Anti-slip duplicated raw stone ceramic tile and preparation method thereof

Abstract

The invention discloses an anti-slip duplicated raw stone ceramic tile and a preparation method thereof, and belongs to the technical field of ceramic tile preparation. The anti-slip re-carved raw stone ceramic tile comprises a green body base layer, a glaze layer and a modified wear-resistant layer, and the green body base layer is prepared from the following materials in parts by weight: 40-60 parts of kaolin, 20-35 parts of quartz sand, 15-20 parts of potassium feldspar, 5-10 parts of calcite, 1-2 parts of wollastonite and 1-4 parts of talc; the glaze layer material consists of 15-22 parts of a glass forming agent, 3.2-8 parts of a fluxing agent, 2-7.2 parts of an opacifier, 0.4-2 parts of a coloring agent, 2-3.6 parts of an anti-skid complexing agent and 0.8-4 parts of a suspending agent; the modified wear-resistant layer material is composed of 1.2-2.1 parts of a modified wear-resistant agent and 5-10 parts of epoxy resin. The ceramic tile prepared by the method has excellent skid resistance, antifouling property and wear resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of tile preparation, and in particular relates to a non-slip replica original stone tile and a preparation method thereof. Background Art

[0002] As people's living standards improve, the requirements for comfort and safety of the home environment are also increasing. Traditional stone materials, such as marble and granite, have long been the preferred materials for high-end home decoration with their unique naturally formed texture and texture, as well as excellent physical properties. However, the mining and processing of these natural stones not only puts great pressure on the environment, but the limited stone resources also limit their wide application. In addition, natural stones often have deficiencies in anti-slip performance, especially in humid environments, which can easily cause slip accidents and bring safety hazards to people's daily lives. Therefore, the development of a new type of tile that can perfectly replicate the texture and texture of stone and has good anti-slip performance has become an urgent need in the current field of decorative materials.

[0003] Patent CN109369166A discloses imitation original stone ceramic tile and its preparation method, the ceramic tile comprises a body material layer, a base glaze material layer and a coloring glaze material layer, wherein the body material layer is made of the following raw materials: Yantai porcelain clay, Rizhao clay, plaster strips, high-strength mud, high-alumina mud, potassium feldspar, sodium feldspar, cooked coke, Hainan mud, Wenzu stone, pyrophyllite; the base glaze material layer is made of the following raw materials: potassium feldspar, sodium feldspar, calcined soil, washed kaolin, burned talc, quartz, zinc oxide, frit and zirconium silicate; the coloring glaze material layer is made of the following raw materials: potassium feldspar, dolomite, corundum, zinc oxide, washed kaolin, barium carbonate, frit and whisker material. The ceramic tile prepared by the method has strong fire resistance, strong antifreeze, high surface hardness and excellent anti-slip performance, but the anti-slip performance, stain resistance and wear resistance of the ceramic tile prepared by the method still have room for improvement. Summary of the invention

[0004] The object of the present invention is to provide a non-slip replica stone tile and a preparation method thereof, so as to solve the technical problems of poor non-slip performance, stain resistance and wear resistance of tiles in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: The invention provides an anti-skid replica original stone tile, comprising a body base, a glaze layer and a modified wear-resistant layer, wherein, by weight, the body base material consists of 40-60 parts of kaolin, 20-35 parts of quartz sand, 15-20 parts of potassium feldspar, 5-10 parts of calcite, 1-2 parts of wollastonite and 1-4 parts of talc; the glaze layer material consists of 15-22 parts of a glass former, 3.2-8 parts of a flux, 2-7.2 parts of an emulsifier, 0.4-2 parts of a colorant, 2-3.6 parts of an anti-skid compound and 0.8-4 parts of a suspending agent; and the modified wear-resistant layer material consists of 1.2-2.1 parts of a modified wear-resistant agent and 5-10 parts of an epoxy resin.

[0006] Preferably, the method for preparing the anti-slip composite comprises the following steps: Q1: Add p-bromophenol, potassium hydroxide, dimethyl sulfoxide and m-xylene to a container equipped with a water separator, a condenser and a vacuum pump. After heating and stirring, turn on the diaphragm pump to vacuum the reaction. After the reaction is completed, cool it down, and then use a constant pressure dropping funnel to drop 2,4-bis(trifluoromethyl)bromobenzene into the container. After stirring, heat it up to react, then quench the reaction, extract, wash, dry, rotary evaporate, and purify to obtain compound 1; Q2: The magnesium chips are washed, filtered, and dried to obtain activated magnesium chips, and the activated magnesium chips, iodine and anhydrous tetrahydrofuran are added into a container, nitrogen is introduced, and stirred, and then an anhydrous tetrahydrofuran solution containing chlorodimethylsilane is slowly added dropwise into the container, and then an anhydrous tetrahydrofuran solution containing compound 1 is slowly added dropwise into the container under ice bath conditions, after heating to react, react at room temperature, and then quench the reaction, extract, wash, dry, rotary evaporate, and purify to obtain compound 2; Q3: Under a nitrogen atmosphere, compound 2, dichloromethane and tri(pentafluorophenyl)borane were added to a container, stirred to dissolve, and then a dichloromethane solution containing methyltrimethoxysilane was added dropwise. After stirring at room temperature, the mixture was concentrated under reduced pressure, purified, and rotary evaporated to obtain an anti-slip composite.

