Soft light brick with super anti-fouling coating and preparation method of soft light brick

Abstract

The invention discloses a soft light brick with a super anti-fouling coating and a preparation method of the soft light brick, and belongs to the technical field of soft light brick preparation. The preparation method of the soft light brick with the super anti-fouling coating comprises the following steps: step 1, mixing kaolin, quartz sand, feldspar, clay and a dispersing agent, carrying out wet ball milling, and standing after ball milling to obtain a mixture; 2, the mixture is pressed, subjected to microwave drying and sintered, and a matrix is obtained; and step 3, carrying out sand blasting treatment on the matrix, then spraying a hardening agent, then spraying a composite anti-fouling agent, curing and polishing to obtain the soft light brick with the super anti-fouling coating. The soft light brick prepared by the method has excellent stain resistance, hardness, wear resistance and weather resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of soft light tiles, and particularly relates to a soft light tile with a super anti-fouling coating and a preparation method thereof. Background Art

[0002] With the rapid development of society and the continuous improvement of people's living standards, home decoration is no longer limited to beauty and practicality, but pays more attention to the durability, easy cleaning and environmental protection performance of materials. As an indispensable part of home decoration, the improvement and innovation of the performance of ceramic tiles have become the focus of the industry development. Traditional ceramic tile products, whether bright tiles or matte tiles, have certain limitations. Bright tiles, although with a high-profile and bright decorative effect, are prone to excessive visual stimulation, causing sensory depression, and the problem of light pollution is becoming increasingly prominent. Matte ceramic tiles, although with less reflection, can create a low-key and introverted space atmosphere, but insufficient reflection is likely to cause dull light, making it difficult to achieve an ideal decoration and matching effect. Against this background, soft light tiles came into being. It combines the advantages of bright tiles and matte ceramic tiles. Through the dynamic soft light wax polishing technology, the reflectivity of the product is reduced, and the surface light produces a scattering effect, so as to achieve a comfortable visual experience for the human body and a space decoration effect without light pollution.

[0003] However, soft light tiles also face some technical problems. Among them, the most prominent one is their insufficient anti-fouling performance. Since the surface glossiness of soft light tiles is moderate, it is neither as smooth and easy to clean as bright tiles nor as rough on the surface and not easy to adsorb stains as matte tiles. Therefore, their anti-fouling performance is relatively weak. In daily use, stains such as water stains and oil stains are easy to penetrate into the tile surface and are difficult to clean, which not only affects the beauty of the ceramic tiles but also shortens their service life.

[0004] Patent CN119409479A discloses a super anti-fouling soft light tile and a preparation method thereof. 60-80 parts of kaolin, 40-60 parts of talcum powder, 20-40 parts of quartz stone, 20-30 parts of orthoclase, and 15-25 parts of fly ash are put into a mixer for stirring, grinding, forming, and sintering to obtain a green body; ceramic glaze and titanium dioxide are ball-milled with water to obtain a glaze slurry, and then the glaze slurry is applied to the green body, dried, calcined, and polished to form a glaze layer; 5-15 parts of epoxy resin, 4-10 parts of polyurethane resin, 3-8 parts of an additive, and 110-120 parts of a diluent are mixed and coated on the surface of the glaze layer and cured to form a protective coating, and then the tile is obtained. The additive containing fluorine element, quaternary ammonium salt structure and silane oxy group stably exists in the protective coating, and the glaze layer contains titanium dioxide, and the adhesion between the coating and the glaze layer is good. The three of them act together with the green body, making the tile of the present invention excellent and stable in hydrophobicity, antibacterial property and soft light property. However, there is still room for improvement in the stain resistance, hardness, wear resistance and weather resistance of the tile prepared by this method. Summary of the Invention

[0005] The object of the present invention is to provide a soft light brick with a super anti-fouling coating and a preparation method thereof, which is used to solve the technical problems of poor stain resistance, hardness, abrasion resistance and weather resistance of soft light bricks in the prior art.

[0006] To achieve the above object, the present invention adopts the following technical solutions: The present invention provides a preparation method of a soft light brick with a super anti-fouling coating, comprising the following steps: Step 1: Mix kaolin, quartz sand, feldspar, clay and a dispersant, and perform wet ball milling. After the ball milling is completed, let it stand still to obtain a mixed material; Step 2: Press the mixed material, perform microwave drying and sintering to obtain a substrate; Step 3: Perform sandblasting on the substrate, then spray a hardening agent, and then spray a composite anti-fouling agent, cure and polish to obtain a soft light brick with a super anti-fouling coating.

[0007] Preferably, in the said Step 1, the dosage ratio of kaolin, quartz sand, feldspar, clay and the dispersant is (40 - 50) g : (22 - 28) g : (18 - 23) g : (8 - 13) g : (0.4 - 0.8) g. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, and it is ground at 300 - 500 rpm for 4 - 6 h. The fineness of the slurry is controlled to be ≤5 μm, and it stands still at 25°C for 40 - 50 h.

[0008] Preferably, in the said Step 2, during the pressing process, it is kept under pressure at 30 - 35 MPa for 110 - 140 s, the microwave drying frequency is 2.45 GHz, and the sintering process is as follows: it is heated from room temperature to 300°C at a heating rate of 3°C / min, held for 30 - 45 min, then heated from 300°C to 1180°C at a heating rate of 5°C / min, held for 80 - 100 min, and then naturally cooled to 200 - 220°C and taken out of the furnace; in the said Step 3, during the sandblasting treatment, 120-mesh corundum sand is used, the compressed air pressure is 0.5 - 0.8 MPa, and the spraying distance is 20 - 30 cm.

