High-temperature-resistant non-stick ceramic coating and preparation method thereof

Abstract

The application discloses a high-temperature-resistant non-stick ceramic coating and a preparation method thereof. The ceramic coating comprises an A component and a B component in a mass ratio of 1-3:1. The A component comprises the following raw materials in parts by mass: 100 parts of an inorganic adhesive, 1-30 parts of pigments, 10-20 parts of fillers, and 1-5 parts of a dispersing agent. The B component comprises the following components in parts by mass: 0.3-2 parts of a catalyst, 40-100 parts of silane, 1-10 parts of a non-stick additive, 2-10 parts of an auxiliary agent, and 1-10 parts of a solvent. The silane comprises polyether silane and phenyl silane, the polyether silane accounts for 20-30% of the total mass of the silane, and the phenyl silane accounts for 10-20% of the total mass of the silane. The application can effectively solve the problems of existing non-stick ceramic coatings, such as easy cracking and peeling due to excessive rigidity and insufficient toughness, and attenuation of non-stick performance.

Description

Technical Field

[0001] This application relates to the field of ceramic coatings, and in particular to a high-temperature resistant non-stick ceramic coating and its preparation method. Background Technology

[0002] Non-stick ceramic coatings are widely used in kitchenware, home appliances, industrial molds, and other fields requiring heat resistance and non-stick properties due to their excellent high-temperature resistance, good surface non-stickness, and high surface hardness. Compared with traditional organic non-stick coatings (such as polytetrafluoroethylene), ceramic coatings are mainly composed of inorganic materials, exhibiting higher thermal stability and wear resistance, and are less likely to release harmful substances during use, thus attracting increasing attention. Currently, commercially available non-stick ceramic coatings typically use inorganic sols such as silica sol and alumina sol as the main film-forming substances, combined with silane coupling agents or siloxane compounds, forming a three-dimensional network structure through hydrolysis and condensation reactions during the sol-gel process.

[0003] To further improve the hardness and scratch resistance of the coating, existing technologies often add inorganic fillers to the coating system. For example, CN117511268A discloses a non-stick ceramic coating, its preparation method, and its application, which includes hard particles such as zirconium oxide, silicon carbide, alumina, and silica. This technical approach achieves high hardness and high wear resistance in the coating to a certain extent, meeting the wear resistance requirements of daily use. However, due to the strong rigidity of the network formed by the cross-linking of inorganic sol and silane, coupled with the introduction of a large amount of inorganic fillers, the brittleness of the coating is further aggravated, resulting in poor overall toughness. Specifically, high-hardness but low-toughness coatings are prone to microcracks or even peeling during use due to external impacts, thermal expansion and contraction of the substrate, or mechanical deformation. Especially under repeated thermal cycles, friction, or local impacts, the internal stress of the coating is difficult to release effectively, and cracks propagate rapidly. This not only affects the long-term adhesion stability between the coating and the substrate but also significantly reduces the non-stick performance. Summary of the Invention

[0004] This application aims to solve the problem that existing high-temperature resistant non-stick ceramic coatings are prone to cracking and peeling, and their non-stick performance is reduced due to excessive rigidity and insufficient toughness.

[0005] In a first aspect, this application provides a high-temperature resistant non-stick ceramic coating, comprising component A and component B in a mass ratio of 1 to 3:1. Component A comprises the following raw materials in parts by mass: 100 parts inorganic binder, 1 to 30 parts pigment, 10 to 20 parts filler, and 1 to 5 parts dispersant. Component B comprises the following components in parts by mass: 0.3 to 2 parts catalyst, 40 to 100 parts silane, 1 to 10 parts non-stick additive, 2 to 10 parts auxiliary agent, and 1 to 10 parts solvent. The silane comprises polyether silane and phenyl silane, wherein the polyether silane accounts for 20 to 30% of the total mass of silane, and the phenyl silane accounts for 10 to 20% of the total mass of silane.

[0006] In any of the above technical solutions, the polyether silane is prepared by hydrosilylation of allyl polyether and hydrogen-containing siloxane in a molar ratio of 1:1 to 1.1.

[0007] In any of the above technical solutions, the phenylsilane is prepared by hydrosilylation of phenyl vinyl silicone oil and hydrogen-containing siloxane in a mass ratio of 7 to 12:1.

[0008] In any of the above technical solutions, the dynamic viscosity of the phenyl vinyl silicone oil is 300-6000 mPa·s (25°C).

[0009] In any of the above technical solutions, the hydrogen-containing siloxane is selected from at least one of trimethoxysilane, triethoxysilane, methyldimethoxysilane, and ethyldimethoxysilane.

[0010] The application proposes a compounding method using polyether silane and phenyl silane to synergistically resolve the contradiction between high hardness and low toughness in ceramic coatings. Specifically, the polyether silane is prepared by hydrosilylation of allyl polyether and hydrosiloxane. Its molecular structure contains both flexible polyether segments and siloxane groups that can participate in sol-gel crosslinking. When the polyether silane is added to component B and mixed with the inorganic binder of component A, its siloxane groups bond to the inorganic network through hydrolytic condensation. This introduces the flexible polyether segments into the three-dimensional network framework in the form of covalent bonds, effectively reducing the rigidity of the crosslinking points and increasing the mobility of the molecular segments. This allows the coating to release internal stress through segment rearrangement when subjected to external forces or thermal stress, significantly improving flexibility and crack resistance.

