阅读说明：本技术 一种特效纳米瓷砖阻滑防护剂及其制备方法 (Special-effect nano tile anti-slip protective agent and preparation method thereof ) 是由 王永生 于 2021-07-07 设计创作，主要内容包括：本发明属于瓷砖表面处理技术领域,特别涉及一种特效纳米瓷砖阻滑防护剂及其制备方法。按重量份计,包括以下组分：缓蚀剂3-7份、保湿剂5-10份、氟盐18-25份、表面活性剂12-18份、分散稳定剂0.5-7份、消泡剂6-12份、渗透剂4-6份、助剂3-10份、纳米氧化铝4-6份,余量为水。本发明通过将纳米氧化铝均匀分散在阻滑防护剂中,使得纳米氧化铝被包裹在阻滑防护剂内部,阻滑防护剂涂膜由于有纳米氧化铝的存在增加了阻滑防护剂涂膜的耐磨性,另一方面由于纳米氧化铝的存在使得阻滑防护剂涂膜表面存在微小的颗粒状的凸起,进一步增大了阻滑防护剂表面的摩擦力。(The invention belongs to the technical field of ceramic tile surface treatment, and particularly relates to a special-effect nano ceramic tile anti-slip protective agent and a preparation method thereof. The paint comprises the following components in parts by weight: 3-7 parts of corrosion inhibitor, 5-10 parts of humectant, 18-25 parts of villiaumite, 12-18 parts of surfactant, 0.5-7 parts of dispersion stabilizer, 6-12 parts of defoaming agent, 4-6 parts of penetrating agent, 3-10 parts of auxiliary agent, 4-6 parts of nano aluminum oxide and the balance of water. According to the invention, the nano alumina is uniformly dispersed in the anti-slip protective agent, so that the nano alumina is wrapped in the anti-slip protective agent, the anti-slip protective agent coating film has the advantages that the wear resistance of the anti-slip protective agent coating film is increased due to the existence of the nano alumina, and on the other hand, the anti-slip protective agent coating film has tiny granular protrusions on the surface due to the existence of the nano alumina, so that the friction force on the surface of the anti-slip protective agent is further increased.)

1. The special-effect nano tile anti-slip protective agent is characterized by comprising the following components in parts by weight: 3-7 parts of corrosion inhibitor, 5-10 parts of humectant, 18-25 parts of villiaumite, 12-18 parts of surfactant, 0.5-7 parts of dispersion stabilizer, 6-12 parts of defoaming agent, 4-6 parts of penetrating agent, 3-10 parts of auxiliary agent, 4-6 parts of nano aluminum oxide and the balance of water.

2. The special-effect nano tile slip-resistant protective agent according to claim 1, wherein the preparation steps of the nano alumina are as follows:

(1) preparing an aluminum sulfate solution and a sodium hydroxide solution;

(2) dropwise adding a sodium hydroxide solution into an aluminum sulfate solution, and heating to 80 ℃ under a stirring state until a suspension with a pH value of 5 is formed;

(3) adding stearic acid into the suspension obtained in the step (2), and dropwise adding a sodium hydroxide solution to obtain an aluminum hydroxide suspension;

(4) adding the aluminum hydroxide suspension obtained in the step (3) into a high-pressure kettle, reacting for 6 hours at 200 ℃, naturally cooling and reducing the temperature after the reaction is finished, taking out the suspension when the pressure is reduced to normal pressure, carrying out suction filtration under reduced pressure, washing with deionized water for three times, and drying in a 120 ℃ oven for 4 hours to obtain an aluminum oxide precursor;

(5) and (4) putting the alumina precursor obtained in the step (4) into a muffle furnace, calcining for 2h at 800 ℃, and grinding to obtain the nano alumina.

3. The specific nano tile slip-resistant protective agent according to claim 1, wherein the corrosion inhibitor is sodium oxalate and sulfur, the humectant is polyethylene glycol or maltitol, the fluoride salt is ammonium fluoride, the dispersion stabilizer is at least one of ethylene glycol ethyl ether, ethylene glycol butyl ether and diethylene glycol dimethyl ether, the antifoaming agent is polyoxyethylene polyoxypropylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether, and the auxiliary agent is triethanolamine.

4. The special-effect nano-ceramic tile slip-resistant protective agent according to claim 1, wherein the special-effect nano-ceramic tile slip-resistant protective agent is coated on a surface to be coated of a nano-ceramic tile;

the nano ceramic tile is prepared from the following raw materials in parts by weight: 16-20 parts of kaolin, 15-26 parts of montmorillonite, 20-26 parts of volcanic rock, 8-12 parts of jade powder, 5-10 parts of talc mud, 17-23 parts of potassium-sodium stone powder and 6-10 parts of nano aluminum oxide;

the preparation method of the nano ceramic tile comprises the following steps:

A. preparing nano ceramic tile slurry: mixing kaolin, montmorillonite, volcanic rock, jade powder, talc mud, potassium-sodium stone powder and nano alumina in proportion, adding water and ball milling to obtain nano ceramic tile slurry;

B. treating the nano ceramic tile slurry: spray drying the prepared nano ceramic tile slurry, and pressing and forming the dried material;

C. and (3) sintering: sintering the pressed and molded nano ceramic tile blank at 1100-1250 ℃ for 80min to obtain the special-effect nano ceramic tile;

D. and C, coating the prepared anti-slip protective agent on the surface to be coated of the special-effect nano ceramic tile prepared in the step C by using a roller.