[0009] Preferably, the preparation method of the said hardening agent comprises the following steps: Q1: Under an ice bath environment, drop phosphorus oxychloride into N,N-dimethylformamide. After the dropping is completed, stir at room temperature to obtain a mixed solution 1. Then add 2,7-dimethoxynaphthalene to dichloromethane, stir and dissolve to obtain a mixed solution 2. Drop the mixed solution 1 into the mixed solution 2. After the dropping is completed, stir at room temperature, then add it to deionized water, stir, adjust the pH, extract, dry, perform reduced pressure rotary evaporation, recrystallize, and vacuum dry to obtain intermediate 1; Q2: Add intermediate 1 into dichloromethane. Under a nitrogen and ice bath environment, slowly dropwise add boron tribromide solution. After the addition is complete, stir the reaction at room temperature. After the reaction ends, dropwise add the product into a container filled with deionized water under an ice bath environment. After the addition is complete, continue to stir the reaction at room temperature, adjust the pH, extract, dry, rotary evaporate under reduced pressure, and purify to obtain intermediate 2; Q3: Under a nitrogen atmosphere, add diglycolic acid into the acid anhydride, heat and stir under reflux. After the reflux ends, add phosphoric acid to catalyze the reaction. After the reaction ends, rotary evaporate under reduced pressure, concentrate, crystallize at low temperature, and filter to obtain intermediate 3; Add pyrrolidine into a container filled with dichloromethane, then add intermediate 3, and stir the reaction at room temperature. After the reaction ends, rotary evaporate and crystallize at low temperature to obtain intermediate 4; Q4: Add intermediate 2 into N,N-dimethylformamide, add intermediate 4 under stirring conditions, then dropwise add concentrated sulfuric acid, heat and stir the reaction, extract, adjust the pH, extract, dry, distill and concentrate under reduced pressure, and purify to obtain the hardening agent.

[0010] In the above process, the synthesis reaction formula of the hardening agent is as follows: The results of mass spectrometry analysis of intermediate 1 are: m / z: 216.08 (100.0%), 217.08 (14.3%); The results of mass spectrometry analysis of intermediate 2 are: m / z: 188.05 (100.0%), 189.05 (12.1%), 190.05 (1.3%); The results of mass spectrometry analysis of intermediate 3 are: m / z: 116.01 (100.0%), 117.01 (4.3%); The results of mass spectrometry analysis of intermediate 4 are: m / z: 187.08 (100.0%), 188.09 (9.0%), 189.09 (1.2%); The results of mass spectrometry analysis of the hardening agent are: m / z: 526.20 (100.0%), 527.20 (29.9%), 528.20 (6.4%).

[0011] Preferably, in Q1, the dosage ratio of phosphorus oxychloride, N,N-dimethylformamide, 2,7-dimethoxynaphthalene and dichloromethane is (8 - 10) mL: (3 - 5) mL: (2 - 3) g: (10 - 12) mL; In Q2, the dosage ratio of intermediate 1, dichloromethane and boron tribromide solution is (0.45 - 0.65) g: (8 - 10) mL: (5 - 7) mL, and the concentration of the boron tribromide solution is 0.526 g / mL.

[0012] Preferably, in Q3, the dosage ratio of diglycolic acid, acid anhydride and phosphoric acid is (45 - 55) g : (120 - 145) mL : (0.07 - 0.09) mL; the dosage ratio of pyrrolidine, dichloromethane and intermediate 3 is (10.2 - 11.4) g : (140 - 160) mL : (17.1 - 17.8) g; in Q4, the dosage ratio of intermediate 2, N,N-dimethylformamide, intermediate 4 and concentrated sulfuric acid is (2.068 - 2.124) g : (20 - 25) mL : (3.5 - 3.83) g : (0.03 - 0.04) g.

[0013] Preferably, the preparation method of the composite anti-fouling agent comprises the following steps: S1: Under an ice bath environment, add dodecyl mercaptan, methyltrioctylammonium chloride and acetone into a reaction vessel in sequence, then dropwise add sodium hydroxide solution, stir, then continue to add acetone and carbon disulfide, react, then add chloroform and sodium hydroxide solution, after dropping, stir under ice bath, after stirring ends, purify to obtain product A; S2: Add 4-vinylbenzyl chloride and triphenylphosphine into a container filled with acetone in sequence, stir, heat and react after evacuating, after the reaction ends, sediment, wash, vacuum filter, dry to obtain product B; S3: Add product A, product B and methanol into a container in sequence, then add azobisisobutyronitrile, stir, evacuate, heat and react, quench the reaction in a liquid nitrogen environment, freeze, dialyze, vacuum dry to obtain product C; add product C, divinylbenzene, methanol and azobisisobutyronitrile into a container in sequence, stir and react, evacuate, heat and react, quench the reaction in liquid nitrogen, sediment, purify to obtain the composite anti-fouling agent.

[0014] In the above process, dodecyl mercaptan undergoes a nucleophilic addition reaction with carbon disulfide under alkaline conditions, and then undergoes a nucleophilic substitution reaction with chloroform to obtain product A. Using 4-vinylbenzyl chloride and triphenylphosphine as raw materials, product B is prepared. Then, product A and product B undergo RAFT polymerization under the condition of azobisisobutyronitrile as an initiator to obtain product C. Subsequently, product C and divinylbenzene undergo RAFT polymerization to obtain the composite anti-fouling agent.

[0015] Preferably, in S1, the dosage ratio of dodecyl mercaptan, methyltrioctylammonium chloride, carbon disulfide and chloroform is (20.12 - 20.4) g : (0.98 - 1.05) g : (7.2 - 8.1) g : (17.12 - 18.74) g; in S2, the dosage ratio of 4-vinylbenzyl chloride, triphenylphosphine and acetone is (9.01 - 9.32) g : (18.45 - 19.12) g : (90 - 120) mL.

[0016] Preferably, in S3, the dosage ratio of product A, product B, methanol and azobisisobutyronitrile is (4.01 - 4.33) g : (0.08 - 0.1) g : (12 - 15) mL : (0.02 - 0.05) g; the dosage ratio of product C, divinylbenzene, methanol and azobisisobutyronitrile is (0.01 - 0.032) g : (0.028 - 0.034) g : (4 - 6) mL : (0.002 - 0.005) g.

[0017] Preferably, a kind of soft light brick with a super anti - pollution coating prepared by the preparation method of the soft light brick with a super anti - pollution coating.

