tetramethylammonium hydroxide aqueous solution, then heated to 100°C, 0.01 times the mass of octamethylcyclotetrasiloxane was added with 1,3-bis(aminopropyl)tetramethyldisiloxane, then heated to 115°C, reacted for 6 hours, continued to heat to 140°C, reacted for 40 minutes, then cooled to 135°C and distilled under reduced pressure to obtain vinyl-terminated amino silicone oil;

[0024] (2) vinyl-terminated amino silicone oil, 2-amino-4-pyridinemethyl mercaptan, azobisisobutyronitrile and anhydrous toluene were mixed in a mass ratio of 1:4.1):0.1:10, and the mixture was heated to 100°C in an anhydrous and oxygen-free environment under an argon atmosphere, and reacted for 2 hours. After cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution with a volume of 4 times that of anhydrous toluene was added, and extracted with ethyl acetate. The organic phase was washed 4 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed 4 times with pure water. Finally, the pre-modified polysiloxane was obtained by rotary evaporation at 80°C for 10 minutes.

[0025] (3) Weigh pre-modified polysiloxane and 2-(diphenylphosphine)benzaldehyde in a mass ratio of 1:3, mix pre-modified polysiloxane, potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:3:20, heat to 100°C and stir for 4 hours to obtain a pre-modified polysiloxane solution, mix 2-(diphenylphosphine)benzaldehyde and N,N-dimethylformamide in a mass ratio of 1:20 to obtain a 2-(diphenylphosphine)benzaldehyde solution, add the 2-(diphenylphosphine)benzaldehyde solution dropwise to the pre-modified polysiloxane solution at a dropping rate of 1 mL / min, continue to react at 100°C for 4 hours after the addition is completed, cool to room temperature, add pure water 10 times the mass of the pre-modified polysiloxane, cool to 0°C and let stand for 3 hours, add acetone 3 times the mass of the pre-modified polysiloxane solution, filter and dry at 60°C for 12 hours to obtain modified polysiloxane;

[0026] (4) Clay and pure water were mixed in a mass ratio of 3:10 to obtain a clay dispersion, the mixed iron salt solution and the clay dispersion were mixed in a mass ratio of 1:2 for 7 minutes, 10M sodium hydroxide solution (3 times the mass of the mixed iron salt solution) was added, and the mixture was stirred at a speed of 200 r / min for 60 minutes to prepare raw material balls with a particle size of 5 mm. The raw material balls were dried at 267 Pa and 90° C. for 12 hours to obtain modified clay;

[0027] (5) Weigh the following raw materials by mass: 28 parts of modified clay, 7 parts of magnesium trisilicate, 9 parts of titanium carbide, 11 parts of zirconium diboride, 3 parts of aluminum oxide, and 3 parts of boron nitride; mix the above raw materials and grind them in a ball mill to obtain powder. The ball mill speed is 200 rpm / min and the grinding time is 6 hours. Pour the powder into a mold and use a press to form a blank. The press pressure is 50 tons. Place the blank in a dryer at a temperature of 280°C for drying. After drying, place it in a high-temperature furnace. The sintering process parameters are: heating to 760°C at a rate of 10°C / min and keeping for 5 hours, then heating to 1210°C at a rate of 13°C / min and keeping for 3 hours, then heating to 1780°C at a rate of 8°C / min and keeping for 3 hours, then cooling to 930°C and keeping for 3 hours to obtain a ceramic tile precursor; spraying modified polysiloxane on the surface of the ceramic tile precursor, and naturally drying to obtain high-temperature resistant ceramic tiles for construction.

[0028] Example 2:

[0029] A method for preparing high-temperature resistant ceramic tiles for construction, comprising the following steps:

[0030] (1) Octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane were mixed in a mass ratio of 4:1, heated to 80°C, 0.025 times the mass of octamethylcyclotetrasiloxane was added with a 25 wt% tetramethylammonium hydroxide aqueous solution, then heated to 100°C, 0.015 times the mass of octamethylcyclotetrasiloxane was added with 1,3-bis(aminopropyl)tetramethyldisiloxane, then heated to 115°C, reacted for 6 hours, continued to heat to 140°C, reacted for 40 minutes, then cooled to 135°C and distilled under reduced pressure to obtain vinyl-terminated amino silicone oil;

[0031] (2) Vinyl-terminated amino silicone oil, 2-amino-4-pyridylmethyl mercaptan, azobisisobutyronitrile and anhydrous toluene were mixed in a mass ratio of 1:4.15:0.2:11, and the mixture was heated to 100°C in an anhydrous and oxygen-free environment under an argon atmosphere. The mixture was reacted for 2 hours, and after cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution with a volume 4.5 times that of anhydrous toluene was added, and the mixture was extracted with ethyl acetate. The organic phase was washed 3 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed 3 times with pure water. Finally, the mixture was rotary evaporated at 80°C for 7 minutes to obtain a pre-modified polysiloxane.