[0007] In the above process, the synthetic reaction formula of the anti-slip compound is as follows: The results of mass spectrometry analysis of compound 1 were: m / z: 383.96 (100.0%), 385.96 (97.5%), 384.96(15.3%), 386.96 (14.8%), 387.96 (1.2%), 385.97 (1.1%); the results of mass spectrometry analysis of compound 2 were: m / z: 364.07 (100.0%), 365.08 (17.5%), 365.07 (5.1%), 366.07 (4.2%), 366.08(1.7%); the results of mass spectrometry analysis of the anti-slip compound were: m / z: 1180.18 (100.0%), 1181.18 (74.0%),1182.18 (27.6%), 1182.17 (13.4%), 1183.18 (11.8%), 1184.18 (3.5%), 1183.19(2.5%), 1183.17 (2.0%), 1184.19 (1.0%).

[0008] Preferably, in Q1, the dosage ratio of p-bromophenol, potassium hydroxide, dimethyl sulfoxide, m-xylene and 2,4-bis(trifluoromethyl)bromobenzene is (120-130) g: (45-48) g: (300-350) mL: (70-90) mL: (200-218) g, the heating and stirring temperature is 80-90°C, the vacuum reaction time is 66-88h, after stirring for 1-2h, the temperature is raised to 45-65°C and the reaction is carried out for 10-12h, distilled water is added to quench the reaction, the extraction is carried out with dichloromethane, the extraction is washed with distilled water, and the extraction is dried with anhydrous sodium sulfate.

[0009] Preferably, in Q2, the magnesium chips are washed 3-5 times with 10vt% hydrochloric acid, then washed 3-5 times with distilled water, then washed 3-5 times with anhydrous acetone, and finally washed 3-5 times with anhydrous ether. The drying temperature is 80-85°C, the time is 20-24h, the amount ratio of activated magnesium chips, iodine, chlorodimethylsilane and compound 1 is (1.32-1.58)g: (0.2-0.5)g: (10-13.94)g: (14-18)g, the stirring time is 20-30min, the temperature reaction is 50-60°C, the reaction time is 4-7h, the room temperature reaction time is 10-15h, the reaction is quenched with distilled water and n-hexane, extracted with dichloromethane, washed with distilled water, and dried with anhydrous sodium sulfate.

[0010] Preferably, in Q3, the usage ratio of compound 2, tri(pentafluorophenyl)borane and methyltrimethoxysilane is (3-4.2) g: (0.03-0.05) g: (0.88-0.96) g, and the stirring time at room temperature is 2-4 h.

[0011] Preferably, the preparation method of the modified wear-resistant agent comprises the following steps: S1: 2-chlorobenzothiazole, hydroquinone, potassium carbonate and N,N-dimethylformamide are added to a container, heated and stirred for reaction, and after the reaction is completed, extraction, washing, drying, vacuum distillation and purification are performed to obtain intermediate A; intermediate A, potassium carbonate and epibromopropane are added to a container containing N,N-dimethylformamide in sequence, heated and stirred for reaction, and after the reaction is completed, extraction, washing, drying, vacuum distillation and purification are performed to obtain intermediate B; S2: Add intermediate B, potassium carbonate and 4-hydroxypiperidine to a container containing isopropanol in sequence, heat and stir to react, extract, wash, dry, distill under reduced pressure, and purify to obtain intermediate C; add intermediate C, 3,3'-diaminobenzophenone and N,N-dimethylacetamide to a container, stir to dissolve, cool, add isophthaloyl chloride, stir, heat and stir, then add calcium hydroxide, continue stirring, wash, and dry to obtain a modified wear-resistant agent.

[0012] In the above process, the synthetic reaction formula of the modified wear-resistant agent is as follows: The results of mass spectrometry analysis of intermediate A were: m / z: 243.04 (100.0%), 244.04 (14.2%), 245.03(4.5%), 245.04 (1.5%), 244.03 (1.2%); the results of mass spectrometry analysis of intermediate B were: m / z: 299.06(100.0%), 300.06 (18.5%), 301.06 (4.7%), 301.07 (2.1%); the results of mass spectrometry analysis of intermediate C were: m / z: 400.15 (100.0%), 401.15 (23.9%), 402.14 (4.5%), 402.15 (3.7%), 403.14(1.1%).

[0013] Preferably, in S1, the amount ratio of 2-chlorobenzothiazole, hydroquinone, potassium carbonate and N,N-dimethylformamide is (10-15) g: (11-15) g: (10-15.1) g: (50-65) mL, the heating and stirring temperature is 110-120°C, and the reaction time is 8-10 h; the amount ratio of intermediate A, potassium carbonate, epibromopropane and N,N-dimethylformamide is (8-10) g: (5-6) g: (3-3.5) mL: (50-75) mL, the heating and stirring temperature is 50-60°C, and the reaction time is 10-14 h.