[0018] In summary, due to the adoption of the above - mentioned technical solutions, the beneficial effects of the present invention are as follows: 1. Firstly, using phosphorus oxychloride, 2,7 - dimethoxynaphthalene, boron tribromide solution, diglycolic acid and pyrrolidine as the main raw materials, a hardening agent is prepared. Subsequently, using n - dodecyl mercaptan, carbon disulfide, methyltrioctylammonium chloride, 4 - vinylbenzyl chloride, triphenylphosphine and divinylbenzene as the main raw materials, a composite anti - pollution agent is prepared. Adding the hardening agent and the composite anti - pollution agent to the preparation process of the soft light brick can effectively improve its hardness, weather resistance, anti - pollution performance, wear resistance and self - repair performance.

[0019] 2. Adding the prepared hardening agent to the preparation process of the soft light brick can effectively improve its hardness, wear resistance and weather resistance. The naphthalene ring contained in the hardening agent has extremely high rigidity, forming a molecular scaffold in the soft light brick, restricting the movement of polymer segments, enhancing the overall hardness of the soft light brick. And the carbonyl group and hydroxyl group form a hydrogen - bond network, enhancing the interfacial bonding force, thereby improving the hardness. The nitrogen atom in the five - membered heterocyclic ring can participate in the electron - cloud delocalization of the soft light brick matrix, forming a flexible buffer layer to disperse local stress and improve wear resistance. At the same time, the ether bond contained has hydrophobicity, reducing water penetration and inhibiting the swelling and shrinkage of the matrix caused by hydration, improving weather resistance.

[0020] 3. Adding the prepared composite anti - pollution agent to the preparation process of the soft light brick can effectively improve its anti - pollution performance, wear resistance and self - repair performance. The long - chain alkyl group contained in the composite anti - pollution agent can form a hydrophobic layer on the surface of the soft light brick, reducing the surface energy and reducing the adsorption of water molecules and oily pollutants. At the same time, the benzene - ring structure contained can form a dense shielding layer on the surface of the soft light layer, preventing the penetration of corrosive ions, making the soft light brick have excellent anti - pollution performance. The cross - linked structure contained in the composite anti - pollution agent can absorb impact energy, improve wear resistance, and the presence of disulfide bonds can break and recombine under the action of light or heat to repair surface cracks and improve its self - repair ability. Specific embodiments

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0022] Embodiment 1: This embodiment discloses a preparation method of a hardening agent, including the following steps: Q1: Under an ice bath environment, 9 mL of phosphorus oxychloride is added dropwise to 4 mL of N,N-dimethylformamide. After the addition is completed, it is stirred at room temperature for 30 min to obtain a mixed solution 1. Then, 2.5 g of 2,7-dimethoxynaphthalene is added to 11 mL of dichloromethane, and stirred until dissolved to obtain a mixed solution 2. The mixed solution 1 is added dropwise to the mixed solution 2. After the addition is completed, it is stirred at room temperature for 10 h, then added to 300 mL of deionized water, stirred for 3 h, the pH is adjusted to 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, recrystallized, and vacuum dried to obtain intermediate 1; Q2: 0.55 g of intermediate 1 is added to 9 mL of dichloromethane. Under a nitrogen and ice bath environment, 6 mL of a boron tribromide solution with a concentration of 0.526 g / mL is slowly added dropwise. After the addition is completed, it is stirred at room temperature for 12 h. After the reaction is completed, the product is added dropwise to a container containing 100 mL of deionized water under an ice bath environment. After the addition is completed, it is continuously stirred at room temperature for 3 h, the pH is adjusted to 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, and purified to obtain intermediate 2; Q3: Under a nitrogen atmosphere, 50 g of diglycolic acid is added to 132 mL of acid anhydride, heated and stirred under reflux for 10 h. After the reflux is completed, 0.08 mL of phosphoric acid is added to catalyze the reaction for 2 h. After the reaction is completed, it is rotary evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3; 10.8 g of pyrrolidine is added to a container containing 150 mL of dichloromethane, and then 17.4 g of intermediate 3 is added, and stirred at room temperature for 2 h. After the reaction is completed, it is rotary evaporated and crystallized at low temperature to obtain intermediate 4; Q4: 2.086 g of intermediate 2 is added to 22.5 mL of N,N-dimethylformamide. Under stirring conditions, 3.61 g of intermediate 4 is added, and then 0.035 g of concentrated sulfuric acid with a mass fraction of 98 wt% is added dropwise. It is heated and stirred at 45 °C for 6 h, extracted, the pH is adjusted, extracted, dried, distilled and concentrated under reduced pressure, and purified to obtain the hardening agent.

[0023] This embodiment discloses a preparation method of a composite anti-fouling agent, including the following steps: S1: Under an ice bath environment, 20.27 g of dodecyl mercaptan, 1.02 g of methyltrioctylammonium chloride, and 55 g of acetone were successively added to a reaction vessel. Subsequently, 20 mL of a sodium hydroxide solution with a mass fraction of 50 wt% was added dropwise, and the mixture was stirred for 20 min. Then, 10 g of acetone and 7.6 g of carbon disulfide were added, and the reaction was carried out. Then, 17.93 g of chloroform and 40 mL of a sodium hydroxide solution with a mass fraction of 50 wt% were added. After the addition was complete, the mixture was stirred in an ice bath for 12 h. After the stirring was completed, purification was carried out to obtain product A; S2: 9.16 g of 4-vinylbenzyl chloride and 18.83 g of triphenylphosphine were successively added to a container containing 105 mL of acetone, and the mixture was stirred for 10 min. After evacuating the air, the reaction was heated at 62 °C for 48 h. After the reaction was completed, sedimentation, washing, vacuum filtration, and drying were carried out to obtain product B; S3: 4.17 g of product A, 0.09 g of product B, and 13.5 mL of methanol were successively added to a container. Then, 0.035 g of azobisisobutyronitrile was added, and the mixture was stirred for 10 min. After evacuating the air, the reaction was heated at 65 °C for 20 h. The reaction was quenched in a liquid nitrogen environment, frozen, dialyzed, and vacuum dried to obtain product C; 0.021 g of product C, 0.031 g of divinylbenzene, 5 mL of methanol, and 0.003 g of azobisisobutyronitrile were successively added to a container, and the mixture was stirred and reacted for 10 min. After evacuating the air, the reaction was heated at 70 °C for 15 h. The reaction was quenched in liquid nitrogen, sedimented, and purified to obtain the composite anti-fouling agent.