[0032] (3) Weigh pre-modified polysiloxane and 2-(diphenylphosphino)benzaldehyde in a mass ratio of 1:3.2, mix pre-modified polysiloxane, potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:3.2:20, heat to 95°C and stir for 3.5h to obtain a pre-modified polysiloxane solution, mix 2-(diphenylphosphino)benzaldehyde and N,N-dimethylformamide in a mass ratio of 1:20 to obtain a 2-(diphenylphosphino)benzaldehyde solution. liquid, adding the 2-(diphenylphosphine)benzaldehyde solution dropwise to the pre-modified polysiloxane solution at a dropping rate of 1 mL / min, continuing to react at 95°C for 3.5 hours, cooling to room temperature, adding pure water 11 times the mass of the pre-modified polysiloxane, cooling to 0°C and standing for 2.5 hours, adding acetone 3.5 times the mass of the pre-modified polysiloxane solution, filtering and drying at 55°C for 12 hours to obtain modified polysiloxane;

[0033] (4) Clay and pure water were mixed in a mass ratio of 3:10 to obtain a clay dispersion, a mixed iron salt solution and a clay dispersion were mixed in a mass ratio of 1:2.5 for 7 minutes, a 10M sodium hydroxide solution (3.5 times the mass of the mixed iron salt solution) was added, and the mixture was stirred at a speed of 150 r / min for 60 minutes to prepare raw material balls with a particle size of 5 mm. The raw material balls were dried at 267 Pa and 90° C. for 12 hours to obtain modified clay;

[0034] (5) Weigh the following raw materials by mass: 30 parts of modified clay, 10 parts of magnesium trisilicate, 12 parts of titanium carbide, 13 parts of zirconium diboride, 4 parts of aluminum oxide, and 3.5 parts of boron nitride; mix the above raw materials and grind them in a ball mill to obtain powder. The ball mill speed is 200 rpm / min and the grinding time is 6 hours. Pour the powder into a mold and use a press to form a blank. The press pressure is 50 tons. Place the blank in a dryer at a temperature of 280°C for drying. After drying, place it in a high-temperature furnace. The sintering process parameters are: heating to 720°C at a rate of 7°C / min and keeping for 4 hours, then heating to 1190°C at a rate of 12°C / min and keeping for 2.5 hours, then heating to 1750°C at a rate of 7°C / min and keeping for 2 hours, then cooling to 925°C and keeping for 2.5 hours; obtaining a ceramic tile precursor; spraying modified polysiloxane on the surface of the ceramic tile precursor, and naturally drying to obtain high-temperature resistant ceramic tiles for construction.

[0035] Example 3:

[0036] A method for preparing high-temperature resistant ceramic tiles for construction, comprising the following steps:

[0037] (1) Octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane were mixed in a mass ratio of 4:1, heated to 80°C, 0.03 times the mass of octamethylcyclotetrasiloxane was added with a 25 wt% tetramethylammonium hydroxide aqueous solution, then heated to 100°C, 0.02 times the mass of octamethylcyclotetrasiloxane was added with 1,3-bis(aminopropyl)tetramethyldisiloxane, then heated to 115°C, reacted for 6 hours, continued to heat to 140°C, reacted for 40 minutes, then cooled to 135°C and distilled under reduced pressure to obtain vinyl-terminated amino silicone oil;

[0038] (2) Vinyl-terminated amino silicone oil, 2-amino-4-pyridinemethyl mercaptan, azobisisobutyronitrile and anhydrous toluene were mixed in a mass ratio of 1:4.2:0.3:12, and the mixture was heated to 100°C in an anhydrous and oxygen-free environment under an argon atmosphere. The mixture was reacted for 2 hours, and after cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution with a volume 5 times that of anhydrous toluene was added, and the mixture was extracted with ethyl acetate. The organic phase was washed 3 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed 3 times with pure water. Finally, the mixture was rotary evaporated at 80°C for 5 minutes to obtain a pre-modified polysiloxane.