[0014] Preferably, in S2, the amount ratio of intermediate B, potassium carbonate, 4-hydroxypiperidine and isopropanol is (0.2-0.3) g: (0.11-0.17) g: (0.08-0.12) g: (5-7.5) mL, the heating and stirring temperature is 80-90°C, and the reaction time is 10-12 h; the amount ratio of intermediate C, 3,3'-diaminobenzophenone, N,N-dimethylacetamide, isophthaloyl chloride and calcium hydroxide is (1.21-1.65) g: (0.93-1.21) g: (90-105) mL: (0.83-0.89) g: (7-7.8) g, the heating and stirring temperature is 60-70°C, the stirring time is 1-2 h, and the continued stirring time is 15-30 min.

[0015] Preferably, the method for preparing the anti-slip replica original stone tile comprises the following steps: Step 1: crushing, grinding, pressing, drying and bisque firing kaolin, quartz sand, potassium feldspar, calcite, wollastonite and talc to obtain a green base; Step 2: Mix the glass former, flux, opacifier, colorant, anti-slip compound and suspending agent, ball-mill, pour onto the base of the green body, and then glaze and fire to obtain a semi-finished tile; Step 3: Mix the modified wear-resistant agent and epoxy resin, then spray them evenly onto the surface of the semi-finished tile, heat-cure, cut and polish to obtain non-slip replica original stone tiles.

[0016] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. The present invention first uses p-bromophenol, 2,4-bis(trifluoromethyl)bromobenzene, chlorodimethylsilane and methyltrimethoxysilane as raw materials to prepare an anti-slip composite agent, and then uses 2-chlorobenzothiazole, hydroquinone, epibromopropane, 4-hydroxypiperidine, 3,3'-diaminobenzophenone and isophthaloyl chloride as raw materials to prepare a modified wear-resistant agent. In the preparation process of anti-slip replica original stone tiles, adding the anti-slip composite agent and the modified wear-resistant agent can effectively improve the anti-fouling performance, anti-slip performance and wear resistance of the tiles.

[0017] 2. The anti-slip composite agent prepared by the present invention is added to the preparation process of ceramic tiles, which can effectively improve the anti-slip and anti-fouling properties of the ceramic tiles. The siloxy groups contained in the anti-slip composite agent can form a layer of microscopic rough structure after curing on the ceramic tile surface. Through the hydrolysis and condensation reaction of methyltrimethoxysilane, a three-dimensional cross-linked siloxane network is generated, and micro-nano-scale protrusions are formed during the curing process. The presence of the protrusions increases the roughness of the ceramic tile surface, thereby improving the surface friction. The trifluoromethyl group contained in the anti-slip composite agent is hydrophobic, which can reduce the formation of water film on the ceramic tile surface and avoid the slippery phenomenon caused by water film on the ceramic tile surface, thereby maintaining the high anti-slip property of the ceramic tile under various environments. The trifluoromethyl group is not only hydrophobic, but also because of its strong electronegativity and low surface energy characteristics, the ceramic tile surface exhibits super hydrophobicity / oleophobicity. The compactness of the siloxane network structure further prevents the penetration of stains, making the ceramic tile surface easy to clean.

[0018] 3. The present invention adds the prepared modified wear-resistant agent to the preparation process of ceramic tiles, which can effectively improve their wear resistance. The polyamide structure contained in the modified wear-resistant agent is tightly connected by covalent bonds to form a stable molecular structure, which can effectively transmit and disperse stress and slow down the wear rate of ceramic tiles. The polyamide structure has high mechanical strength, toughness and self-lubricating properties. During the friction process, the ceramic tiles containing the modified wear-resistant agent can still maintain a long service life under high-speed operation or frequent friction. The presence of ester bonds with excellent stability can increase the chemical stability of ceramic tiles and improve their wear resistance. The addition of ester bonds can change the arrangement and interaction mode of molecular chains, making the molecular chains more compact and orderly, which helps to better disperse stress and reduce wear during the friction process. The interaction between the two can effectively improve the wear resistance of ceramic tiles. DETAILED DESCRIPTION

[0019] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0020] Example 1: This example discloses a method for preparing an anti-slip composite, comprising the following steps: Q1: 125 g of p-bromophenol, 46.5 g of potassium hydroxide, 325 mL of dimethyl sulfoxide and 80 mL of m-xylene were added to a container equipped with a water separator, a condenser and a vacuum pump. After heating to 85°C and stirring, the diaphragm pump was turned on and the vacuum reaction was carried out for 72 hours. After the reaction was completed, it was cooled, and then 209 g of 2,4-bis(trifluoromethyl)bromobenzene was added dropwise to the container using a constant pressure dropping funnel. After stirring for 2 hours, the temperature was raised to 45°C and the reaction was carried out for 12 hours. Subsequently, distilled water was added to quench the reaction, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 1; Q2: The magnesium chips were washed with 10vt% hydrochloric acid for 3 times, then washed with distilled water for 3 times, then washed with anhydrous acetone for 3 times, and finally washed with anhydrous ether for 3 times, filtered, and dried at 80°C for 24 hours to obtain activated magnesium chips. 1.45g of activated magnesium chips, 0.35g of iodine and 60mL of anhydrous tetrahydrofuran were added to a container, nitrogen was introduced, and stirred for 30 minutes. Then, 60mL of anhydrous tetrahydrofuran solution containing 11.97g of chlorodimethylsilane was slowly added dropwise to the container. Then, under ice bath conditions, 48mL of anhydrous tetrahydrofuran solution containing 16g of compound 1 was slowly added dropwise to the container. After heating at 60°C for 6 hours, the reaction was reacted at room temperature for 12 hours, and then the reaction was quenched with distilled water and n-hexane, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 2; Q3: Under a nitrogen atmosphere, 3.6 g of compound 2, 4 mL of dichloromethane and 0.04 g of tri(pentafluorophenyl)borane were added to a container, stirred to dissolve, and then 2 mL of dichloromethane solution containing 0.92 g of methyltrimethoxysilane was added dropwise. After stirring at room temperature for 4 h, the mixture was concentrated under reduced pressure, purified, and rotary evaporated to obtain an anti-slip composite.