5. The specific nano tile slip-resistant protective agent according to claim 4, wherein the talc mud mainly comprises: SiO 2₂67.34％、Al₂O₃4.23％、Fe₂O₃1.66％、TiO₂0.15％、CaO0.63％、MgO20.22％、K₂O0.26％、Na₂0.76 percent of O and 4.75 percent of loss on ignition.

6. The specific nano tile skid-resistant protective agent according to claim 4, wherein the potassium-sodium stone powder mainly comprises the following components: SiO 2₂74.42％、Al₂O₃14.03％、Fe₂O₃0.67％、TiO₂0.16％、CaO1.42％、MgO0.24％、K₂O3.20％、Na₂3.56 percent of O and 2.30 percent of loss on ignition.

7. The preparation method of the special-effect nano-ceramic tile anti-slip protective agent according to any one of claims 1 to 6, characterized in that the anti-slip protective agent is obtained by mixing a corrosion inhibitor, a humectant, a villiaumite, a surfactant, a dispersion stabilizer, a defoaming agent, a penetrating agent, an auxiliary agent and nano-alumina in proportion, adding water, performing ultrasonic treatment for 25min, and uniformly stirring at the rotation speed of 800-1000 rpm.

Technical Field

The invention relates to the technical field of ceramic tile surface treatment, in particular to a special-effect nano ceramic tile anti-slip protective agent and a preparation method thereof.

Background

The ceramic tile is made up of refractory metal oxide and semimetal oxide through grinding, mixing, pressing, glazing and sintering, and features high resistance to acid and alkali, high strength and toughness, and unique and better performance.

The ceramic tile is as novel architectural decoration material, by the wide application in the fitment construction of building, nevertheless because ceramic tile surface is smooth, produce the phenomenon of skidding easily during the walking, consequently, the coefficient of friction on ceramic tile surface should arouse people's concern, to the smooth phenomenon in ceramic tile surface, use and hinder smooth protective agent in order to increase ceramic tile surface friction, because of the effectual concern that receives people, but the ceramic tile is in the use, through the friction, the ceramic tile surface will receive the loss, influence the use, consequently, it hinders smooth protective agent and becomes the focus that people studied to prepare a safe durable difficult ceramic tile of wearing and tearing.

Patent application No. 201910780771.X discloses a tile anti-slip agent and a preparation method thereof, the tile anti-slip agent uses hypochlorous acid and hydrochloric acid as main raw materials for corroding the tile surface of a tile, a large number of micro grooves are formed on the tile surface of the tile, a high polymer foaming material is fixed in the micro grooves under the action of a silane coupling agent and a dispersing agent, when the high polymer foaming material is pressurized and extrudes gas adsorbed on the high polymer foaming material, the high polymer foaming material is promoted to adsorb the foot surface, and the anti-slip effect is increased.

The patent with the application number of 201811560895.9 provides a safe, environment-friendly, stain-resistant and anti-slip agent and a preparation method thereof, wherein a system formed by organic acid, inorganic acid, auxiliary agent and fluorine salt is cooperated with one another to form nanoscale holes with uniform size and depth on a floor tile, so that the anti-slip coefficient of the floor tile is improved. After the floor tile is treated by the anti-slip agent, matte can not be caused, subsequent polishing treatment is not needed, the floor tile keeps the glossiness, and the effect is durable.

Disclosure of Invention

The invention provides a special-effect nano tile anti-slip protective agent and a preparation method thereof, aiming at solving the problems that the surface of the existing tile is too smooth and the coating layer of the existing anti-slip agent is easy to wear.

The technical scheme for solving the problems is as follows:

the special-effect nano tile slip-resistant protective agent comprises the following components in parts by weight: 3-7 parts of corrosion inhibitor, 5-10 parts of humectant, 18-25 parts of villiaumite, 12-18 parts of surfactant, 0.5-7 parts of dispersion stabilizer, 6-12 parts of defoaming agent, 4-6 parts of penetrating agent, 3-10 parts of auxiliary agent, 4-6 parts of nano aluminum oxide and the balance of water.

The invention has the following beneficial effects: when the anti-slip protective agent is prepared, nano aluminum oxide is uniformly dispersed in the anti-slip protective agent, the anti-slip protective agent is cured on the surface of a ceramic tile when the anti-slip protective agent is used, the nano aluminum oxide is wrapped inside the anti-slip protective agent, the wear resistance of a coating film of the anti-slip protective agent is improved due to the existence of the nano aluminum oxide in the coating film of the anti-slip protective agent, and on the other hand, tiny granular protrusions exist on the surface of the coating film of the anti-slip protective agent due to the existence of the nano aluminum oxide, so that the friction force on the surface of the anti-slip protective agent is further increased.

Drawings

FIG. 1 is a scanning electron microscope image of nano-alumina prepared in the present invention.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Example 1

The embodiment provides a special-effect nano-ceramic tile slip-resistant protective agent, and the special-effect nano-ceramic tile slip-resistant protective agent is coated on the surface to be coated of a nano-ceramic tile.