[0039] (3) Weigh pre-modified polysiloxane and 2-(diphenylphosphine)benzaldehyde in a mass ratio of 1:3.5, mix pre-modified polysiloxane, potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:3.5:20, heat to 90°C and stir for 3 hours to obtain a pre-modified polysiloxane solution, mix 2-(diphenylphosphine)benzaldehyde and N,N-dimethylformamide in a mass ratio of 1:20 to obtain a 2-(diphenylphosphine)benzaldehyde solution, add the 2-(diphenylphosphine)benzaldehyde solution dropwise to the pre-modified polysiloxane solution at a dropping rate of 1 mL / min, continue to react at 900°C for 3 hours after the addition is completed, cool to room temperature, add pure water 12 times the mass of the pre-modified polysiloxane, cool to 0°C and let stand for 2 hours, add acetone 4 times the mass of the pre-modified polysiloxane solution, filter and dry at 60°C for 12 hours to obtain modified polysiloxane;

[0040] (4) Clay and pure water were mixed in a mass ratio of 3:10 to obtain a clay dispersion, the mixed iron salt solution and the clay dispersion were mixed in a mass ratio of 1:3 for 5 minutes, 10M sodium hydroxide solution with a mass of 4 times that of the mixed iron salt solution was added, and the mixture was stirred at a speed of 100 r / min for 60 minutes to prepare raw material balls with a particle size of 5 mm. The raw material balls were dried at 267 Pa and 90° C. for 12 hours to obtain modified clay;

[0041] (5) Weigh the following raw materials by mass: 33 parts of modified clay, 11 parts of magnesium trisilicate, 14 parts of titanium carbide, 15 parts of zirconium diboride, 5 parts of aluminum oxide, and 4 parts of boron nitride; mix the above raw materials and grind them in a ball mill to obtain powder. The ball mill speed is 200 rpm / min and the grinding time is 6 hours. Pour the powder into a mold and use a press to form a blank. The press pressure is 50 tons. The blank is placed in a dryer at a temperature of 280°C for drying. It is then sintered in a high-temperature furnace, and the sintering process parameters are: heating to 700°C at a rate of 6°C / min and maintaining for 3 hours, then heating to 1180°C at a rate of 11°C / min and maintaining for 3 hours, then heating to 1740°C at a rate of 6°C / min and maintaining for 1 hour, then cooling to 900°C and maintaining for 2 hours to obtain a ceramic tile precursor; the modified polysiloxane is sprayed on the surface of the ceramic tile precursor, and naturally dried to obtain high-temperature resistant ceramic tiles for construction.

[0042] Comparative Example 1:

[0043] The difference between the preparation method of high-temperature resistant building ceramic tiles in Comparative Example 1 and Example 2 is that step (5) is modified as follows: the following raw materials are weighed in parts by mass: 30 parts of modified clay, 10 parts of magnesium trisilicate, 12 parts of titanium carbide, 13 parts of zirconium diboride, 4 parts of aluminum oxide, and 3.5 parts of boron nitride; the above raw materials are mixed and ground in a ball mill to obtain a powder, the ball mill speed is 200 rpm / min, the grinding time is 6 hours, the powder is poured into a mold and a blank is formed by a press, and the press is pressed. The machine pressure is 50 tons, the blank is placed in a dryer at a temperature of 280°C for drying, and then sintered in a high-temperature furnace. The sintering process parameters are: the sintering process parameters are: heating to 720°C at a rate of 7°C / minute and maintaining for 3 hours, then heating to 1190°C at a rate of 12°C / minute and maintaining for 2 hours, then heating to 1750°C at a rate of 7°C / minute and maintaining for 2 hours, then cooling to 925°C and maintaining for 2.5 hours; high-temperature resistant ceramic tiles for construction are obtained.