[0011] However, the introduction of polyether segments also brings the risk of decreased heat resistance. Polyethers are prone to oxidative degradation or thermal decomposition at high temperatures, leading to coating weight loss, destruction of the cross-linking network, and consequently shortening service life. To address this issue, this application further introduces phenylsilane. This phenylsilane is not a simple small-molecule phenylsilane coupling agent, but a polymeric silane obtained by hydrosilylation reaction of macromolecular phenyl vinyl silicone oil with hydrogen-containing siloxane. The product not only retains a large number of rigid phenyl groups but also forms a flexible siloxane backbone with a moderate cross-linking density. The rigid phenyl groups can significantly improve the heat resistance of the coating, compensating for the insufficient heat resistance of the polyether segments. Simultaneously, the flexibility of the siloxane backbone ensures that the phenylsilane does not degrade the toughness of the coating, improving toughness without sacrificing surface hardness, forming a network structure with a rigid-flexible balance with the polyether silane. Compared to small-molecule phenylsilane coupling agents, this phenylsilane molecule has more siloxane active sites, which can further participate in the cross-linking reaction, enhance the density of the coating and the chemical bonding with the substrate, thereby improving adhesion and wear resistance.

[0012] In any of the above technical solutions, the inorganic adhesive is selected from at least one of silica sol, alumina sol, or zirconium oxide sol.

[0013] In any of the above technical solutions, the filler is selected from one or more of the following: silicon micro powder, silicon nitride, barium sulfate, alumina, mica powder, zirconium boride, silica, talc powder, ceramic powder, whisker silicon, and quartz powder.

[0014] In any of the above technical solutions, the pigment is selected from one or more of titanium dioxide, copper chromium black, iron oxide black, carbon black, manganese iron black, iron oxide yellow, phthalocyanine blue, phthalocyanine green, titanium yellow, bismuth yellow, iron oxide red, cobalt blue, cobalt green, and iron oxide green.

[0015] In any of the above technical solutions, the non-stick additive is selected from one or more of dimethyl silicone oil, hydrogen-containing silicone oil, phenolic hydroxyl silicone oil, amino silicone oil, alcoholic hydroxyl silicone oil, and mercapto silicone oil.

[0016] In any of the above technical solutions, the catalyst is selected from formic acid, acetic acid, or citric acid.

[0017] In any of the above technical solutions, the additives include, but are not limited to, leveling agents and defoamers.

[0018] In any of the above technical solutions, the solvent is selected from alcohol solvents or ether solvents.

[0019] In any of the above technical solutions, the silane further includes one or more of tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and γ-(2,3-epoxypropoxy)propyltriethoxysilane.

[0020] In any of the above technical solutions, the filler contains at least 30-50 wt% modified mesoporous silica, and its preparation method is as follows: Mesoporous silica is impregnated in silicone oil to obtain a carrier filler; Vinyl silicone oil, vinyl silane coupling agent, hydrogen-containing silicone oil, inhibitor and catalyst are mixed to obtain a modified mixture, which is then coated on the surface of the carrier filler and cured by heating. The mass ratio of the vinyl silicone oil, vinyl silane coupling agent, and hydrogen-containing silicone oil is 100:1 to 5:1 to 30, and the amounts of inhibitor and catalyst are 100 to 500 ppm and 5 to 10 ppm, respectively.

[0021] In any of the above technical solutions, the kinematic viscosity of the vinyl silicone oil is 1000–10000 mm.2 / s (25℃).

[0022] In any of the above technical solutions, the silicone oil is selected from one or more of dimethyl silicone oil, hydroxyl silicone oil, and amino silicone oil.

[0023] In any of the above technical solutions, the average particle size of the mesoporous silica is 1–20 μm, and the specific surface area is 200–800 m². 2 / g; its preparation method can be either template method or precipitation method.

[0024] In any of the above technical solutions, the inhibitor is selected from alkynol compounds, including but not limited to etynylcyclohexanol and methylbutynol, preferably etynylcyclohexanol.

[0025] In any of the above technical solutions, the catalyst is a platinum catalyst.

[0026] Traditional ceramic coatings often incorporate silicone oil as a non-stick agent, utilizing its migration to the coating surface to form a low-surface-energy oil film for a non-stick effect. However, free silicone oil tends to rapidly precipitate and leak out under prolonged use or high-temperature environments, leading to a rapid decline in non-stick performance. To address this issue, existing technologies attempt to use porous carriers to adsorb and load silicone oil, achieving slow release through capillary forces within the pores. However, the slow-release period of ordinary porous carriers is limited, and their surfaces easily adsorb dark grease or protein caramelization produced during cooking, compromising the coating's appearance and cleanliness.

[0027] This application modifies mesoporous silica by first impregnating it in silicone oil to fully adsorb the silicone oil within the pores, forming a carrier filler. Then, a silicone rubber layer is coated onto its surface, formed by platinum-catalyzed crosslinking of vinyl silicone oil, vinyl silane coupling agent, and hydrogen-containing silicone oil. This silicone rubber layer has a three-dimensional crosslinked structure, which can physically seal the pores of the mesoporous silica, significantly slowing down the release rate of the internal silicone oil and achieving oil storage and controlled release effects. More importantly, the mesoporous silica particles coated with silicone rubber themselves become an organosilicon elastomer filler; their flexibility and elasticity can buffer the negative impact of rigid inorganic fillers on the coating toughness. When the coating is subjected to external impact or thermal expansion and contraction, these elastomer fillers can undergo reversible deformation, preventing crack propagation. Crucially, after the crosslinking reaction, the siloxane groups on the vinyl silane coupling agent added to the coating raw material are retained in the silicone rubber layer. When modified mesoporous silica is applied and cured in coatings, these siloxane groups undergo hydrolysis and polycondensation reactions with inorganic binders to form strong covalent bonds. This allows the modified filler to chemically bond with the coating matrix, rather than simply being physically filled. On one hand, this ensures uniform dispersion and stable anchoring of the filler in the coating, preventing stress concentration or filler detachment due to interfacial debonding. On the other hand, chemical bonding also provides a channel for stress transmission, enabling the silicone rubber elastomer filler to more effectively absorb and buffer internal stress in the coating, thus improving impact resistance and abrasion resistance.