The special-effect nano tile slip-resistant protective agent comprises the following components in parts by weight: 3 parts of corrosion inhibitor, 5 parts of humectant, 18 parts of villiaumite, 12 parts of surfactant, 0.5 part of dispersion stabilizer, 6 parts of defoaming agent, 4 parts of penetrating agent, 3 parts of auxiliary agent, 4 parts of nano-alumina and the balance of water, wherein the corrosion inhibitor is sodium oxalate and sulfur, the humectant is polyethylene glycol, the villiaumite is ammonium fluoride, the dispersion stabilizer is ethylene glycol ethyl ether, the defoaming agent is polyoxyethylene polyoxypropylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether and the auxiliary agent is triethanolamine.

The preparation method of the surfactant comprises the following steps:

s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I, wherein the reaction equation is as follows:

s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine esters, wherein the main reaction equation is as follows:

s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product, in the esterification reaction process, the inventor adopts the copper sulfate as a catalyst, on one hand, the copper sulfate is difficult to dissolve in alcohol, acid and ester, and after the reaction is finished, the copper sulfate can be separated only by filtering, so that the separation process is simplified, on the other hand, the copper sulfate has stable performance and good repeatability in the use process, and can be repeatedly used after the reaction, the filtration and the separation, so that the cost is saved, and the reaction equation is as follows:

the silicon oil generally has no color or is slightly yellowish, has no obvious smell, has small toxicity and extremely small volatility, can increase the glossiness of the surface of a coated object, but has stable chemical property and is not easy to react with other substances, wherein the low-hydrogen-content silicon oil contains Si-H bonds, the H on the low-hydrogen-content silicon oil is more active and is easy to generate a series of reactions, thereby endowing the low-hydrogen-content silicon oil with some new performances, in the invention, the chloroplatinic acid-isopropanol is used as a catalyst, the trans-3-pentenoic acid and the low-hydrogen-content silicon oil are subjected to a hydrosilylation reaction to obtain carboxyl modified silicon oil, the carboxyl modified silicon oil and the fatty acid triethanolamine ester are further subjected to an esterification reaction, so that the surfactant generated by the reaction has improved adsorption performance on the nano ceramic tile due to the existence of nitrogen atoms and has the property of the modified silicon oil, so that the prepared surfactant has good fluidity.

Wherein, the preparation steps of the nano-alumina are as follows:

(1) preparing an aluminum sulfate solution and a sodium hydroxide solution: dissolving 13.8g of aluminum sulfate in 80ml of distilled water to obtain an aluminum sulfate solution, and dissolving 5.1g of sodium hydroxide in 80ml of distilled water to obtain a sodium hydroxide solution;

(2) dropwise adding a sodium hydroxide solution into an aluminum sulfate solution, heating to 80 ℃ under a stirring state, and testing the pH of the solution by using a pH meter every 10min in the reaction process until a suspension with the pH value of 5 is formed;

(3) adding 0.5g of stearic acid into the suspension obtained in the step (2), and dropwise adding a sodium hydroxide solution to obtain an aluminum hydroxide suspension;

(4) adding the aluminum hydroxide suspension obtained in the step (3) into a high-pressure kettle, reacting for 6 hours at 200 ℃, naturally cooling and reducing the temperature after the reaction is finished, taking out the suspension when the pressure is reduced to normal pressure, carrying out suction filtration under reduced pressure, washing with deionized water for three times, and drying in a 120 ℃ oven for 4 hours to obtain an aluminum oxide precursor;

(5) and (4) putting the alumina precursor obtained in the step (4) into a muffle furnace, calcining for 2h at 800 ℃, and grinding to obtain the nano alumina.

The scanning electron microscope test is carried out on the prepared nano aluminum oxide, the obtained result is shown in figure 1, and the obtained nano aluminum oxide can form irregular tiny bulges, so that after the anti-slip protective agent is coated on the surface of the ceramic tile, the unevenness of the surface can be increased without affecting the ornamental value, and the friction coefficient of a contact surface can be increased.

A preparation method of a special-effect nano tile anti-slip protective agent comprises the steps of mixing 3 parts of a corrosion inhibitor, 5 parts of a humectant, 18 parts of villiaumite, 12 parts of a surfactant, 0.5 part of a dispersion stabilizer, 6 parts of a defoaming agent, 4 parts of a penetrating agent, 3 parts of an auxiliary agent and 4 parts of nano alumina in proportion, adding water, performing ultrasonic treatment for 25min, and uniformly stirring at the rotating speed of 800rpm to obtain the anti-slip protective agent.

The nano ceramic tile is prepared from the following raw materials in parts by weight: 16 parts of kaolin, 15 parts of montmorillonite, 20 parts of volcanic rock, 8 parts of jade powder, 5 parts of talc mud, 17 parts of potassium-sodium stone powder and 6 parts of nano aluminum oxide.

Wherein, the main composition of the talcum mud is as follows: SiO 2₂67.34％、Al₂O₃4.23％、Fe₂O₃1.66％、TiO₂0.15％、CaO0.63％、MgO20.22％、K₂O0.26％、Na₂0.76 percent of O and 4.75 percent of loss on ignition.

Wherein, the main components of the potassium-sodium stone powder are as follows: SiO 2₂74.42％、Al₂O₃14.03％、Fe₂O₃0.67％、TiO₂0.16％、CaO1.42％、MgO0.24％、K₂O3.20％、Na₂3.56 percent of O and 2.30 percent of loss on ignition.