[0044] Comparative Example 2:

[0045] The difference between the preparation method of high-temperature resistant building ceramic tiles in Comparative Example 2 and Example 2 is that step (5) is modified as follows: weigh the following raw materials by mass: 30 parts of modified clay; mix the above raw materials and grind them in a ball mill to obtain powder, the ball mill speed is 200 rpm / min, the grinding time is 6 hours, the powder is poured into a mold and a press is used to form a blank, the press pressure is 50 tons, the blank is placed in a dryer at a temperature of 280°C for drying, and after drying, it is placed in a high temperature dryer. The sintering is carried out in a furnace, and the sintering process parameters are: the sintering process parameters are: heating to 720°C at a rate of 7°C / min and keeping for 3 hours, then heating to 1190°C at a rate of 12°C / min and keeping for 2 hours, then heating to 1750°C at a rate of 7°C / min and keeping for 2 hours, then cooling to 925°C and keeping for 2.5 hours; obtaining a ceramic tile precursor; spraying modified polysiloxane on the surface of the ceramic tile precursor, and naturally drying to obtain high-temperature resistant ceramic tiles for construction.

[0046] Tests of high temperature resistance and self-cleaning performance:

[0047] High temperature resistance test:

[0048] Test Method: Fracture toughness testing was conducted on ceramic tiles produced in Examples and Comparative Examples using a C45.105 testing machine in accordance with GB / T 23806-2009. The tile specimens measured 36 mm x 4 mm x 3 mm. After being held at 1520°C for 22 hours, the fracture toughness was retested, and the fracture toughness retention was calculated. The results are shown in Table 1.

[0049] Self-cleaning performance test:

[0050] Test method: The water drop contact angle was measured using an XG-CAM contact angle meter. The results are shown in Table 1.

[0051] Table 1 Test results of high temperature resistance and self-cleaning performance

[0052] Fracture toughness retention rate (%) Contact angle (°) Example 1 96.43 Example 1 154 Example 2 96.86 Example 2 155 Example 3 97.31 Example 3 155 Comparative Example 1 57.43 Comparative Example 1 85 Comparative Example 2 52.26 Comparative Example 2 150

[0053] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the high-temperature resistant ceramic tiles for construction prepared by the present invention have good high-temperature resistance and self-cleaning properties.

[0054] By comparison, the fracture toughness retention rates of Examples 1 to 3 are greater than those of Comparative Examples 1 to 2, and the contact angles of Examples 1 to 3 are greater than the contact angle of Comparative Example 1. The above test results are explained as follows: First, the vinyl-terminated amino silicone oil is subjected to a click reaction between the thiol group and the double bond and the thiol group on 2-amino-4-pyridine methyl mercaptan to be grafted with aminopyridine, and aminopyridine is subjected to a Schiff base reaction between the amino group and 2-(diphenylphosphine)benzaldehyde to obtain a phosphorus-containing ligand; secondly, clay and a mixed iron salt solution are mixed and co-precipitated under the action of sodium hydroxide, and magnetic ferrosoferric oxide particles can be generated in the subsequent high-temperature calcination process to prepare ceramic tiles; finally, the modified clay, magnesium trisilicate, and carbonized Titanium, zirconium diboride, aluminum oxide, and boron nitride are mixed and ground, pressed into blanks, dried and sintered, and then sprayed with modified polysiloxane to obtain high-temperature resistant building ceramic tiles; magnesium trisilicate, titanium carbide, zirconium diboride, aluminum oxide, and boron nitride can greatly improve the high-temperature resistance of ceramic tiles. The spraying of modified polysiloxane modifies the surface of the ceramic tiles with a hydrophobic layer, which can provide the ceramic tiles with good hydrophobic and self-cleaning properties. The iron particles contained in the modified clay and other components containing metal elements in the ceramic tiles can form metal ligands with the phosphorus-containing ligands in the modified polysiloxane on the surface, thereby giving the ceramic tiles photocatalytic degradation properties, which can degrade some small molecular organic matter, thereby further improving the self-cleaning ability of the ceramic tiles.