[0028] This application further limits the kinematic viscosity of the vinyl silicone oil. A suitable viscosity ensures sufficient cross-linking with the hydrogen-containing silicone oil to form a complete coating layer while maintaining good heat resistance and structural stability at high temperatures; it also prevents loss of elasticity due to excessive cross-linking. Therefore, the modified mesoporous silica of this application achieves long-term sustained release of the non-stick additive, improves the toughness of the coating as an elastomer, and avoids direct adsorption of dark-colored contaminants due to its silicone rubber coating, thus comprehensively improving the coating's service life and appearance stability.

[0029] Secondly, this application provides a method for preparing a high-temperature resistant non-stick ceramic coating, comprising: The inorganic binder, pigment, filler and dispersant are mixed according to the mass fractions of component A and stirred evenly to obtain component A; According to the mass fractions of component B, the catalyst, silane, non-sticking agent, additive and solvent are mixed and stirred evenly to obtain component B; Mix component A and component B at a mass ratio of 1 to 3:1 and stir until homogeneous to obtain a high-temperature resistant non-stick ceramic coating.

[0030] In summary, this application has the following beneficial effects: This application employs a specific structure of polyether silane and phenyl silane compounding to introduce flexible polyether segments and heat-resistant phenyl segments into the crosslinked network, achieving a balance between rigidity and toughness. This significantly improves the coating's crack resistance and adhesion, ensuring excellent non-stick and abrasion resistance. Furthermore, the use of silicone rubber-coated modified mesoporous silica as a filler enables both long-term, controllable release of the non-stick additive and utilizes the elastomer's properties to buffer internal stress in the coating, thus improving the toughness degradation defects of traditional rigid fillers. In summary, the coating of this application exhibits excellent flexibility, long-lasting non-stick properties, heat aging resistance, and appearance retention at high temperatures, resulting in a significantly extended service life. Detailed Implementation

[0031] Preparation Example Preparation Example 1-1, polyether silane, was prepared according to the following method: 145.6 g (0.2 mol) of allyl polyether (APEG-700) and 150 mL of toluene were added to a reaction flask as solvents. The mixture was stirred and heated to 70 °C. Nitrogen gas was purged into the flask to purge air, and the nitrogen atmosphere was maintained. The mixture was stirred and heated to 95 °C. A chloroplatinic acid-isopropanol solution (Pt concentration 0.1 mol / L) was added, at a rate of 8 ppm of the total mass of the reaction system (based on platinum atoms). Then, 24.5 g (0.2 mol) of trimethoxysilane was added dropwise. The reaction was exothermic during the addition, and the reaction temperature was controlled at 110–115 °C using a constant temperature water bath. After the addition was complete, the reaction was maintained at this temperature for 4 hours. After the reaction was complete, the reaction system was cooled to below 60 °C, and the toluene solvent and unreacted low-boiling components were removed under vacuum conditions not lower than -0.09 MPa to obtain polyether silane.

[0032] Preparation Examples 1-2: Polyether silanes were prepared according to the following method: 92.8 g (0.16 mol) of allyl polyether (APEG-580) was added to a reaction flask, along with 100 mL of toluene as a solvent. The air in the flask was purged with nitrogen, and the atmosphere was maintained while stirring and heating to 100 °C. A chloroplatinic acid-isopropanol solution (Pt concentration 0.1 mol / L) was added, at a rate of 5 ppm of the total mass of the reaction system (based on platinum atoms). Then, 21.1 g (0.173 mol) of trimethoxysilane was added dropwise, maintaining the reaction temperature between 100 and 105 °C. After the addition was complete, the reaction was maintained at this temperature for 5 hours. After the reaction was complete, the reaction system was cooled to 50 °C, and the toluene solvent and unreacted components were removed under vacuum conditions not lower than -0.09 MPa to obtain polyether silane.

[0033] Preparation Examples 1-3, polyether silanes, were prepared according to the following method: 240.0 g (0.24 mol) of allyl polyether (APEG-1000) and 250 mL of toluene were added to a reaction flask as solvent. The mixture was stirred and heated to 80 °C. Nitrogen gas was purged into the flask to purge air, and the nitrogen atmosphere was maintained. The mixture was stirred and heated to 105 °C. A chloroplatinic acid-isopropanol solution (Pt concentration 0.1 mol / L) was added, at a rate of 10 ppm of the total mass of the reaction system based on platinum atoms. Then, 43.4 g (0.264 mol) of triethoxysilane (hydrosiloxane, purity ≥98%) was added dropwise. The reaction was exothermic during the dropwise addition, and a constant temperature water bath was used to control the reaction temperature at 110–115 °C. After the dropwise addition was complete, the reaction was maintained at this temperature for 6 hours. After the reaction was complete, the reaction system was cooled to 60 °C, and the toluene solvent and unreacted low-boiling components were removed under vacuum conditions not lower than -0.095 MPa to obtain polyether silane.