[0024] This example discloses a preparation method of a soft light brick with a super anti-fouling coating, including the following steps: Step 1: 45 g of kaolin, 25 g of quartz sand, 20.5 g of feldspar, 10.5 g of clay, and 0.6 g of dispersant were mixed, and wet ball milling was carried out. During the wet ball milling process, the ball-to-material ratio was 2:1, zirconia balls were used as the grinding medium, and the mixture was ground at 300 - 500 rpm for 6 h. The fineness of the slurry was controlled to be ≤5 μm. After the ball milling was completed, the mixture was left standing at 25 °C for 48 h to obtain a mixed material; Step 2: The mixed material was pressed at 35 MPa for 120 s and dried by 2.45 GHz microwave. The sintering process was as follows: The temperature was raised from room temperature to 300 °C at a heating rate of 3 °C / min, held for 45 min, then the temperature was raised from 300 °C to 1180 °C at a heating rate of 5 °C / min, held for 90 min, and then naturally cooled to 200 °C and taken out of the furnace to obtain the substrate; Step 3: The substrate was sandblasted with 120-mesh corundum sand, the compressed air pressure was 0.6 MPa, and the spraying distance was 25 cm. Then, a hardening agent was sprayed, and then the composite anti-fouling agent was sprayed, cured, and polished to obtain a soft light brick with a super anti-fouling coating.

[0025] Example 2: This example discloses a preparation method of a hardening agent, including the following steps: Q1: Under an ice bath environment, 8 mL of phosphorus oxychloride was added dropwise to 5 mL of N,N-dimethylformamide. After the addition was completed, the mixture was stirred at room temperature for 30 min to obtain mixed solution 1. Then, 3 g of 2,7-dimethoxynaphthalene was added to 10 mL of dichloromethane and stirred until dissolved to obtain mixed solution 2. Mixed solution 1 was added dropwise to mixed solution 2. After the addition was completed, the mixture was stirred at room temperature for 10 h, then added to 300 mL of deionized water, stirred for 3 h, the pH was adjusted to 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, recrystallized, and vacuum dried to obtain intermediate 1; Q2: 0.45 g of intermediate 1 was added to 10 mL of dichloromethane. Under a nitrogen and ice bath environment, 5 mL of boron tribromide solution with a concentration of 0.526 g / mL was slowly added dropwise. After the addition was completed, the mixture was stirred at room temperature for 12 h. After the reaction was completed, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath environment. After the addition was completed, the mixture was stirred at room temperature for another 3 h, the pH was adjusted to 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, and purified to obtain intermediate 2; Q3: Under a nitrogen atmosphere, 45 g of diglycolic acid was added to 120 mL of acid anhydride, heated and stirred under reflux for 10 h. After the reflux was completed, 0.09 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction was completed, rotary evaporation was carried out under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3; 10.2 g of pyrrolidine was added to a container containing 140 mL of dichloromethane, and then 17.1 g of intermediate 3 was added. The mixture was stirred at room temperature for 2 h. After the reaction was completed, rotary evaporation was carried out, and crystallization was carried out at low temperature to obtain intermediate 4; Q4: 2.068 g of intermediate 2 was added to 20 mL of N,N-dimethylformamide. Under stirring conditions, 3.5 g of intermediate 4 was added, and then 0.03 g of concentrated sulfuric acid with a mass fraction of 98 wt% was added dropwise. The mixture was heated and stirred at 45 °C for 6 h, extracted, the pH was adjusted, extracted, dried, distilled and concentrated under reduced pressure, and purified to obtain the hardening agent.

[0026] This example discloses a preparation method of a composite anti-fouling agent, including the following steps: S1: Under an ice bath environment, 20.12 g of n-dodecyl mercaptan, 0.98 g of methyltrioctylammonium chloride, and 55 g of acetone were successively added to a reaction vessel. Subsequently, 20 mL of sodium hydroxide solution with a mass fraction of 50 wt% was added dropwise, and the mixture was stirred for 20 min. Then, 10 g of acetone and 7.2 g of carbon disulfide were added and reacted. Then, 17.12 g of chloroform and 40 mL of sodium hydroxide solution with a mass fraction of 50 wt% were added. After the addition was completed, the mixture was stirred at an ice bath for 12 h. After the stirring was completed, purification was carried out to obtain product A; S2: Add 9.01 g of 4-vinylbenzyl chloride and 18.45 g of triphenylphosphine into a container containing 90 mL of acetone in sequence, stir for 10 min, heat and react at 62 °C for 48 h after evacuating the air. After the reaction ends, settle, wash, filter under vacuum, and dry to obtain product B; S3: Add 4.01 g of product A, 0.1 g of product B and 15 mL of methanol into a container in sequence, then add 0.02 g of azobisisobutyronitrile, stir for 10 min, evacuate the air, heat and react at 65 °C for 20 h, quench the reaction in a liquid nitrogen environment, freeze, dialyze, and dry under vacuum to obtain product C; Add 0.01 g of product C, 0.028 g of divinylbenzene, 4 mL of methanol and 0.002 g of azobisisobutyronitrile into a container in sequence, stir and react for 10 min, evacuate the air, heat and react at 70 °C for 15 h, quench the reaction in liquid nitrogen, settle, and purify to obtain the composite anti-fouling agent.