[0021] This embodiment discloses a method for preparing a modified anti-wear agent, comprising the following steps: S1: 12.5 g 2-chlorobenzothiazole, 13 g hydroquinone, 12.5 g potassium carbonate and 57.5 mL N, N-dimethylformamide were added to a container, heated and stirred at 120°C for 10 h, and after the reaction was completed, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate A; 9 g intermediate A, 5.5 g potassium carbonate and 3.25 mL epibromopropane were added to a container containing 62.5 mL N, N-dimethylformamide in sequence, heated and stirred at 55°C for 12 h, and after the reaction was completed, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate B; S2: 0.25g of intermediate B, 0.14g of potassium carbonate and 0.1g of 4-hydroxypiperidine were added to a container containing 6.25mL of isopropanol in sequence, heated and stirred at 85°C for 12h, extracted, washed, dried, and distilled under reduced pressure for purification to obtain intermediate C; 1.43g of intermediate C, 1.02g of 3,3'-diaminobenzophenone and 95mL of N,N-dimethylacetamide were added to a container, stirred and dissolved, cooled, 0.85g of isophthaloyl chloride was added, stirred, heated and stirred at 65°C for 2h, then 7.4g of calcium hydroxide was added, stirring was continued for 30min, washed, and dried to obtain a modified wear-resistant agent.

[0022] The present embodiment discloses an anti-slip replica original stone tile, comprising a body base, a glaze layer and a modified wear-resistant layer, wherein, by weight, the body base material consists of 50 parts of kaolin, 27.5 parts of quartz sand, 17.5 parts of potassium feldspar, 7.5 parts of calcite, 1.5 parts of wollastonite and 2.5 parts of talc; the glaze layer material consists of 17.5 parts of a glass former, 5.6 parts of a flux, 4.6 parts of an emulsifier, 1.2 parts of a colorant, 2.8 parts of an anti-slip compound and 2.4 parts of a suspending agent; and the modified wear-resistant layer material consists of 1.5 parts of a modified wear-resistant agent and 7.5 parts of an epoxy resin.

[0023] This embodiment discloses a method for preparing a non-slip replica stone tile, comprising the following steps: Step 1: crushing, grinding, pressing, drying and bisque firing kaolin, quartz sand, potassium feldspar, calcite, wollastonite and talc to obtain a green base; Step 2: Mix the glass former, flux, opacifier, colorant, anti-slip compound and suspending agent, ball-mill, pour onto the base of the green body, and then glaze and fire to obtain a semi-finished tile; Step 3: Mix the modified wear-resistant agent and epoxy resin, then spray them evenly onto the surface of the semi-finished tile, heat-cure, cut and polish to obtain non-slip replica original stone tiles.

[0024] Example 2: This example discloses a method for preparing an anti-slip composite, comprising the following steps: Q1: 120 g of p-bromophenol, 45 g of potassium hydroxide, 300 mL of dimethyl sulfoxide and 70 mL of m-xylene were added to a container equipped with a water separator, a condenser and a vacuum pump. After stirring at 85°C, the diaphragm pump was turned on and the reaction was vacuumed for 72 hours. After the reaction was completed, it was cooled, and then 200 g of 2,4-bis(trifluoromethyl)bromobenzene was added dropwise to the container using a constant pressure dropping funnel. After stirring for 2 hours, the temperature was raised to 45°C and the reaction was carried out for 12 hours. Subsequently, distilled water was added to quench the reaction, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 1; Q2: The magnesium chips were washed with 10vt% hydrochloric acid for 3 times, then washed with distilled water for 3 times, then washed with anhydrous acetone for 3 times, and finally washed with anhydrous ether for 3 times, filtered, and dried at 80°C for 24 hours to obtain activated magnesium chips. 1.32g of activated magnesium chips, 0.2g of iodine and 60mL of anhydrous tetrahydrofuran were added to a container, nitrogen was introduced, and stirred for 30 minutes. Then, 60mL of anhydrous tetrahydrofuran solution containing 10g of chlorodimethylsilane was slowly added dropwise to the container. Then, under ice bath conditions, 48mL of anhydrous tetrahydrofuran solution containing 14g of compound 1 was slowly added dropwise to the container. After heating at 60°C for 6 hours, the reaction was reacted at room temperature for 12 hours, and then the reaction was quenched with distilled water and n-hexane. The mixture was extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 2; Q3: Under a nitrogen atmosphere, 3 g of compound 2, 4 mL of dichloromethane and 0.03 g of tri(pentafluorophenyl)borane were added to a container, stirred to dissolve, and then 2 mL of dichloromethane solution containing 0.88 g of methyltrimethoxysilane was added dropwise. After stirring at room temperature for 4 h, the mixture was concentrated under reduced pressure, purified, and rotary evaporated to obtain an anti-slip composite.