[0034] Preparation Example 2-1, phenylsilane, was prepared by the following operation: Add 250.0 g of phenyl vinyl silicone oil (Runhe RH-510V-500, viscosity approximately 500 mPa·s) to a reaction flask, along with 200 mL of toluene as a solvent. Purge the air from the flask with nitrogen and maintain the nitrogen atmosphere. Stir and heat to 80°C to ensure complete dissolution of the raw materials. Add a chloroplatinic acid-isopropanol solution (Pt concentration 0.1 mol / L), the amount being 10 ppm of the total mass of the reaction system (based on platinum atoms). Then, begin dropwise addition of 25 g of trimethoxysilane, maintaining the reaction temperature at 110–115°C using a constant-temperature water bath. After the addition is complete, continue the reaction at this temperature for 5 hours. After the reaction is complete, cool the reaction system to below 60°C and remove the toluene solvent and unreacted low-boiling components under vacuum conditions not lower than -0.09 MPa to obtain phenylsilane.

[0035] Preparation Example 2-2, phenylsilane, was prepared by the following operation: 160.0 g of phenyl vinyl silicone oil (Runhe RH-510V-1000, kinematic viscosity approximately 1000 mPa·s) was added to a reaction flask, along with 150 mL of toluene as a solvent. The air in the flask was purged with nitrogen to maintain the nitrogen atmosphere, and the mixture was stirred and heated to 85 °C to ensure complete dissolution of the reactants. A chloroplatinic acid-isopropanol solution (Pt concentration 0.1 mol / L) was added, at a rate of 8 ppm of the total mass of the reaction system (based on platinum atoms). Then, 22.9 g of trimethoxysilane was added dropwise, maintaining the reaction temperature between 100 and 105 °C. After the addition was complete, the reaction was maintained at this temperature for 5 hours. After the reaction was complete, the reaction system was cooled to 50 °C, and the toluene solvent and unreacted components were removed under vacuum conditions not lower than -0.09 MPa to obtain phenylsilane.

[0036] Preparation Example 2-3, phenylsilane, was prepared by the following operation: Add 300.0 g of phenyl vinyl silicone oil (Runhe RH-510V-5000, kinematic viscosity approximately 5000 mPa·s) to a reaction flask, along with 250 mL of toluene as a solvent. Purge the air from the flask with nitrogen and maintain the nitrogen atmosphere. Stir and heat to 90°C to ensure complete dissolution of the raw materials. Add a chloroplatinic acid-isopropanol solution (Pt concentration 0.1 mol / L), at a rate of 12 ppm of the total mass of the reaction system (based on platinum atoms). Then, begin dropwise addition of 25.0 g of triethoxysilane, maintaining the reaction temperature at 110–115°C using a constant-temperature water bath. After the addition is complete, continue the reaction at this temperature for 6 hours. After the reaction is complete, cool the reaction system to 60°C and remove the toluene solvent and unreacted low-boiling components under a vacuum of at least -0.095 MPa to obtain phenylsilane.

[0037] Preparation Example 3-1: Modified mesoporous silica. The preparation steps are as follows: Add mesoporous silica (average particle size 3 μm, specific surface area approximately 350 m²) to the beaker 2 Add 40.0g of dimethyl silicone oil (kinematic viscosity 500 mmHg) to the solution. 2 60.0 g of mesoporous silica and silicone oil were stirred to ensure thorough mixing. The mixture was then allowed to stand at room temperature for 24 hours, with stirring every 6 hours during this period. After impregnation, the mixture was transferred to a Buchner funnel and filtered under a vacuum of 0.06 MPa to remove excess silicone oil from the surface, yielding the carrier filler.

[0038] Take double-ended vinyl silicone oil (kinematic viscosity approximately 5000 mm). 2 100.0g of vinyltrimethoxysilane (at 25°C, vinyl content approximately 0.16wt%), 2.5g of hydrogen-containing silicone oil (hydrogen content 0.36wt%, kinematic viscosity 10-20mm). 2 Add 9.0 g of ( / s) to a flask, add 200 mL of toluene as a solvent, purge the air in the flask with nitrogen and maintain a nitrogen atmosphere, stir and heat to 50 °C to fully dissolve and mix all components, add ethynylcyclohexanol as an inhibitor (300 ppm, based on the total mass of vinyl silicone oil and hydrogen-containing silicone oil), and continue stirring for 5 min. Add platinum catalyst (chloroplatinic acid-isopropanol solution, Pt concentration 0.1 mol / L, 10 ppm, based on the total mass of vinyl silicone oil and hydrogen-containing silicone oil), and stir for 10 min to obtain a modified mixture.

[0039] Add 100.0g of carrier filler to the material tank of the fluidized bed coating machine, turn on the fan to fluidize the material, set the inlet air temperature to 60℃, control the material temperature at 50-55℃, and the atomization pressure to 0.15MPa. Atomize the modified mixture into the fluidized bed, so that the modified mixture uniformly coats the surface of the fluidized carrier filler particles. After spraying, raise the fluidized bed inlet air temperature to 110℃ and continue fluidization, drying, and curing for 2 hours to obtain modified mesoporous silica.