[0027] This example discloses a preparation method of a soft light brick with a super anti-fouling coating, including the following steps: Step 1: Mix 40 g of kaolin, 22 g of quartz sand, 18 g of feldspar, 8 g of clay and 0.4 g of dispersant, and perform wet ball milling. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, grind at 300 - 500 rpm for 6 h, control the fineness of the slurry to be ≤5 μm. After the ball milling ends, let it stand at 25 °C for 48 h to obtain the mixed material; Step 2: Press the mixed material at 35 MPa for 120 s, dry it with 2.45 GHz microwave, and sinter. The sintering process is as follows: Heat from room temperature to 300 °C at a heating rate of 3 °C / min, hold for 45 min, then heat from 300 °C to 1180 °C at a heating rate of 5 °C / min, hold for 90 min, and then naturally cool to 200 °C and take it out of the furnace to obtain the substrate; Step 3: Sandblast the substrate with 120-mesh corundum sand, the compressed air pressure is 0.6 MPa, the spraying distance is 25 cm, then spray the hardening agent, and then spray the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0028] Example 3: This example discloses a preparation method of a hardening agent, including the following steps: Q1: Under an ice bath environment, 10 mL of phosphorus oxychloride was added dropwise to 3 mL of N,N-dimethylformamide. After the addition was completed, the mixture was stirred at room temperature for 30 min to obtain mixed solution 1. Then, 2 g of 2,7-dimethoxynaphthalene was added to 12 mL of dichloromethane and stirred until dissolved to obtain mixed solution 2. Mixed solution 1 was added dropwise to mixed solution 2. After the addition was completed, the mixture was stirred at room temperature for 10 h, then added to 300 mL of deionized water, stirred for 3 h, adjusted to pH = 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, recrystallized, and vacuum dried to obtain intermediate 1; Q2: 0.65 g of intermediate 1 was added to 8 mL of dichloromethane. Under a nitrogen and ice bath environment, 7 mL of boron tribromide solution with a concentration of 0.526 g / mL was slowly added dropwise. After the addition was completed, the mixture was stirred at room temperature for 12 h. After the reaction was completed, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath environment. After the addition was completed, the mixture was stirred at room temperature for 3 h, adjusted to pH = 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, and purified to obtain intermediate 2; Q3: Under a nitrogen atmosphere, 55 g of diglycolic acid was added to 145 mL of acid anhydride, heated and stirred under reflux for 10 h. After the reflux was completed, 0.07 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction was completed, rotary evaporation was carried out under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3; 11.4 g of pyrrolidine was added to a container containing 160 mL of dichloromethane, and then 17.8 g of intermediate 3 was added. The mixture was stirred at room temperature for 2 h. After the reaction was completed, rotary evaporation was carried out, and crystallization was carried out at low temperature to obtain intermediate 4; Q4: 2.124 g of intermediate 2 was added to 25 mL of N,N-dimethylformamide. Under stirring conditions, 3.83 g of intermediate 4 was added, and then 0.04 g of concentrated sulfuric acid with a mass fraction of 98 wt% was added dropwise. The mixture was heated and stirred at 45 °C for 6 h, extracted, the pH was adjusted, extracted, dried, distilled and concentrated under reduced pressure, and purified to obtain a hardening agent.

[0029] This example discloses a preparation method of a composite anti-fouling agent, which includes the following steps: S1: Under an ice bath environment, 20.4 g of n-dodecyl mercaptan, 1.05 g of methyltrioctylammonium chloride, and 55 g of acetone were successively added to a reaction vessel. Subsequently, 20 mL of sodium hydroxide solution with a mass fraction of 50 wt% was added dropwise, and the mixture was stirred for 20 min. Then, 10 g of acetone and 8.1 g of carbon disulfide were added and reacted. Then, 18.74 g of chloroform and 40 mL of sodium hydroxide solution with a mass fraction of 50 wt% were added. After the addition was completed, the mixture was stirred at an ice bath for 12 h. After the stirring was completed, purification was carried out to obtain product A; S2: Add 9.32 g of 4-vinylbenzyl chloride and 19.12 g of triphenylphosphine into a container filled with 120 mL of acetone in sequence, stir for 10 min, heat and react at 62 °C for 48 h after evacuating the air. After the reaction ends, sediment, wash, filter under vacuum, and dry to obtain product B; S3: Add 4.33 g of product A, 0.08 g of product B, and 12 mL of methanol into a container in sequence, then add 0.05 g of azobisisobutyronitrile, stir for 10 min, evacuate the air, heat and react at 65 °C for 20 h, quench the reaction in a liquid nitrogen environment, freeze, dialyze, and dry under vacuum to obtain product C; Add 0.032 g of product C, 0.034 g of divinylbenzene, 6 mL of methanol, and 0.005 g of azobisisobutyronitrile into a container in sequence, stir and react for 10 min, evacuate the air, heat and react at 70 °C for 15 h, quench the reaction in liquid nitrogen, sediment, and purify to obtain the composite anti-fouling agent.

[0030] This example discloses a preparation method of a soft light brick with a super anti-fouling coating, including the following steps: Step 1: Mix 50 g of kaolin, 28 g of quartz sand, 23 g of feldspar, 13 g of clay, and 0.8 g of dispersant, and perform wet ball milling. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, grind at 300 - 500 rpm for 6 h, control the fineness of the slurry to be ≤ 5 μm. After the ball milling ends, let it stand at 25 °C for 48 h to obtain the mixed material; Step 2: Press the mixed material at 35 MPa for 120 s, dry it with 2.45 GHz microwave, and sinter. The sintering process is as follows: Heat from room temperature to 300 °C at a heating rate of 3 °C / min, hold for 45 min, then heat from 300 °C to 1180 °C at a heating rate of 5 °C / min, hold for 90 min, and then naturally cool to 200 °C and take it out of the furnace to obtain the substrate; Step 3: Sandblast the substrate with 120-mesh corundum sand, the compressed air pressure is 0.6 MPa, the spraying distance is 25 cm, then spray the hardening agent, and then spray the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0031] Example 4: This example discloses a preparation method of a hardening agent, including the following steps: Q1: Under an ice bath environment, 8.5 mL of phosphorus oxychloride was added dropwise to 3.2 mL of N,N-dimethylformamide. After the addition was complete, the mixture was stirred at room temperature for 30 min to obtain mixed solution 1. Then, 2.1 g of 2,7-dimethoxynaphthalene was added to 10.5 mL of dichloromethane and stirred until dissolved to obtain mixed solution 2. Mixed solution 1 was added dropwise to mixed solution 2. After the addition was complete, the mixture was stirred at room temperature for 10 h, then added to 300 mL of deionized water, stirred for 3 h, adjusted to pH = 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, recrystallized, and vacuum dried to obtain intermediate 1; Q2: 0.5 g of intermediate 1 was added to 8.5 mL of dichloromethane. Under a nitrogen and ice bath environment, 6.5 mL of boron tribromide solution with a concentration of 0.526 g / mL was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 h. After the reaction was complete, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath environment. After the addition was complete, the mixture was stirred at room temperature for another 3 h, adjusted to pH = 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, and purified to obtain intermediate 2; Q3: Under a nitrogen atmosphere, 48 g of diglycolic acid was added to 128 mL of acid anhydride, and the mixture was heated, stirred, and refluxed for 10 h. After refluxing was complete, 0.075 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction was complete, the mixture was rotary evaporated under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3; 10.5 g of pyrrolidine was added to a container containing 145 mL of dichloromethane, and then 17.3 g of intermediate 3 was added. The mixture was stirred at room temperature for 2 h. After the reaction was complete, it was rotary evaporated and crystallized at low temperature to obtain intermediate 4; Q4: 2.073 g of intermediate 2 was added to 22 mL of N,N-dimethylformamide. Under stirring conditions, 3.55 g of intermediate 4 was added, and then 0.032 g of concentrated sulfuric acid with a mass fraction of 98 wt% was added dropwise. The mixture was heated and stirred at 45 °C for 6 h, extracted, the pH was adjusted, extracted again, dried, distilled and concentrated under reduced pressure, and purified to obtain a hardening agent.