[0025] This embodiment discloses a method for preparing a modified anti-wear agent, comprising the following steps: S1: 10 g 2-chlorobenzothiazole, 11 g hydroquinone, 10 g potassium carbonate and 50 mL N, N-dimethylformamide were added to a container, heated and stirred at 120°C for 10 h, and after the reaction was completed, the mixture was extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate A; 10 g intermediate A, 5 g potassium carbonate and 3 mL epibromopropane were added to a container containing 50 mL N, N-dimethylformamide in sequence, heated and stirred at 55°C for 12 h, and after the reaction was completed, the mixture was extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate B; S2: 0.2g of intermediate B, 0.11g of potassium carbonate and 0.08g of 4-hydroxypiperidine were added to a container containing 5mL of isopropanol in sequence, heated and stirred at 85°C for 12h, extracted, washed, dried, and distilled under reduced pressure for purification to obtain intermediate C; 1.21g of intermediate C, 0.93g of 3,3'-diaminobenzophenone and 90mL of N,N-dimethylacetamide were added to a container, stirred and dissolved, cooled, 0.83g of isophthaloyl chloride was added, stirred, heated and stirred at 65°C for 2h, then 7g of calcium hydroxide was added, stirring was continued for 30min, washed, and dried to obtain a modified wear-resistant agent.

[0026] The present embodiment discloses an anti-slip replica original stone tile, comprising a body base, a glaze layer and a modified wear-resistant layer, wherein, by weight, the body base material consists of 40 parts of kaolin, 20 parts of quartz sand, 15 parts of potassium feldspar, 5 parts of calcite, 1 part of wollastonite and 1 part of talc; the glaze layer material consists of 15 parts of glass former, 3.2 parts of flux, 2 parts of emulsifier, 0.4 parts of colorant, 2 parts of anti-slip compound and 0.8 parts of suspending agent; the modified wear-resistant layer material consists of 1.2 parts of modified wear-resistant agent and 5 parts of epoxy resin.

[0027] This embodiment discloses a method for preparing a non-slip replica stone tile, comprising the following steps: Step 1: crushing, grinding, pressing, drying and bisque firing kaolin, quartz sand, potassium feldspar, calcite, wollastonite and talc to obtain a green base; Step 2: Mix the glass former, flux, opacifier, colorant, anti-slip compound and suspending agent, ball-mill, pour onto the base of the green body, and then glaze and fire to obtain a semi-finished tile; Step 3: Mix the modified wear-resistant agent and epoxy resin, then spray them evenly onto the surface of the semi-finished tile, heat-cure, cut and polish to obtain non-slip replica original stone tiles.

[0028] Example 3: This example discloses a method for preparing an anti-slip composite, comprising the following steps: Q1: 130 g of p-bromophenol, 48 g of potassium hydroxide, 350 mL of dimethyl sulfoxide and 90 mL of m-xylene were added to a container equipped with a water separator, a condenser and a vacuum pump. After heating to 85°C and stirring, the diaphragm pump was turned on and the vacuum reaction was carried out for 72 hours. After the reaction was completed, it was cooled, and then 218 g of 2,4-bis(trifluoromethyl)bromobenzene was added dropwise to the container using a constant pressure dropping funnel. After stirring for 2 hours, the temperature was raised to 45°C and the reaction was carried out for 12 hours. Subsequently, distilled water was added to quench the reaction, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 1; Q2: The magnesium chips were washed with 10vt% hydrochloric acid for 3 times, then washed with distilled water for 3 times, then washed with anhydrous acetone for 3 times, and finally washed with anhydrous ether for 3 times, filtered, and dried at 80°C for 24 hours to obtain activated magnesium chips. 1.58g of activated magnesium chips, 0.5g of iodine and 60mL of anhydrous tetrahydrofuran were added to a container, nitrogen was introduced, and stirred for 30 minutes. Then, 60mL of anhydrous tetrahydrofuran solution containing 13.94g of chlorodimethylsilane was slowly added dropwise to the container. Then, under ice bath conditions, 48mL of anhydrous tetrahydrofuran solution containing 18g of compound 1 was slowly added dropwise to the container. After heating at 60°C for 6 hours, the reaction was reacted at room temperature for 12 hours, and then the reaction was quenched with distilled water and n-hexane, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 2; Q3: Under a nitrogen atmosphere, 4.2 g of compound 2, 4 mL of dichloromethane and 0.05 g of tri(pentafluorophenyl)borane were added to a container, stirred to dissolve, and then 2 mL of dichloromethane solution containing 0.96 g of methyltrimethoxysilane was added dropwise. After stirring at room temperature for 4 h, the mixture was concentrated under reduced pressure, purified, and rotary evaporated to obtain an anti-slip composite.