[0040] Preparation Example 3-2: Modified mesoporous silica. The preparation steps are as follows: Add mesoporous silica (average particle size 3 μm, specific surface area approximately 350 m²) to the beaker 2 24.0g of hydroxyl silicone oil (kinematic viscosity 300 mmHg) was added. 2 56.0 g of mesoporous silica was stirred to ensure thorough mixing with the silicone oil. The mixture was then allowed to stand at room temperature for 24 hours, with stirring every 6 hours during this period. After impregnation, the mixture was transferred to a Buchner funnel and filtered under a vacuum of 0.06 MPa to remove excess silicone oil from the surface, yielding the carrier filler.

[0041] Take double-ended vinyl silicone oil (kinematic viscosity approximately 1000 mm). 2 100.0g of vinyltrimethoxysilane (at 25°C, vinyl content approximately 0.32wt%), 1.5g of hydrogen-containing silicone oil (hydrogen content 0.55wt%, kinematic viscosity 50-70mm). 2 Add 5.0 g of ( / s) to a flask, add 150 mL of toluene as a solvent, purge the air in the flask with nitrogen and maintain a nitrogen atmosphere, stir and heat to 45 °C to fully dissolve and mix all components, add ethynylcyclohexanol as an inhibitor (200 ppm, based on the total mass of vinyl silicone oil and hydrogen-containing silicone oil), and continue stirring for 5 min. Add platinum catalyst (chloroplatinic acid-isopropanol solution, Pt concentration 0.1 mol / L, 10 ppm, based on the total mass of vinyl silicone oil and hydrogen-containing silicone oil), and stir for 10 min to obtain a modified mixture.

[0042] Add 70.0g of carrier filler to the material tank of the fluidized bed coating machine, turn on the fan to fluidize the material, set the inlet air temperature to 55℃, control the material temperature between 48 and 52℃, and the atomization pressure to 0.12MPa. Atomize the modified mixture into the fluidized bed, so that the modified mixture uniformly coats the surface of the fluidized carrier filler particles. After spraying, raise the inlet air temperature of the fluidized bed to 110℃ and continue fluidization, drying, and curing for 2 hours to obtain modified mesoporous silica.

[0043] Preparation Example 3-3: Modified mesoporous silica. The preparation steps are as follows: Add mesoporous silica (average particle size 3 μm, specific surface area approximately 350 m²) to the beaker2 Add 45.0g of dimethyl silicone oil (kinematic viscosity 500 mmHg) to the solution. 2 55.0 g of mesoporous silica and silicone oil were mixed thoroughly by stirring. The mixture was then left to stand at room temperature for 24 hours, with stirring every 6 hours. After impregnation, the mixture was transferred to a Buchner funnel and filtered under a vacuum of 0.06 MPa to remove excess silicone oil from the surface, yielding the carrier filler.

[0044] Take double-ended vinyl silicone oil (kinematic viscosity approximately 5000 mm). 2 100.0g of vinyltrimethoxysilane (at 25°C, vinyl content approximately 0.16wt%), 5.0g of hydrogen-containing silicone oil (hydrogen content 0.36wt%, kinematic viscosity 10-20mm). 2 13.0 g of [amount] was added to a flask, along with 250 mL of toluene as a solvent. Nitrogen gas was purged to replace the air in the flask, and the nitrogen atmosphere was maintained. The mixture was stirred and heated to 50°C to ensure complete dissolution and mixing of all components. Ethynylcyclohexanol was added as an inhibitor (500 ppm, based on the total mass of vinyl silicone oil and hydrogen-containing silicone oil), and stirring was continued for 5 min. A platinum catalyst (chloroplatinic acid-isopropanol solution, Pt concentration 0.1 mol / L, 10 ppm, based on the total mass of vinyl silicone oil and hydrogen-containing silicone oil) was added, and the mixture was stirred for 10 min to obtain the modified mixture.

[0045] Add 90.0g of carrier filler to the material tank of the fluidized bed coating machine, turn on the fan to fluidize the material, set the inlet air temperature to 65℃, control the material temperature between 55 and 60℃, and the atomization pressure to 0.15MPa. Atomize the modified mixture into the fluidized bed, so that the modified mixture uniformly coats the surface of the fluidized carrier filler particles. After spraying, raise the inlet air temperature of the fluidized bed to 110℃ and continue fluidization, drying, and curing for 3 hours to obtain modified mesoporous silica.

[0046] Preparation Example 3-4, modified mesoporous silica, differs from Preparation Example 3-1 in that an equal amount of dual-terminated vinyl silicone oil (kinematic viscosity approximately 5000 mm) is used. 2 (at 25°C and with a vinyl content of approximately 0.16 wt%), replacing vinyltrimethoxysilane.

[0047] Preparation Example 3-5, modified mesoporous silica, differs from Preparation Example 3-1 in that the surface is not coated with silicone rubber, and the resulting carrier filler is modified mesoporous silica.

[0048] Example Example 1: A high-temperature resistant non-stick ceramic coating is prepared according to the following steps: Add 100.0 g of silica sol (30 wt% solids, pH 9.5–10.5, particle size 10–15 nm), 15.0 g of titanium dioxide (rutile type, average particle size 0.25–0.35 μm), and 16.0 g of filler mixture, including 8.0 g of modified mesoporous silica (prepared in Example 3-1) and 8.0 g of silica micropowder (average particle size approximately 10 μm), and 3.0 g of dispersant (BYK-190). Disperse the mixture at 1200 rpm for 30 min using a high-speed disperser, then transfer it to a sand mill and grind it to a fineness ≤15 μm to obtain component A.