[0032] This example discloses a preparation method of a composite anti-fouling agent, which includes the following steps: S1: Under an ice bath environment, 20.18 g of n-dodecyl mercaptan, 1.01 g of methyltrioctylammonium chloride, and 55 g of acetone were successively added to a reaction vessel. Subsequently, 20 mL of a sodium hydroxide solution with a mass fraction of 50 wt% was added dropwise, and the mixture was stirred for 20 min. Then, 10 g of acetone and 7.4 g of carbon disulfide were added and reacted. Then, 17.51 g of chloroform and 40 mL of a sodium hydroxide solution with a mass fraction of 50 wt% were added dropwise. After the addition was complete, the mixture was stirred at ice bath for 12 h. After stirring was complete, it was purified to obtain product A; S2: Add 9.08 g of 4-vinylbenzyl chloride and 18.62 g of triphenylphosphine into a container containing 95 mL of acetone in sequence, stir for 10 min, heat and react at 62 °C for 48 h after evacuating the air. After the reaction ends, sediment, wash, filter under vacuum, and dry to obtain product B; S3: Add 4.09 g of product A, 0.085 g of product B, and 14 mL of methanol into a container in sequence, then add 0.03 g of azobisisobutyronitrile, stir for 10 min, evacuate the air, heat and react at 65 °C for 20 h, quench the reaction in a liquid nitrogen environment, freeze, dialyze, and dry under vacuum to obtain product C; Add 0.018 g of product C, 0.029 g of divinylbenzene, 4.5 mL of methanol, and 0.004 g of azobisisobutyronitrile into a container in sequence, stir and react for 10 min, evacuate the air, heat and react at 70 °C for 15 h, quench the reaction in liquid nitrogen, sediment, and purify to obtain the composite anti-fouling agent.

[0033] This example discloses a preparation method of a soft light brick with a super anti-fouling coating, including the following steps: Step 1: Mix 42 g of kaolin, 23 g of quartz sand, 19 g of feldspar, 9 g of clay, and 0.5 g of dispersant, and perform wet ball milling. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, grind at 300 - 500 rpm for 6 h, control the fineness of the slurry to be ≤5 μm. After the ball milling ends, let it stand at 25 °C for 48 h to obtain the mixed material; Step 2: Press the mixed material at 35 MPa for 120 s, dry it with 2.45 GHz microwave, and sinter. The sintering process is as follows: heat from room temperature to 300 °C at a heating rate of 3 °C / min, hold for 45 min, then heat from 300 °C to 1180 °C at a heating rate of 5 °C / min, hold for 90 min, and then naturally cool to 200 °C and take it out of the furnace to obtain the substrate; Step 3: Sandblast the substrate with 120-mesh corundum sand, the compressed air pressure is 0.6 MPa, the spraying distance is 25 cm, then spray the hardening agent, and then spray the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0034] Example 5: This example discloses a preparation method of a hardening agent, including the following steps: Q1: Under an ice bath environment, 9.5 mL of phosphorus oxychloride was added dropwise to 4.8 mL of N,N-dimethylformamide. After the addition was completed, the mixture was stirred at room temperature for 30 min to obtain mixed solution 1. Then, 2.9 g of 2,7-dimethoxynaphthalene was added to 11.5 mL of dichloromethane and stirred until dissolved to obtain mixed solution 2. Mixed solution 1 was added dropwise to mixed solution 2. After the addition was completed, the mixture was stirred at room temperature for 10 h, then added to 300 mL of deionized water, stirred for 3 h, the pH was adjusted to 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, recrystallized, and vacuum dried to obtain intermediate 1; Q2: 0.6 g of intermediate 1 was added to 9.5 mL of dichloromethane. Under a nitrogen and ice bath environment, 7.5 mL of boron tribromide solution with a concentration of 0.526 g / mL was slowly added dropwise. After the addition was completed, the mixture was stirred at room temperature for 12 h. After the reaction was completed, the product was added dropwise to a container containing 100 mL of deionized water under an ice bath environment. After the addition was completed, the mixture was stirred at room temperature for another 3 h, the pH was adjusted to 7 with saturated sodium bicarbonate solution, extracted with dichloromethane, dried, rotary evaporated under reduced pressure, and purified to obtain intermediate 2; Q3: Under a nitrogen atmosphere, 52 g of diglycolic acid was added to 141 mL of acid anhydride, heated and stirred under reflux for 10 h. After the reflux was completed, 0.085 mL of phosphoric acid was added to catalyze the reaction for 2 h. After the reaction was completed, rotary evaporation was carried out under reduced pressure, concentrated, crystallized at low temperature, and filtered to obtain intermediate 3; 11.1 g of pyrrolidine was added to a container containing 155 mL of dichloromethane, and then 17.6 g of intermediate 3 was added. The mixture was stirred at room temperature for 2 h. After the reaction was completed, rotary evaporation was carried out, and crystallization was carried out at low temperature to obtain intermediate 4; Q4: 2.095 g of intermediate 2 was added to 24 mL of N,N-dimethylformamide. Under stirring conditions, 3.71 g of intermediate 4 was added, and then 0.038 g of concentrated sulfuric acid with a mass fraction of 98 wt% was added dropwise. The mixture was heated and stirred at 45 °C for 6 h, extracted, the pH was adjusted, extracted again, dried, distilled and concentrated under reduced pressure, and purified to obtain a hardening agent.