The preparation method of the nano ceramic tile comprises the following steps:

A. preparing nano ceramic tile slurry: mixing 16 parts of kaolin, 15 parts of montmorillonite, 20 parts of volcanic rock, 8 parts of jade powder, 5 parts of talc mud, 17 parts of potassium-sodium stone powder and 6 parts of nano alumina in proportion, adding water, and performing ball milling to obtain nano tile slurry, wherein the ball milling conditions are as follows: ball milling for 12h at a speed of 100 r/min;

B. treating the nano ceramic tile slurry: spray drying the prepared nano ceramic tile slurry, and pressing and forming the dried material;

C. and (3) sintering: sintering the pressed and molded nano ceramic tile blank at 1100 ℃ for 80min to obtain the special-effect nano ceramic tile;

D. and C, coating the prepared anti-slip protective agent on the surface to be coated of the special-effect nano ceramic tile prepared in the step C by using a roller wheel to obtain the nano ceramic tile with the anti-slip coating.

Example 2

The embodiment provides a special-effect nano-ceramic tile slip-resistant protective agent, and the special-effect nano-ceramic tile slip-resistant protective agent is coated on the surface to be coated of a nano-ceramic tile.

The special-effect nano tile slip-resistant protective agent comprises the following components in parts by weight: 3 parts of corrosion inhibitor, 5 parts of humectant, 18 parts of villiaumite, 12 parts of surfactant, 0.5 part of dispersion stabilizer, 6 parts of defoaming agent, 4 parts of penetrating agent, 3 parts of auxiliary agent, 4 parts of nano-alumina and the balance of water, wherein the corrosion inhibitor is sodium oxalate and sulfur, the humectant is polyethylene glycol, the villiaumite is ammonium fluoride, the dispersion stabilizer is ethylene glycol ethyl ether, the defoaming agent is polyoxyethylene polyoxypropylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether and the auxiliary agent is triethanolamine.

The preparation method of the surfactant comprises the following steps:

s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I;

s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine ester, wherein a diester product is mainly used;

s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product.

Wherein, the preparation steps of the nano-alumina are as follows:

(1) preparing an aluminum sulfate solution and a sodium hydroxide solution: dissolving 13.8g of aluminum sulfate in 80ml of distilled water to obtain an aluminum sulfate solution, and dissolving 5.1g of sodium hydroxide in 80ml of distilled water to obtain a sodium hydroxide solution;

(2) dropwise adding a sodium hydroxide solution into an aluminum sulfate solution, heating to 80 ℃ under a stirring state, and testing the pH of the solution by using a pH meter every 10min in the reaction process until a suspension with the pH value of 5 is formed;

(3) adding 0.5g of stearic acid into the suspension obtained in the step (2), and dropwise adding a sodium hydroxide solution to obtain an aluminum hydroxide suspension;

(4) adding the aluminum hydroxide suspension obtained in the step (3) into a high-pressure kettle, reacting for 6 hours at 200 ℃, naturally cooling and reducing the temperature after the reaction is finished, taking out the suspension when the pressure is reduced to normal pressure, carrying out suction filtration under reduced pressure, washing with deionized water for three times, and drying in a 120 ℃ oven for 4 hours to obtain an aluminum oxide precursor;

(5) and (4) putting the alumina precursor obtained in the step (4) into a muffle furnace, calcining for 2h at 800 ℃, and grinding to obtain the nano alumina.

A preparation method of a special-effect nano tile anti-slip protective agent comprises the steps of mixing 3 parts of a corrosion inhibitor, 5 parts of a humectant, 18 parts of villiaumite, 12 parts of a surfactant, 0.5 part of a dispersion stabilizer, 6 parts of a defoaming agent, 4 parts of a penetrating agent, 3 parts of an auxiliary agent and 4 parts of nano alumina in proportion, adding water, performing ultrasonic treatment for 25min, and uniformly stirring at the rotating speed of 1000rpm to obtain the anti-slip protective agent.

The nano ceramic tile is prepared from the following raw materials in parts by weight: 20 parts of kaolin, 26 parts of montmorillonite, 26 parts of volcanic rock, 12 parts of jade powder, 10 parts of talc mud, 23 parts of potassium-sodium stone powder and 10 parts of nano aluminum oxide.

Wherein, the main composition of the talcum mud is as follows: SiO 2₂67.34％、Al₂O₃4.23％、Fe₂O₃1.66％、TiO₂0.15％、CaO0.63％、MgO20.22％、K₂O0.26％、Na₂0.76 percent of O and 4.75 percent of loss on ignition.

Wherein, the main components of the potassium-sodium stone powder are as follows: SiO 2₂74.42％、Al₂O₃14.03％、Fe₂O₃0.67％、TiO₂0.16％、CaO1.42％、MgO0.24％、K₂O3.20％、Na₂3.56 percent of O and 2.30 percent of loss on ignition.