[0049] Add 6.0g of isopropanol, 1.0g of formic acid, and dimethyl silicone oil (kinematic viscosity 500 mmHg) to another mixing container. 2 5.0 g of polyether silane (prepared in Preparation Example 1-1) was added, along with 80.0 g of a silane mixture, comprising 18.0 g of polyether silane (prepared in Preparation Example 1-1), 12.0 g of phenyl silane (prepared in Preparation Example 2-1), 30.0 g of methyltrimethoxysilane, and 20.0 g of tetramethoxysilane (polyether silane accounts for 22.5%, and phenyl silane accounts for 15.0%). 2 g of leveling agent (BYK-331) was added, and the mixture was stirred at 500 rpm for 15 min at room temperature using a magnetic stirrer to obtain component B.

[0050] Mix component A and component B at a mass ratio of 2:1 and stir at 800 rpm for 20 minutes using a high-speed disperser to obtain a high-temperature resistant non-stick ceramic coating.

[0051] Example 2: A high-temperature resistant non-stick ceramic coating is prepared according to the following steps: Add 100.0 g of silica sol (30 wt% solids, pH 9.5–10.5, particle size 10–15 nm), 5.0 g of titanium dioxide (rutile type, average particle size 0.25–0.35 μm), and 10.0 g of filler mixture, including 3.0 g of modified mesoporous silica (prepared in Preparation Example 3-2) and 7.0 g of silica micropowder (average particle size approximately 10 μm), and 3.0 g of dispersant (BYK-190). Disperse the mixture at 1000 rpm for 20 min using a high-speed disperser, then transfer it to a sand mill and grind it to a fineness ≤15 μm to obtain component A.

[0052] Add 2.0g of isopropanol, 0.3g of formic acid, and dimethyl silicone oil (kinematic viscosity 500 mmHg) to another mixing container. 21.5g of polyether silane (prepared in Preparation Examples 1-2) and 40.0g of tetramethoxysilane were added, including 8.0g of polyether silane (prepared in Preparation Examples 1-2), 4.0g of phenyl silane (prepared in Preparation Examples 2-2), 12.0g of methyltrimethoxysilane, and 16.0g of tetramethoxysilane (polyether silane accounts for 20% and phenyl silane accounts for 10.0%). 2g of leveling agent (BYK-331) was added, and the mixture was stirred at 500 rpm for 10 min at room temperature using a magnetic stirrer to obtain component B.

[0053] Mix component A and component B at a mass ratio of 1:1 and stir at 800 rpm for 10 minutes using a high-speed disperser to obtain a high-temperature resistant non-stick ceramic coating.

[0054] Example 3: A high-temperature resistant non-stick ceramic coating is prepared according to the following steps: Add 100.0 g of silica sol (30 wt% solids, pH 9.5–10.5, particle size 10–15 nm), 30.0 g of titanium dioxide (rutile type, average particle size 0.25–0.35 μm), and 20.0 g of filler mixture, including 10.0 g of modified mesoporous silica (prepared in Preparation Example 3-3) and 10.0 g of silica micropowder (average particle size approximately 10 μm), and 5.0 g of dispersant (BYK-190). Disperse the mixture at 1200 rpm for 30 min using a high-speed disperser, then transfer it to a sand mill and grind it to a fineness ≤15 μm to obtain component A.

[0055] Add 10.0g of isopropanol, 2.0g of formic acid, and dimethyl silicone oil (kinematic viscosity 500 mmHg) to another mixing container. 2 10.0 g of a silane mixture was added, comprising 30.0 g of polyether silane (prepared in Preparation Examples 1-3), 20.0 g of phenyl silane (prepared in Preparation Examples 2-3), 30.0 g of methyltrimethoxysilane, and 20.0 g of vinyltrimethoxysilane (polyether silane accounts for 30%, and phenyl silane accounts for 20%). 5 g of leveling agent (BYK-331) was added, and the mixture was stirred at 600 rpm for 15 min at room temperature using a magnetic stirrer to obtain component B.

[0056] Mix component A and component B at a mass ratio of 3:1 and stir at 1000 rpm for 20 minutes using a high-speed disperser to obtain a high-temperature resistant non-stick ceramic coating.

[0057] Example 4, a high-temperature resistant non-stick ceramic coating, differs from Example 1 in that an equal amount of modified mesoporous silica from Preparation Example 3-4 is used to replace the modified mesoporous silica from Preparation Example 3-1.

[0058] Example 5, a high-temperature resistant non-stick ceramic coating, differs from Example 1 in that an equal amount of modified mesoporous silica from Preparation Examples 3-5 is used to replace the modified mesoporous silica from Preparation Example 3-1.

[0059] Comparative Example Comparative Example 1 is a high-temperature resistant non-stick ceramic coating, which differs from Example 1 in that an equal amount of polyether silane (prepared in Preparation Example 1-1) is used instead of phenyl silane (prepared in Preparation Example 2-1).

[0060] Comparative Example 2, a high-temperature resistant non-stick ceramic coating, differs from Example 1 in that an equal amount of phenylsilane (prepared in Preparation Example 2-1) is used instead of polyethersilane (prepared in Preparation Example 1-1).

[0061] Comparative Example 3, a high-temperature resistant non-stick ceramic coating, differs from Example 1 in that an equal amount of phenyltrimethoxysilane is used to replace phenylsilane (prepared in Preparation Example 2-1).