[0035] This example discloses a preparation method of a composite anti-fouling agent, including the following steps: S1: Under an ice bath environment, 20.33 g of n-dodecyl mercaptan, 1.03 g of methyltrioctylammonium chloride and 55 g of acetone were successively added to a reaction vessel. Subsequently, 20 mL of sodium hydroxide solution with a mass fraction of 50 wt% was added dropwise, and the mixture was stirred for 20 min. Then, 10 g of acetone and 8 g of carbon disulfide were added and reacted. Then, 18.53 g of chloroform and 40 mL of sodium hydroxide solution with a mass fraction of 50 wt% were added. After the addition was completed, the mixture was stirred at an ice bath for 12 h. After the stirring was completed, purification was carried out to obtain product A; S2: Add 9.24 g of 4-vinylbenzyl chloride and 19.01 g of triphenylphosphine into a container containing 115 mL of acetone in sequence, stir for 10 min, evacuate the air, heat and react at 62 °C for 48 h. After the reaction, sediment, wash, filter under vacuum, and dry to obtain product B. S3: Add 4.23 g of product A, 0.095 g of product B and 13 mL of methanol into a container in sequence, then add 0.04 g of azobisisobutyronitrile, stir for 10 min, evacuate the air, heat and react at 65 °C for 20 h, quench the reaction in a liquid nitrogen environment, freeze, dialyze, and dry under vacuum to obtain product C. Add 0.027 g of product C, 0.033 g of divinylbenzene, 5.5 mL of methanol and 0.0045 g of azobisisobutyronitrile into a container in sequence, stir and react for 10 min, evacuate the air, heat and react at 70 °C for 15 h, quench the reaction in liquid nitrogen, sediment, and purify to obtain the composite anti-fouling agent.

[0036] This example discloses a preparation method of a soft light brick with a super anti-fouling coating, including the following steps: Step 1: Mix 48 g of kaolin, 26 g of quartz sand, 22 g of feldspar, 11 g of clay and 0.7 g of dispersant, and perform wet ball milling. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, grind at 300 - 500 rpm for 6 h, control the fineness of the slurry ≤ 5 μm. After the ball milling, let it stand at 25 °C for 48 h to obtain the mixed material. Step 2: Press the mixed material at 35 MPa for 120 s, dry it with 2.45 GHz microwave, and sinter. The sintering process is as follows: heat from room temperature to 300 °C at a heating rate of 3 °C / min, hold for 45 min, then heat from 300 °C to 1180 °C at a heating rate of 5 °C / min, hold for 90 min, and then naturally cool to 200 °C and take it out of the furnace to obtain the substrate. Step 3: Sandblast the substrate with 120-mesh corundum sand, the compressed air pressure is 0.6 MPa, the spraying distance is 25 cm, then spray the hardening agent, and then spray the composite anti-fouling agent, cure, and polish to obtain a soft light brick with a super anti-fouling coating.

[0037] Comparative Example 1: Compared with Example 1, in the process of preparing the soft light brick in Comparative Example 1, the hardening agent is not sprayed, and other conditions remain unchanged.

[0038] Comparative Example 2: Compared with Example 1, in the process of preparing the soft light brick in Comparative Example 2, the composite anti-fouling agent is not sprayed, and other conditions remain unchanged.

[0039] Experimental Example: Test the soft light bricks prepared in Examples 1 - 5 and Comparative Examples 1 - 2, and test the performance of the samples according to GB / T 4100 - 2015. The test results are shown in Table 1: Table 1 As can be seen from the test results in Table 1, the soft light bricks prepared in Examples 1-5 of the present invention have excellent hardness, weather resistance, stain resistance and wear resistance. By comparing Comparative Example 1 with Examples 1-5, it can be seen that spraying a hardening agent can effectively improve its hardness, wear resistance and weather resistance; by comparing Comparative Example 2 with Examples 1-5, it can be seen that spraying a composite anti-stain agent can effectively improve its stain resistance and wear resistance.

[0040] As described above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

[0041] 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 present invention to only the specific embodiments. Obviously, many modifications and changes can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A preparation method of a soft light brick with a super anti-fouling coating, characterized in that, It includes the following steps: Step 1: Mix kaolin, quartz sand, feldspar, clay and a dispersant, and adopt wet ball milling. After the ball milling is completed, let it stand still to obtain a mixed material. Step 2: Press the mixed material, dry it by microwave, and sinter it to obtain a substrate. Step 3: Sandblast the substrate, then spray a hardening agent, and then spray a composite anti-fouling agent, cure it, and polish it to obtain a soft light brick with a super anti-fouling coating. Among them, the hardening agent is prepared from phosphorus oxychloride, 2,7-dimethoxynaphthalene, boron tribromide solution, diglycolic acid and pyrrolidine as the main raw materials, and the composite anti-fouling agent is prepared from n-dodecyl mercaptan, carbon disulfide, methyltrioctylammonium chloride, 4-vinylbenzyl chloride, triphenylphosphine and divinylbenzene as the main raw materials.

2. The preparation method of a soft light tile with a super anti-fouling coating according to claim 1, characterized in that, In the said Step 1, the dosage ratio of kaolin, quartz sand, feldspar, clay and the dispersant is (40 - 50) g : (22 - 28) g : (18 - 23) g : (8 - 13) g : (0.4 - 0.8) g. During the wet ball milling process, the ball-to-material ratio is 2:1, zirconia balls are used as the grinding medium, grind at 300 - 500 rpm for 4 - 6 h, control the fineness of the slurry ≤ 5 μm, and let it stand still at 25 °C for 40 - 50 h.