[0029] This embodiment discloses a method for preparing a modified anti-wear agent, comprising the following steps: S1: 15 g 2-chlorobenzothiazole, 15 g hydroquinone, 15.1 g potassium carbonate and 65 mL N, N-dimethylformamide were added to a container, heated and stirred at 120°C for 10 h, and after the reaction, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate A; 8 g intermediate A, 6 g potassium carbonate and 3.5 mL epibromopropane were added to a container containing 75 mL N, N-dimethylformamide in sequence, heated and stirred at 55°C for 12 h, and after the reaction, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate B; S2: 0.3g of intermediate B, 0.17g of potassium carbonate and 0.12g of 4-hydroxypiperidine were added to a container containing 7.5mL of isopropanol in sequence, heated and stirred at 85°C for 12h, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate C; 1.65g of intermediate C, 1.21g of 3,3'-diaminobenzophenone and 105mL of N,N-dimethylacetamide were added to the container, stirred and dissolved, cooled, 0.89g of isophthaloyl chloride was added, stirred, heated and stirred at 65°C for 2h, then 7.8g of calcium hydroxide was added, stirring was continued for 30min, washed, and dried to obtain a modified wear-resistant agent.

[0030] The present embodiment discloses an anti-slip replica original stone tile, comprising a body base, a glaze layer and a modified wear-resistant layer, wherein, by weight, the body base material consists of 60 parts of kaolin, 35 parts of quartz sand, 20 parts of potassium feldspar, 10 parts of calcite, 2 parts of wollastonite and 4 parts of talc; the glaze layer material consists of 22 parts of a glass former, 8 parts of a flux, 7.2 parts of an emulsifier, 2 parts of a colorant, 3.6 parts of an anti-slip compound and 4 parts of a suspending agent; and the modified wear-resistant layer material consists of 2.1 parts of a modified wear-resistant agent and 10 parts of an epoxy resin.

[0031] This embodiment discloses a method for preparing a non-slip replica stone tile, comprising the following steps: Step 1: crushing, grinding, pressing, drying and bisque firing kaolin, quartz sand, potassium feldspar, calcite, wollastonite and talc to obtain a green base; Step 2: Mix the glass former, flux, opacifier, colorant, anti-slip compound and suspending agent, ball-mill, pour onto the base of the green body, and then glaze and fire to obtain a semi-finished tile; Step 3: Mix the modified wear-resistant agent and epoxy resin, then spray them evenly onto the surface of the semi-finished tile, heat-cure, cut and polish to obtain non-slip replica original stone tiles.

[0032] Example 4: This example discloses a method for preparing an anti-slip composite, comprising the following steps: Q1: 128 g of p-bromophenol, 46 g of potassium hydroxide, 310 mL of dimethyl sulfoxide and 75 mL of m-xylene were added to a container equipped with a water separator, a condenser and a vacuum pump. After heating to 85°C and stirring, the diaphragm pump was turned on and the vacuum reaction was carried out for 72 hours. After the reaction was completed, it was cooled, and then 203 g of 2,4-bis(trifluoromethyl)bromobenzene was added dropwise to the container using a constant pressure dropping funnel. After stirring for 2 hours, the temperature was raised to 45°C and the reaction was carried out for 12 hours. Subsequently, distilled water was added to quench the reaction, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 1; Q2: The magnesium chips were washed with 10vt% hydrochloric acid for 3 times, then washed with distilled water for 3 times, then washed with anhydrous acetone for 3 times, and finally washed with anhydrous ether for 3 times, filtered, and dried at 80°C for 24 hours to obtain activated magnesium chips. 1.38g of activated magnesium chips, 0.3g of iodine and 60mL of anhydrous tetrahydrofuran were added to a container, nitrogen was introduced, and stirred for 30 minutes. Then, 60mL of anhydrous tetrahydrofuran slow solution containing 10.83g of chlorodimethylsilane was slowly added dropwise to the container, and then, under ice bath conditions, 48mL of anhydrous tetrahydrofuran solution containing 15g of compound 1 was slowly added dropwise to the container. After heating at 60°C for 6 hours, the reaction was reacted at room temperature for 12 hours, and then the reaction was quenched with distilled water and n-hexane, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, rotary evaporated, and purified to obtain compound 2; Q3: Under a nitrogen atmosphere, 3.3 g of compound 2, 4 mL of dichloromethane and 0.04 g of tri(pentafluorophenyl)borane were added to a container, stirred to dissolve, and then 2 mL of dichloromethane solution containing 0.9 g of methyltrimethoxysilane was added dropwise. After stirring at room temperature for 4 h, the mixture was concentrated under reduced pressure, purified, and rotary evaporated to obtain an anti-slip composite.

[0033] This embodiment discloses a method for preparing a modified anti-wear agent, comprising the following steps: S1: 11 g 2-chlorobenzothiazole, 12 g hydroquinone, 11 g potassium carbonate and 55 mL N, N-dimethylformamide were added to a container, heated and stirred at 120°C for 10 h, and after the reaction was completed, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate A; 8.5 g intermediate A, 5.2 g potassium carbonate and 3.1 mL epibromopropane were added to a container containing 55 mL N, N-dimethylformamide in sequence, heated and stirred at 55°C for 12 h, and after the reaction was completed, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate B; S2: 0.22g of intermediate B, 0.12g of potassium carbonate and 0.09g of 4-hydroxypiperidine were added to a container containing 5.5mL of isopropanol in sequence, heated and stirred at 85°C for 12h, extracted, washed, dried, distilled under reduced pressure, and purified to obtain intermediate C; 1.33g of intermediate C, 0.98g of 3,3'-diaminobenzophenone and 92mL of N,N-dimethylacetamide were added to a container, stirred and dissolved, cooled, 0.84g of isophthaloyl chloride was added, stirred, heated and stirred at 65°C for 2h, then 7.2g of calcium hydroxide was added, stirring was continued for 30min, washed, dried, and a modified wear-resistant agent was obtained.