[0062] Comparative Example 4, a high-temperature resistant non-stick ceramic coating, differs from Example 1 in that an equal amount of methyltrimethoxysilane is used to replace phenylsilane (prepared in Preparation Example 2-1) and polyether silane (prepared in Preparation Example 1-1).

[0063] Performance testing Sample Preparation: An aluminum plate (3003 aluminum alloy) with dimensions of 150mm × 70mm × 1.0mm was used as the substrate. A mixture of 60-mesh and 80-mesh white corundum abrasive sand at a 1:1 mass ratio was used for sandblasting, with the surface roughness controlled at 3.0–3.5 μm. The surface sand particles and dust were then blown away with compressed air, and oil stains were removed by wiping with anhydrous ethanol. The substrate was preheated to 50–60℃, and the prepared non-stick ceramic coating was uniformly sprayed onto the substrate surface using compressed air. The spray gun nozzle diameter was 1.0–1.5mm, the atomization pressure was 0.25–0.30MPa, and the dry film thickness was controlled at 30–40 μm. After spraying, the coating was first dried at 80–100℃ for 7–10 minutes, and then cured at 260–280℃ for 15–20 minutes to obtain the test sample.

[0064] Experiment 1: Non-stickiness test Non-stick test for fried eggs: The non-stick test for fried eggs was conducted according to GB / T 32095.2-2015 "Specifications for the Performance and Testing of Non-stick Surfaces of Household Food Metal Cooking Utensils Part 2: Test Specifications for Non-stick and Abrasion Resistance". The test sample was placed on a heating oven and heated to a surface temperature of 195–205℃. Approximately 1g of cooking oil was evenly applied to the coating surface. When the oil temperature reached 180–200℃, a fresh egg (approximately 50g) was cracked onto the coating surface. Heating was maintained for 30 seconds, then the heat source was turned off. The egg was then attempted to be lifted from the coating surface using a silicone spatula. The adhesion between the egg and the coating was observed. After each test, the sample was cleaned and cooled to room temperature. The above operation was repeated, and the number of cycles when the coating non-stick grade decreased from Grade I to Grade II (i.e., slight adhesion occurred but could be easily removed by wiping with a damp sponge or cloth) was recorded. Each test was repeated 3 times, and the average value was taken.

[0065] Experiment 2: Abrasion Resistance Test The abrasion resistance test of the flat surface in GB / T 32095.2-2015 "Specifications for the Performance and Testing of Non-stick Surfaces of Household Food Metal Cooking Utensils Part 2: Test Specifications for Non-stickness and Abrasion Resistance" was conducted using a coating abrasion tester. The test sample was fixed on the test bench, and a 3M 7447 scouring pad was used as the friction medium. A load of 4.9 N was applied, and reciprocating friction was performed at a frequency of 40 times / min, with a friction stroke of 100 mm. A new scouring pad was replaced after every 500 friction cycles, and the number of friction cycles at which significant wear of the coating or exposure of the substrate was recorded. Each test was repeated three times, and the average value was taken.

[0066] Experiment 3: Adhesion Test The test was conducted according to GB / T 9286-2021 "Cross-cut Test for Paints and Varnishes". A 6×6 right-angled grid with a 2mm spacing was cut into the coating surface using a cross-cutting knife, penetrating the coating to the substrate. After lightly brushing away surface debris, 3M tape (model 610) was applied to the grid area, and rolled back and forth 5 times with a rubber roller to ensure full contact between the tape and the coating. After standing for 1 minute, the tape was smoothly peeled off within 0.5–1.0 seconds at an angle close to 60°. The extent of coating peeling in the grid area was observed under standard light, and rated according to the standard's 0–5 grades, where grade 0 indicates completely smooth cut edges with no peeling, and grade 5 indicates a peeling area greater than 65%.

[0067] Experiment 4: Hardness Test The pencil hardness test was conducted according to GB / T 6739-2022 "Determination of Hardness of Paints and Varnishes by Pencil Method". The test sample was horizontally fixed on a stable table. Using a pencil hardness tester, the pencil was held at a 45° angle to the coating surface, and a load of 750g was applied. The pencil was pushed at a speed of approximately 0.5 mm / s, leaving a scratch of approximately 6 mm on the coating surface. Each pencil was replaced with a new lead and sanded smooth with 400-grit sandpaper before testing. Starting with the hardest pencil, the hardness was gradually decreased until no visible scratches or damage appeared on the coating surface. The hardness of this pencil is the pencil hardness of the coating. Each test was repeated three times.

[0068] Test 5: Impact Resistance Test The impact test was conducted according to GB / T 1732-2020, "Test Method for Impact Resistance of Coatings". The test specimen was placed flat on the anvil of the impact tester with the coating facing upwards. A 1000g hammer with an 8mm diameter punch was used. The hammer was raised to a predetermined height and then dropped freely onto the specimen. The coating around the impact point was examined using a 4x magnifying glass for cracks, wrinkles, and peeling. The maximum impact height (cm) without damage to the coating was recorded. Each test was performed three times, and the minimum value was recorded.

[0069] Experiment 6: Thermal Shock Test The test sample was placed in a 300℃ oven for 30 minutes, then removed and completely immersed in 23±2℃ deionized water for cooling within 10 seconds. This constitutes one cycle. This operation was repeated, and the coating was observed for cracking or peeling after every 10 cycles. The number of cycles at which obvious cracking or peeling occurred was recorded. Three samples were tested in each group, and the average value was taken.