3. The preparation method of a soft light tile with a super anti-fouling coating according to claim 1, characterized in that, In the said Step 2, during the pressing process, keep the pressure at 30 - 35 MPa for 110 - 140 s, the microwave drying frequency is 2.45 GHz, and the sintering process is as follows: heat from room temperature to 300 °C at a heating rate of 3 °C / min, keep warm for 30 - 45 min, then heat from 300 °C to 1180 °C at a heating rate of 5 °C / min, keep warm for 80 - 100 min, and then naturally cool to 200 - 220 °C and then take out of the furnace; in the said Step 3, during the sandblasting treatment, use 120-mesh corundum sand, the compressed air pressure is 0.5 - 0.8 MPa, and the spraying distance is 20 - 30 cm.

4. The preparation method of a soft light brick with a super anti-fouling coating according to claim 1, characterized in that, The preparation method of the said hardening agent includes the following steps: Q1: Under an ice bath environment, drop phosphorus oxychloride into N,N-dimethylformamide. After the dropping is completed, stir at room temperature to obtain a mixed solution 1. Then add 2,7-dimethoxynaphthalene to dichloromethane, stir and dissolve to obtain a mixed solution 2. Drop the mixed solution 1 into the mixed solution 2. After the dropping is completed, stir at room temperature, then add it to deionized water, stir, adjust the pH, extract, dry, perform reduced pressure rotary evaporation, recrystallize, and vacuum dry to obtain intermediate 1. Q2: Add intermediate 1 to dichloromethane. Under a nitrogen and ice bath environment, slowly drop the boron tribromide solution. After the dropping is completed, stir and react at room temperature. After the reaction is completed, drop the product into a container filled with deionized water under an ice bath environment. After the dropping is completed, continue to stir and react at room temperature, adjust the pH, extract, dry, perform reduced pressure rotary evaporation, and purify to obtain intermediate 2. Q3: Under a nitrogen atmosphere, add diglycolic acid to an acid anhydride, heat and stir to reflux. After the reflux is completed, add phosphoric acid to catalyze the reaction. After the reaction is completed, perform reduced pressure rotary evaporation, concentrate, crystallize at low temperature, and filter to obtain intermediate 3; add pyrrolidine to a container filled with dichloromethane, then add intermediate 3, stir and react at room temperature. After the reaction is completed, perform rotary evaporation and crystallize at low temperature to obtain intermediate 4. Q4: Add intermediate 2 to N,N-dimethylformamide, add intermediate 4 under stirring conditions, then dropwise add concentrated sulfuric acid, heat and stir for reaction, extract, adjust the pH, extract, dry, concentrate by distillation under reduced pressure, and purify to obtain the hardening agent.

5. The preparation method of a soft light brick with a super anti-fouling coating according to claim 4, characterized in that, In Q1, the dosage ratio of phosphorus oxychloride, N,N-dimethylformamide, 2,7-dimethoxynaphthalene and dichloromethane is (8 - 10) mL : (3 - 5) mL : (2 - 3) g : (10 - 12) mL; in Q2, the dosage ratio of intermediate 1, dichloromethane and boron tribromide solution is (0.45 - 0.65) g : (8 - 10) mL : (5 - 7) mL, and the concentration of the boron tribromide solution is 0.526 g / mL.

6. The preparation method of a soft light tile with a super anti-fouling coating according to claim 4, characterized in that, In Q3, the dosage ratio of diglycolic acid, acid anhydride and phosphoric acid is (45 - 55) g : (120 - 145) mL : (0.07 - 0.09) mL; the dosage ratio of pyrrolidine, dichloromethane and intermediate 3 is (10.2 - 11.4) g : (140 - 160) mL : (17.1 - 17.8) g; in Q4, the dosage ratio of intermediate 2, N,N-dimethylformamide, intermediate 4 and concentrated sulfuric acid is (2.068 - 2.124) g : (20 - 25) mL : (3.5 - 3.83) g : (0.03 - 0.04) g.

7. The preparation method of a soft light brick with a super anti-fouling coating according to claim 1, characterized in that, The preparation method of the composite anti-fouling agent includes the following steps: S1: Under an ice bath environment, add dodecyl mercaptan, methyltrioctylammonium chloride and acetone to the reaction vessel in sequence, then dropwise add sodium hydroxide solution, stir, then continue to add acetone and carbon disulfide, react, then add chloroform and sodium hydroxide solution, after dropping, stir in the ice bath, after the stirring ends, purify to obtain product A; S2: Add 4-vinylbenzyl chloride and triphenylphosphine to the container filled with acetone in sequence, stir, heat the reaction after evacuating, after the reaction ends, sediment, wash, filter by vacuum, and dry to obtain product B; S3: Add product A, product B and methanol to the container in sequence, then add azobisisobutyronitrile, stir, evacuate, heat the reaction, quench the reaction in a liquid nitrogen environment, freeze, dialyze, and dry in vacuum to obtain product C; add product C, divinylbenzene, methanol and azobisisobutyronitrile to the container in sequence, stir and react, evacuate, heat the reaction, quench the reaction in liquid nitrogen, sediment, and purify to obtain the composite anti-fouling agent.

8. The preparation method of a soft light brick with a super anti-fouling coating according to claim 7, characterized in that, In S1, the dosage ratio of dodecyl mercaptan, methyltrioctylammonium chloride, carbon disulfide and chloroform is (20.12 - 20.4) g : (0.98 - 1.05) g : (7.2 - 8.1) g : (17.12 - 18.74) g; in S2, the dosage ratio of 4-vinylbenzyl chloride, triphenylphosphine and acetone is (9.01 - 9.32) g : (18.45 - 19.12) g : (90 - 120) mL.

9. The preparation method of a soft light brick with a super anti-fouling coating according to claim 7, characterized in that, In S3, the dosage ratio of product A, product B, methanol and azobisisobutyronitrile is (4.01 - 4.33) g : (0.08 - 0.1) g : (12 - 15) mL : (0.02 - 0.05) g; the dosage ratio of product C, divinylbenzene, methanol and azobisisobutyronitrile is (0.01 - 0.032) g : (0.028 - 0.034) g : (4 - 6) mL : (0.002 - 0.005) g.

10. A soft light brick with a super anti-fouling coating prepared by the method according to any one of claims 1 - 9.

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