[0034] The present embodiment discloses an anti-slip replica original stone tile, comprising a body base, a glaze layer and a modified wear-resistant layer, wherein, by weight, the body base material consists of 45 parts of kaolin, 25 parts of quartz sand, 16 parts of potassium feldspar, 6 parts of calcite, 1.1 parts of wollastonite and 2 parts of talc; the glaze layer material consists of 16 parts of a glass former, 4.4 parts of a flux, 2.8 parts of an emulsifier, 0.8 parts of a colorant, 2.4 parts of an anti-slip compound and 1.2 parts of a suspending agent; and the modified wear-resistant layer material consists of 1.3 parts of a modified wear-resistant agent and 6 parts of an epoxy resin.

[0035] This embodiment discloses a method for preparing a non-slip replica stone tile, comprising the following steps: Step 1: crushing, grinding, pressing, drying and bisque firing kaolin, quartz sand, potassium feldspar, calcite, wollastonite and talc to obtain a green base; Step 2: Mix the glass former, flux, opacifier, colorant, anti-slip compound and suspending agent, ball-mill, pour onto the base of the green body, and then glaze and fire to obtain a semi-finished tile; Step 3: Mix the modified wear-resistant agent and epoxy resin, then spray them evenly onto the surface of the semi-finished tile, heat-cure, cut and polish to obtain non-slip replica original stone tiles.

[0036] Comparative Example 1: Compared with Example 1, in the process of preparing the anti-slip replica original stone tiles in Comparative Example 1, no 2,4-bis(trifluoromethyl)bromobenzene is added, and other conditions remain unchanged.

[0037] Comparative Example 2: Compared with Example 1, in the process of preparing the anti-slip replica original stone tiles in Comparative Example 2, no 2-chlorobenzothiazole is added, and other conditions remain unchanged.

[0038] Experimental Example: The ceramic tiles prepared in Examples 1-4 and Comparative Examples 1-2 were subjected to performance tests. The anti-pollution performance of the samples was tested according to GB / T3810.14-2016, the anti-slip performance of the samples was tested according to GB / T 35153-2017, and the wear resistance of the samples was tested according to GB / T 3810.7-2016. The test results are shown in Table 1: Table 1 The higher the pollution resistance level, the better the pollution resistance effect; the higher the wet anti-slip value, the better the anti-slip effect; the higher the wear resistance level, the better the wear resistance. It can be seen from the test results in Table 1 that the tiles prepared by Examples 1-4 of the present invention have excellent pollution resistance, anti-slip performance and wear resistance. By comparing Comparative Example 1 with Examples 1-4, it can be seen that the addition of 2,4-bis(trifluoromethyl)bromobenzene can effectively improve the pollution resistance and anti-slip performance of tiles; by comparing Comparative Example 2 with Examples 1-4, it can be seen that the addition of 2-chlorobenzothiazole can improve the wear resistance of tiles.

[0039] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0040] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A non-slip replica stone tile, characterized in that: The invention comprises a base body, a glaze layer and a modified wear-resistant layer, wherein the base body material is composed of 40-60 parts of kaolin, 20-35 parts of quartz sand, 15-20 parts of potassium feldspar, 5-10 parts of calcite, 1-2 parts of wollastonite and 1-4 parts of talc; the glaze layer material is composed of 15-22 parts of glass former, 3.2-8 parts of flux, 2-7.2 parts of emulsifier, 0.4-2 parts of colorant, 2-3.6 parts of anti-skid compound and 0.8-4 parts of suspending agent; and the modified wear-resistant layer material is composed of 1.2-2.1 parts of modified wear-resistant agent and 5-10 parts of epoxy resin.

2. The anti-slip replica original stone tile according to claim 1, characterized in that: The preparation method of the anti-slip composite comprises the following steps: Q1: Add p-bromophenol, potassium hydroxide, dimethyl sulfoxide and m-xylene to a container equipped with a water separator, a condenser and a vacuum pump. After heating and stirring, turn on the diaphragm pump to vacuum the reaction. After the reaction is completed, cool it down, and then use a constant pressure dropping funnel to drop 2,4-bis(trifluoromethyl)bromobenzene into the container. After stirring, heat it up to react, then quench the reaction, extract, wash, dry, rotary evaporate, and purify to obtain compound 1; Q2: The magnesium chips are washed, filtered, and dried to obtain activated magnesium chips, and the activated magnesium chips, iodine and anhydrous tetrahydrofuran are added into a container, nitrogen is introduced, and stirred, and then an anhydrous tetrahydrofuran solution containing chlorodimethylsilane is slowly added dropwise into the container, and then an anhydrous tetrahydrofuran solution containing compound 1 is slowly added dropwise into the container under ice bath conditions, after heating to react, react at room temperature, and then quench the reaction, extract, wash, dry, rotary evaporate, and purify to obtain compound 2; Q3: Under a nitrogen atmosphere, compound 2, dichloromethane and tri(pentafluorophenyl)borane were added to a container, stirred to dissolve, and then a dichloromethane solution containing methyltrimethoxysilane was added dropwise. After stirring at room temperature, the mixture was concentrated under reduced pressure, purified, and rotary evaporated to obtain an anti-slip composite.