The preparation method of the nano ceramic tile comprises the following steps:

A. preparing nano ceramic tile slurry: mixing 20 parts of kaolin, 26 parts of montmorillonite, 26 parts of volcanic rock, 12 parts of jade powder, 10 parts of talc mud, 23 parts of potassium-sodium stone powder and 10 parts of nano alumina in proportion, adding water, and performing ball milling to obtain nano tile slurry, wherein the ball milling conditions are as follows: ball milling for 12h at a speed of 100 r/min;

B. treating the nano ceramic tile slurry: spray drying the prepared nano ceramic tile slurry, and pressing and forming the dried material;

C. and (3) sintering: sintering the pressed and molded nano ceramic tile blank at 1250 ℃ for 80min to obtain the special-effect nano ceramic tile;

D. and C, coating the prepared anti-slip protective agent on the surface to be coated of the special-effect nano ceramic tile prepared in the step C by using a roller wheel to obtain the nano ceramic tile with the anti-slip coating.

Example 3

The embodiment provides a special-effect nano-ceramic tile slip-resistant protective agent, and the special-effect nano-ceramic tile slip-resistant protective agent is coated on the surface to be coated of a nano-ceramic tile.

The special-effect nano tile slip-resistant protective agent comprises the following components in parts by weight: the corrosion inhibitor comprises, by weight, 7 parts of a corrosion inhibitor, 10 parts of a humectant, 25 parts of a villiaumite, 18 parts of a surfactant, 7 parts of a dispersion stabilizer, 12 parts of a defoaming agent, 6 parts of a penetrating agent, 10 parts of an auxiliary agent, 6 parts of nano-alumina and the balance of water, wherein the corrosion inhibitor is sodium oxalate and sulfur, the humectant is polyethylene glycol, the villiaumite is ammonium fluoride, the dispersion stabilizer is ethylene glycol ethyl ether, the defoaming agent is polyoxyethylene polyoxypropylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether, and the auxiliary agent is triethanolamine.

The preparation method of the surfactant comprises the following steps:

s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I;

s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine ester, wherein a diester product is mainly used;

s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product.

Wherein, the preparation steps of the nano-alumina are as follows:

(1) preparing an aluminum sulfate solution and a sodium hydroxide solution: dissolving 13.8g of aluminum sulfate in 80ml of distilled water to obtain an aluminum sulfate solution, and dissolving 5.1g of sodium hydroxide in 80ml of distilled water to obtain a sodium hydroxide solution;

(2) dropwise adding a sodium hydroxide solution into an aluminum sulfate solution, heating to 80 ℃ under a stirring state, and testing the pH of the solution by using a pH meter every 10min in the reaction process until a suspension with the pH value of 5 is formed;

(3) adding 0.5g of stearic acid into the suspension obtained in the step (2), and dropwise adding a sodium hydroxide solution to obtain an aluminum hydroxide suspension;

(4) adding the aluminum hydroxide suspension obtained in the step (3) into a high-pressure kettle, reacting for 6 hours at 200 ℃, naturally cooling and reducing the temperature after the reaction is finished, taking out the suspension when the pressure is reduced to normal pressure, carrying out suction filtration under reduced pressure, washing with deionized water for three times, and drying in a 120 ℃ oven for 4 hours to obtain an aluminum oxide precursor;

(5) and (4) putting the alumina precursor obtained in the step (4) into a muffle furnace, calcining for 2h at 800 ℃, and grinding to obtain the nano alumina.

A preparation method of a special-effect nano tile anti-slip protective agent comprises the steps of mixing 7 parts of a corrosion inhibitor, 10 parts of a humectant, 25 parts of villiaumite, 18 parts of a surfactant, 7 parts of a dispersion stabilizer, 12 parts of a defoaming agent, 6 parts of a penetrating agent, 10 parts of an auxiliary agent and 6 parts of nano alumina in proportion, adding water, performing ultrasonic treatment for 25min, and uniformly stirring at the rotating speed of 800rpm to obtain the anti-slip protective agent.

The nano ceramic tile is prepared from the following raw materials in parts by weight: 16 parts of kaolin, 15 parts of montmorillonite, 20 parts of volcanic rock, 8 parts of jade powder, 5 parts of talc mud, 17 parts of potassium-sodium stone powder and 6 parts of nano aluminum oxide.

Wherein, the main composition of the talcum mud is as follows: SiO 2₂67.34％、Al₂O₃4.23％、Fe₂O₃1.66％、TiO₂0.15％、CaO0.63％、MgO20.22％、K₂O0.26％、Na₂0.76 percent of O and 4.75 percent of loss on ignition.

Wherein, the main components of the potassium-sodium stone powder are as follows: SiO 2₂74.42％、Al₂O₃14.03％、Fe₂O₃0.67％、TiO₂0.16％、CaO1.42％、MgO0.24％、K₂O3.20％、Na₂3.56 percent of O and 2.30 percent of loss on ignition.

The preparation method of the nano ceramic tile comprises the following steps:

A. preparing nano ceramic tile slurry: mixing 16 parts of kaolin, 15 parts of montmorillonite, 20 parts of volcanic rock, 8 parts of jade powder, 5 parts of talc mud, 17 parts of potassium-sodium stone powder and 6 parts of nano alumina in proportion, adding water, and performing ball milling to obtain nano tile slurry, wherein the ball milling conditions are as follows: ball milling for 12h at a speed of 100 r/min;

B. treating the nano ceramic tile slurry: spray drying the prepared nano ceramic tile slurry, and pressing and forming the dried material;

C. and (3) sintering: sintering the pressed and molded nano ceramic tile blank at 1100 ℃ for 80min to obtain the special-effect nano ceramic tile;

D. and C, coating the prepared anti-slip protective agent on the surface to be coated of the special-effect nano ceramic tile prepared in the step C by using a roller wheel to obtain the nano ceramic tile with the anti-slip coating.