[0055] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A method for preparing high temperature resistant ceramic tiles for construction, characterized in that: The method comprises the following preparation steps: (1) Octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane were mixed in a mass ratio of 4:1, heated to 80°C, 25wt% tetramethylammonium hydroxide aqueous solution with a mass of 0.02-0.03 times of octamethylcyclotetrasiloxane was added, then heated to 100°C, 1,3-bis(aminopropyl)tetramethyldisiloxane with a mass of 0.01-0.02 times of octamethylcyclotetrasiloxane was added, then heated to 115°C, reacted for 6h, then heated to 140°C, reacted for 40min, then cooled to 135°C and distilled under reduced pressure to obtain vinyl-terminated amino silicone oil; (2) Vinyl-terminated amino silicone oil, 2-amino-4-pyridinemethyl mercaptan, azobisisobutyronitrile and anhydrous toluene are mixed in a mass ratio of 1: (4.1-4.2): (0.1-0.3): (10-12), and the mixture is heated to 100 ° C in an anhydrous and oxygen-free environment under argon atmosphere. The mixture is reacted for 2 hours, cooled to room temperature, and a 1 mol / L sodium bicarbonate aqueous solution 4-5 times the volume of anhydrous toluene is added. The mixture is extracted with ethyl acetate, and the organic phase is washed 3-4 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed with pure water 3-4 times. Finally, the pre-modified polysiloxane is obtained by rotary evaporation at 80 ° C for 5-10 minutes. (3) Weigh pre-modified polysiloxane and 2-(diphenylphosphino)benzaldehyde in a mass ratio of 1:(3-3.5), mix pre-modified polysiloxane, potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:(3-3.5):20, heat to 90-100 °C and stir for 3-4 hours to obtain pre-modified polysiloxane solution, mix 2-(diphenylphosphino)benzaldehyde and N,N-dimethylformamide in a mass ratio of 1:20 to obtain 2-(diphenylphosphino)benzaldehyde solution, adding the 2-(diphenylphosphine)benzaldehyde solution dropwise to the pre-modified polysiloxane solution at a dropping rate of 1 mL / min, continuing to react at 90-100° C. for 3-4 hours, cooling to room temperature, adding pure water 10-12 times the mass of the pre-modified polysiloxane, cooling to 0° C. and standing for 2-3 hours, adding acetone 3-4 times the mass of the pre-modified polysiloxane solution, filtering and drying at 50-60° C. for 12 hours to obtain modified polysiloxane; (4) Clay and pure water were mixed in a mass ratio of 3:10 to obtain a clay dispersion, the mixed iron salt solution and the clay dispersion were mixed in a mass ratio of 1:(2-3) for 5-10 minutes, 10M sodium hydroxide solution of 3-4 times the mass of the mixed iron salt solution was added, and the mixture was stirred at a speed of 100-200 r / min for 60 minutes to prepare raw material balls with a particle size of 5 mm. The raw material balls were dried at 267 Pa and 90°C for 12 hours to obtain modified clay; (5) Weigh the following raw materials by mass: 28-33 parts of modified clay, 7-11 parts of magnesium trisilicate, 9-14 parts of titanium carbide, 11-15 parts of zirconium diboride, 3-5 parts of aluminum oxide, and 3-4 parts of boron nitride; mix the above raw materials and grind them in a ball mill to obtain powder. The ball mill speed is 200 rpm / min and the grinding time is 6 hours. Pour the powder into a mold and use a press to form a blank. The press pressure is 50 tons. Place the blank in a dryer at a temperature of 280°C and dry it. After drying, sinter it in a high-temperature furnace to obtain a ceramic tile precursor; spray the modified polysiloxane on the surface of the ceramic tile precursor and dry it naturally to obtain a high-temperature resistant ceramic tile for construction.

2. The method for preparing a high-temperature resistant ceramic tile for construction according to claim 1, characterized in that: The preparation method of the mixed iron salt solution in step (1) is as follows: ferric chloride hexahydrate, ferric dichloride tetrahydrate and pure water are stirred and mixed in a mass ratio of 1:0.37:10 for 10 minutes to obtain a mixed iron salt solution.

3. The method for preparing a high temperature resistant ceramic tile for construction according to claim 1, characterized in that: The clay particle size in step (4) is 500-700 mesh.

4. The method for preparing a high temperature resistant ceramic tile for construction according to claim 1, characterized in that: The sintering process parameters of step (5) are as follows: heating to 700-760°C at a rate of 6-10°C / min and keeping it for 3-5 hours, then heating to 1180-1210°C at a rate of 11-13°C / min and keeping it for 2-3 hours, then heating to 1740-1780°C at a rate of 6-8°C / min and keeping it for 1-3 hours, then cooling to 900-930°C and keeping it for 2-3 hours.

5. A high-temperature resistant ceramic tile for construction prepared according to the method according to any one of claims 1 to 4.