3. The anti-slip replica original stone tile according to claim 2, characterized in that: In the Q1, the dosage ratio of p-bromophenol, potassium hydroxide, dimethyl sulfoxide, m-xylene and 2,4-bis(trifluoromethyl)bromobenzene is (120-130) g: (45-48) g: (300-350) mL: (70-90) mL: (200-218) g, the heating and stirring temperature is 80-90°C, the vacuum reaction time is 66-88h, after stirring for 1-2h, the temperature is raised to 45-65°C and the reaction is carried out for 10-12h, distilled water is added to quench the reaction, the product is extracted with dichloromethane, washed with distilled water, and dried with anhydrous sodium sulfate.

4. The anti-slip replica original stone tile according to claim 2, characterized in that: In Q2, the magnesium chips are washed 3-5 times with 10vt% hydrochloric acid, then washed 3-5 times with distilled water, then washed 3-5 times with anhydrous acetone, and finally washed 3-5 times with anhydrous ether. The drying temperature is 80-85°C, the time is 20-24h, the amount ratio of activated magnesium chips, iodine, chlorodimethylsilane and compound 1 is (1.32-1.58)g: (0.2-0.5)g: (10-13.94)g: (14-18)g, the stirring time is 20-30min, the temperature reaction is 50-60°C, the reaction time is 4-7h, the room temperature reaction time is 10-15h, the reaction is quenched with distilled water and n-hexane, extracted with dichloromethane, washed with distilled water, and dried with anhydrous sodium sulfate.

5. The anti-slip replica original stone tile according to claim 2, characterized in that: In Q3, the usage ratio of compound 2, tri(pentafluorophenyl)borane and methyltrimethoxysilane is (3-4.2) g: (0.03-0.05) g: (0.88-0.96) g, and the stirring time at room temperature is 2-4 h.

6. The anti-slip replica original stone tile according to claim 1, characterized in that: The preparation method of the modified anti-wear agent comprises the following steps: S1: 2-chlorobenzothiazole, hydroquinone, potassium carbonate and N,N-dimethylformamide are added to a container, heated and stirred for reaction, and after the reaction is completed, extraction, washing, drying, vacuum distillation and purification are performed to obtain intermediate A; intermediate A, potassium carbonate and epibromopropane are added to a container containing N,N-dimethylformamide in sequence, heated and stirred for reaction, and after the reaction is completed, extraction, washing, drying, vacuum distillation and purification are performed to obtain intermediate B; S2: Add intermediate B, potassium carbonate and 4-hydroxypiperidine to a container containing isopropanol in sequence, heat and stir to react, extract, wash, dry, distill under reduced pressure, and purify to obtain intermediate C; add intermediate C, 3,3'-diaminobenzophenone and N,N-dimethylacetamide to a container, stir to dissolve, cool, add isophthaloyl chloride, stir, heat and stir, then add calcium hydroxide, continue stirring, wash, and dry to obtain a modified wear-resistant agent.

7. The anti-slip replica original stone tile according to claim 6, characterized in that: In S1, the amount ratio of 2-chlorobenzothiazole, hydroquinone, potassium carbonate and N,N-dimethylformamide is (10-15) g: (11-15) g: (10-15.1) g: (50-65) mL, the heating and stirring temperature is 110-120°C, and the reaction time is 8-10 h; the amount ratio of intermediate A, potassium carbonate, epibromopropane and N,N-dimethylformamide is (8-10) g: (5-6) g: (3-3.5) mL: (50-75) mL, the heating and stirring temperature is 50-60°C, and the reaction time is 10-14 h.

8. The anti-slip replica original stone tile according to claim 6, characterized in that: In the S2, the amount ratio of the intermediate B, potassium carbonate, 4-hydroxypiperidine and isopropanol is (0.2-0.3) g: (0.11-0.17) g: (0.08-0.12) g: (5-7.5) mL, the heating and stirring temperature is 80-90°C, and the reaction time is 10-12 h; the amount ratio of the intermediate C, 3,3'-diaminobenzophenone, N,N-dimethylacetamide, isophthaloyl chloride and calcium hydroxide is (1.21-1.65) g: (0.93-1.21) g: (90-105) mL: (0.83-0.89) g: (7-7.8) g, the heating and stirring temperature is 60-70°C, the stirring time is 1-2 h, and the continued stirring time is 15-30 min.

9. A method for preparing a non-slip replica original stone tile according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: crushing, grinding, pressing, drying and bisque firing kaolin, quartz sand, potassium feldspar, calcite, wollastonite and talc to obtain a green base; Step 2: Mix the glass former, flux, opacifier, colorant, anti-slip compound and suspending agent, ball-mill, pour onto the base of the green body, and then glaze and fire to obtain a semi-finished tile; Step 3: Mix the modified wear-resistant agent and epoxy resin, then spray them evenly onto the surface of the semi-finished tile, heat-cure, cut and polish to obtain non-slip replica original stone tiles.

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