Example 4

The embodiment provides a special-effect nano-ceramic tile slip-resistant protective agent, and the special-effect nano-ceramic tile slip-resistant protective agent is coated on the surface to be coated of a nano-ceramic tile.

The special-effect nano tile slip-resistant protective agent comprises the following components in parts by weight: the corrosion inhibitor comprises, by weight, 7 parts of a corrosion inhibitor, 10 parts of a humectant, 25 parts of a villiaumite, 18 parts of a surfactant, 7 parts of a dispersion stabilizer, 12 parts of a defoaming agent, 6 parts of a penetrating agent, 10 parts of an auxiliary agent, 6 parts of nano-alumina and the balance of water, wherein the corrosion inhibitor is sodium oxalate and sulfur, the humectant is polyethylene glycol, the villiaumite is ammonium fluoride, the dispersion stabilizer is ethylene glycol ethyl ether, the defoaming agent is polyoxyethylene polyoxypropylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether, and the auxiliary agent is triethanolamine.

The preparation method of the surfactant comprises the following steps:

s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I;

s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine ester, wherein a diester product is mainly used;

s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product.

Wherein, the preparation steps of the nano-alumina are as follows:

(1) preparing an aluminum sulfate solution and a sodium hydroxide solution: dissolving 13.8g of aluminum sulfate in 80ml of distilled water to obtain an aluminum sulfate solution, and dissolving 5.1g of sodium hydroxide in 80ml of distilled water to obtain a sodium hydroxide solution;

(2) dropwise adding a sodium hydroxide solution into an aluminum sulfate solution, heating to 80 ℃ under a stirring state, and testing the pH of the solution by using a pH meter every 10min in the reaction process until a suspension with the pH value of 5 is formed;

(3) adding 0.5g of stearic acid into the suspension obtained in the step (2), and dropwise adding a sodium hydroxide solution to obtain an aluminum hydroxide suspension;

(4) adding the aluminum hydroxide suspension obtained in the step (3) into a high-pressure kettle, reacting for 6 hours at 200 ℃, naturally cooling and reducing the temperature after the reaction is finished, taking out the suspension when the pressure is reduced to normal pressure, carrying out suction filtration under reduced pressure, washing with deionized water for three times, and drying in a 120 ℃ oven for 4 hours to obtain an aluminum oxide precursor;

(5) and (4) putting the alumina precursor obtained in the step (4) into a muffle furnace, calcining for 2h at 800 ℃, and grinding to obtain the nano alumina.

A preparation method of a special-effect nano tile anti-slip protective agent comprises the steps of mixing 7 parts of a corrosion inhibitor, 10 parts of a humectant, 25 parts of villiaumite, 18 parts of a surfactant, 7 parts of a dispersion stabilizer, 12 parts of a defoaming agent, 6 parts of a penetrating agent, 10 parts of an auxiliary agent and 6 parts of nano alumina in proportion, adding water, performing ultrasonic treatment for 25min, and uniformly stirring at the rotating speed of 1000rpm to obtain the anti-slip protective agent.

The nano ceramic tile is prepared from the following raw materials in parts by weight: 20 parts of kaolin, 26 parts of montmorillonite, 26 parts of volcanic rock, 12 parts of jade powder, 10 parts of talc mud, 23 parts of potassium-sodium stone powder and 10 parts of nano aluminum oxide.

Wherein, the main composition of the talcum mud is as follows: SiO 2₂67.34％、Al₂O₃4.23％、Fe₂O₃1.66％、TiO₂0.15％、CaO0.63％、MgO20.22％、K₂O0.26％、Na₂0.76 percent of O and 4.75 percent of loss on ignition.

Wherein, the main components of the potassium-sodium stone powder are as follows: SiO 2₂74.42％、Al₂O₃14.03％、Fe₂O₃0.67％、TiO₂0.16％、CaO1.42％、MgO0.24％、K₂O3.20％、Na₂3.56 percent of O and 2.30 percent of loss on ignition.

The preparation method of the nano ceramic tile comprises the following steps:

A. preparing nano ceramic tile slurry: mixing 20 parts of kaolin, 26 parts of montmorillonite, 26 parts of volcanic rock, 12 parts of jade powder, 10 parts of talc mud, 23 parts of potassium-sodium stone powder and 10 parts of nano alumina in proportion, adding water, and performing ball milling to obtain nano tile slurry, wherein the ball milling conditions are as follows: ball milling for 12h at a speed of 100 r/min;

B. treating the nano ceramic tile slurry: spray drying the prepared nano ceramic tile slurry, and pressing and forming the dried material;

C. and (3) sintering: sintering the pressed and molded nano ceramic tile blank at 1250 ℃ for 80min to obtain the special-effect nano ceramic tile;

D. and C, coating the prepared anti-slip protective agent on the surface to be coated of the special-effect nano ceramic tile prepared in the step C by using a roller wheel to obtain the nano ceramic tile with the anti-slip coating.

Example 5

The embodiment provides a special-effect nano-ceramic tile slip-resistant protective agent, and the special-effect nano-ceramic tile slip-resistant protective agent is coated on the surface to be coated of a nano-ceramic tile.

The special-effect nano tile slip-resistant protective agent comprises the following components in parts by weight: 5 parts of corrosion inhibitor, 8 parts of humectant, 22 parts of villiaumite, 16 parts of surfactant, 3 parts of dispersion stabilizer, 8 parts of defoaming agent, 5 parts of penetrating agent, 8 parts of auxiliary agent, 5 parts of nano-alumina and the balance of water, wherein the corrosion inhibitor is sodium oxalate and sulfur, the humectant is polyethylene glycol, the villiaumite is ammonium fluoride, the dispersion stabilizer is ethylene glycol ethyl ether, the defoaming agent is polyoxyethylene polyoxypropylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether, and the auxiliary agent is triethanolamine.

The preparation method of the surfactant comprises the following steps:

s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I;

s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine ester, wherein a diester product is mainly used;

s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product.

Wherein, the preparation steps of the nano-alumina are as follows:

(1) preparing an aluminum sulfate solution and a sodium hydroxide solution: dissolving 13.8g of aluminum sulfate in 80ml of distilled water to obtain an aluminum sulfate solution, and dissolving 5.1g of sodium hydroxide in 80ml of distilled water to obtain a sodium hydroxide solution;

(2) dropwise adding a sodium hydroxide solution into an aluminum sulfate solution, heating to 80 ℃ under a stirring state, and testing the pH of the solution by using a pH meter every 10min in the reaction process until a suspension with the pH value of 5 is formed;

(3) adding 0.5g of stearic acid into the suspension obtained in the step (2), and dropwise adding a sodium hydroxide solution to obtain an aluminum hydroxide suspension;

(4) adding the aluminum hydroxide suspension obtained in the step (3) into a high-pressure kettle, reacting for 6 hours at 200 ℃, naturally cooling and reducing the temperature after the reaction is finished, taking out the suspension when the pressure is reduced to normal pressure, carrying out suction filtration under reduced pressure, washing with deionized water for three times, and drying in a 120 ℃ oven for 4 hours to obtain an aluminum oxide precursor;

(5) and (4) putting the alumina precursor obtained in the step (4) into a muffle furnace, calcining for 2h at 800 ℃, and grinding to obtain the nano alumina.

A preparation method of a special-effect nano tile anti-slip protective agent comprises the steps of mixing 5 parts of a corrosion inhibitor, 8 parts of a humectant, 22 parts of villiaumite, 16 parts of a surfactant, 3 parts of a dispersion stabilizer, 8 parts of a defoaming agent, 5 parts of a penetrating agent, 8 parts of an auxiliary agent and 5 parts of nano alumina in proportion, adding water, performing ultrasonic treatment for 25min, and uniformly stirring at the rotating speed of 1000rpm to obtain the anti-slip protective agent.

The nano ceramic tile is prepared from the following raw materials in parts by weight: 18 parts of kaolin, 22 parts of montmorillonite, 24 parts of volcanic rock, 10 parts of jade powder, 8 parts of talc mud, 19 parts of potassium-sodium stone powder and 8 parts of nano aluminum oxide.

Wherein, the main composition of the talcum mud is as follows: SiO 2₂67.34％、Al₂O₃4.23％、Fe₂O₃1.66％、TiO₂0.15％、CaO0.63％、MgO20.22％、K₂O0.26％、Na₂0.76 percent of O and 4.75 percent of loss on ignition.

Wherein, the main components of the potassium-sodium stone powder are as follows: SiO 2₂74.42％、Al₂O₃14.03％、Fe₂O₃0.67％、TiO₂0.16％、CaO1.42％、MgO0.24％、K₂O3.20％、Na₂3.56 percent of O and 2.30 percent of loss on ignition.

The preparation method of the nano ceramic tile comprises the following steps:

A. preparing nano ceramic tile slurry: mixing 18 parts of kaolin, 22 parts of montmorillonite, 24 parts of volcanic rock, 10 parts of jade powder, 8 parts of talc mud, 19 parts of potassium-sodium stone powder and 8 parts of nano alumina in proportion, adding water, and performing ball milling to obtain nano ceramic tile slurry, wherein the ball milling conditions are as follows: ball milling for 12h at a speed of 100 r/min;

B. treating the nano ceramic tile slurry: spray drying the prepared nano ceramic tile slurry, and pressing and forming the dried material;

C. and (3) sintering: sintering the pressed and molded nano ceramic tile blank at 1250 ℃ for 80min to obtain the special-effect nano ceramic tile;

D. and C, coating the prepared anti-slip protective agent on the surface to be coated of the special-effect nano ceramic tile prepared in the step C by using a roller wheel to obtain the nano ceramic tile with the anti-slip coating.

Comparative example

The embodiment provides a special-effect nano-ceramic tile slip-resistant protective agent, and the special-effect nano-ceramic tile slip-resistant protective agent is coated on the surface to be coated of a nano-ceramic tile.

The special-effect nano tile slip-resistant protective agent comprises the following components in parts by weight: 5 parts of corrosion inhibitor, 8 parts of humectant, 22 parts of villiaumite, 16 parts of surfactant, 3 parts of dispersion stabilizer, 8 parts of defoaming agent, 5 parts of penetrating agent, 8 parts of auxiliary agent and the balance of water, wherein the corrosion inhibitor is sodium oxalate and sulfur, the humectant is polyethylene glycol, the villiaumite is ammonium fluoride, the dispersion stabilizer is ethylene glycol ethyl ether, the defoaming agent is polyoxyethylene polyoxypropylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether, and the auxiliary agent is triethanolamine.

The preparation method of the surfactant comprises the following steps:

s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I;

s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine ester, wherein a diester product is mainly used;

s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product.

A preparation method of a special-effect nano tile anti-slip protective agent comprises the steps of mixing 5 parts of a corrosion inhibitor, 8 parts of a humectant, 22 parts of villiaumite, 16 parts of a surfactant, 3 parts of a dispersion stabilizer, 8 parts of a defoaming agent, 5 parts of a penetrating agent and 8 parts of an auxiliary agent in proportion, adding water, performing ultrasonic treatment for 25min, and uniformly stirring at the rotating speed of 1000rpm to obtain the anti-slip protective agent.

The nano ceramic tile is prepared from the following raw materials in parts by weight: 18 parts of kaolin, 22 parts of montmorillonite, 24 parts of volcanic rock, 10 parts of jade powder, 8 parts of talc mud and 19 parts of potassium-sodium stone powder.

Wherein, the main composition of the talcum mud is as follows: SiO 2₂67.34％、Al₂O₃4.23％、Fe₂O₃1.66％、TiO₂0.15％、CaO0.63％、MgO20.22％、K₂O0.26％、Na₂0.76 percent of O and 4.75 percent of loss on ignition.

Wherein, the main components of the potassium-sodium stone powder are as follows: SiO 2₂74.42％、Al₂O₃14.03％、Fe₂O₃0.67％、TiO₂0.16％、CaO1.42％、MgO0.24％、K₂O3.20％、Na₂3.56 percent of O and 2.30 percent of loss on ignition.

The preparation method of the nano ceramic tile comprises the following steps:

A. preparing nano ceramic tile slurry: mixing 18 parts of kaolin, 22 parts of montmorillonite, 24 parts of volcanic rock, 10 parts of jade powder, 8 parts of talc mud and 19 parts of potassium-sodium stone powder in proportion, adding water, and performing ball milling to obtain nano ceramic tile slurry, wherein the ball milling conditions are as follows: ball milling for 12h at a speed of 100 r/min;

B. treating the nano ceramic tile slurry: spray drying the prepared nano ceramic tile slurry, and pressing and forming the dried material;

C. and (3) sintering: sintering the pressed and molded nano ceramic tile blank at 1250 ℃ for 80min to obtain the special-effect nano ceramic tile;

D. and C, coating the prepared anti-slip protective agent on the surface to be coated of the special-effect nano ceramic tile prepared in the step C by using a roller wheel to obtain the nano ceramic tile with the anti-slip coating.

Performance testing

And (3) testing the friction coefficient: and (3) carrying out anti-slip protective agent treatment on the ceramic tile, and drying the ceramic tile treated by the anti-slip protective agent at 30 ℃ for 60 min.

And (3) testing the friction resistance: use canvas to rub repeatedly at the ceramic tile surface that has coated the antiskid protective agent, observe the ceramic tile outward appearance, test condition: 60 times/min for 30 min.

The test results are shown in table 1:

TABLE 1

As can be seen from Table 1, the anti-slip protective agent prepared by the invention can effectively increase the friction coefficient of the ceramic tile, and the surface still keeps good brightness and has no scratches after multiple times of friction. In the invention, the synthesized surfactant contains the polyorganosiloxane with a chain structure, so that the synthesized surfactant has excellent thermal oxidation stability and strong anti-foaming property, and simultaneously can keep good glossiness of the surface of a coated object, and simultaneously, the synthesized surfactant has lone pair electrons on nitrogen atoms, is easy to react with other atoms, and increases the adsorption effect between the anti-slip protective agent and the nano ceramic tile.

In addition, in the invention, nano alumina is added in the preparation process of the nano ceramic tile and the special-effect nano ceramic tile anti-slip protective agent, the nano alumina uniformly distributed in the nano ceramic tile can effectively improve the compactness, the smoothness and the wear resistance of the ceramic tile, meanwhile, when the anti-slip protective agent is prepared, the nano alumina is uniformly dispersed in the nano alumina, when the anti-slip protective agent is used, the anti-slip protective agent is solidified on the surface of the ceramic tile, the nano alumina is wrapped in the anti-slip protective agent, the anti-slip protective agent coating film increases the wear resistance of the anti-slip protective agent coating film due to the existence of the nano alumina, on the other hand, the anti-slip protective agent coating film has tiny granular bulges on the surface due to the existence of the nano alumina, the friction force between the anti-slip protective agent surface coating film and a contact surface is further increased, and the nano alumina particles in the anti-slip protective agent are connected together by virtue of the coating film wrapped outside the anti-slip protective agent, meanwhile, when the anti-slip protective agent is coated on the nano ceramic tile, the surface of the ceramic tile can be corroded to form a large number of irregular tiny depressions, the anti-slip protective agent can enter the depressions at the moment, the anti-slip protective agent and the nano ceramic tile contain nano aluminum oxide inside, large repulsive force generated due to different materials does not exist between the same substances, when pressure is applied, the adhesive force between the anti-slip protective agent and the nano ceramic tile is increased, and the anti-slip protective agent is prevented from being cracked between the anti-slip protective agent and the ceramic tile after being used for a long time.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.