[0070] Test 7: Heat Resistance Test The test sample was placed in a forced-air constant temperature oven and kept at 300℃ for 24 hours. After being taken out and cooled to room temperature, the color and gloss of the paint film were observed, as well as whether there were any phenomena such as blistering, cracking or peeling from the substrate.

[0071] Experiment 8: Non-stick durability simulation test Using a coating abrasion tester, after 1000 cycles of the planar abrasion resistance test method in Test 2, the sample was removed, and the number of cycles of the non-stick test for frying eggs was tested according to the method in Test 1 to evaluate the retention of the non-stick performance of the coating after abrasion.

[0072] Table 1 Test Results

[0073] Analysis of Experimental Results The impact resistance of Examples 1-3 is significantly improved compared to the comparative example, and all samples reach the highest hardness level, indicating that the present invention improves toughness without sacrificing surface hardness.

[0074] Compared to Example 1, Example 4 showed a decrease in indicators such as planar abrasion resistance, non-stick cycle count, and non-stick properties after wear. This may be because, after the crosslinking reaction, the siloxane groups on the vinyl silane coupling agent are retained on the surface of the silicone rubber layer. When the coating is applied and cured, these siloxane groups can undergo hydrolysis and condensation reactions with the inorganic binder to form strong covalent bonds, thereby achieving chemical anchoring between the modified filler and the coating matrix. In Example 4, the coating layer surface lacks siloxane active sites for covalent bonding, and the filler-matrix relationship is mainly physical filling, resulting in weak interfacial bonding and deterioration of mechanical properties. This makes the filler relatively easy to detach under external forces during use, leading to a decrease in abrasion resistance and non-stick properties.

[0075] Example 5 showed a certain decrease in performance indicators such as impact resistance, thermal shock resistance, surface abrasion resistance, and non-stick properties after wear. This may be due to two factors: First, the silicone rubber coating layer effectively blocked the pores of the mesoporous silica, achieving long-term controlled release of internally adsorbed silicone oil. In Example 5, the filler surface lacked silicone rubber coating, resulting in rapid precipitation and loss of adsorbed silicone oil during coating preparation and use, leading to a rapid decline in non-stick properties. Second, the modified mesoporous silica after coating itself becomes an organosilicon elastomer filler, capable of reversible deformation to absorb energy when the coating is subjected to external impact or thermal expansion and contraction, preventing crack propagation. In Example 5, the filler was a rigid porous particle, which not only failed to buffer internal stress but also exacerbated the brittleness of the coating, further deteriorating its toughness and impact resistance.

[0076] Compared to Example 1, Comparative Example 1 showed significant loss of gloss in the heat resistance test, and its thermal shock and adhesion ratings also deteriorated. This indicates that the heat resistance of the coating is significantly reduced when it contains only polyether silane and lacks phenyl silane. This is because, while the polyether segments impart good flexibility to the coating, they are prone to oxidative degradation or thermal decomposition at high temperatures, leading to the destruction of the crosslinking network. The rigid phenyl groups introduced into the phenyl silane can significantly improve the thermal decomposition temperature and oxidation resistance of the coating, compensating for the insufficient heat resistance of the polyether segments. Comparative Example 1, lacking the synergistic effect of phenyl silane, exhibits severely insufficient thermal stability.

[0077] Comparative Example 2 showed a significant decrease in both impact resistance and thermal shock resistance, indicating that the coating's flexibility and impact resistance are significantly insufficient when only phenylsilane is present and polyether silane is lacking. This is because while the cross-linked network formed by phenylsilane possesses excellent heat resistance, it is also highly rigid and lacks the stress-buffering effect of flexible segments. The flexible polyether segments introduced by polyether silane are covalently embedded in the three-dimensional network framework, effectively reducing the rigidity of the cross-linking points and increasing the mobility of molecular segments. Due to the lack of toughening effect from polyether segments, Comparative Example 2 exhibits increased brittleness and decreased crack resistance.

[0078] Comparative Example 3 showed a significant decrease in thermal shock and adhesion indicators. This indicates that polymeric phenylsilanes have a clear technical advantage over small-molecule phenyltrimethoxysilanes. This may be because the polymeric phenylsilane, prepared by hydrosilylation of phenyl vinyl silicone oil and hydrogen-containing siloxanes, not only retains a large number of rigid, heat-resistant phenyl groups but also forms a flexible siloxane backbone with a moderate crosslinking density. The phenyl groups provide heat resistance while the siloxane backbone maintains a certain degree of flexibility, achieving a balance between rigidity and toughness. More importantly, this polymeric phenylsilane molecule has numerous siloxane active sites, which can participate in multiple crosslinking reactions, enhancing the density and interfacial adhesion of the coating. In contrast, the small-molecule phenyltrimethoxysilane used in Comparative Example 3 has a single crosslinking point, resulting in a network structure that is rigid but lacks toughness, with a limited number of active functional groups, failing to achieve sufficient synergy with the polyether silane.

[0079] Comparative Example 4 showed some deterioration in all test indicators, especially in impact resistance and thermal shock resistance. This indicates that the basic properties of the coating are severely degraded when both polyether silane and phenyl silane are lacking. The reason is that while conventional methyltrimethoxysilane can participate in sol-gel crosslinking to form a three-dimensional network, its molecular structure is simple, lacking both the flexible toughening effect of polyether segments and the rigid-toughness balance effect of phenyl silicone oil. The resulting network is highly rigid but lacks toughness, making the coating prone to cracking and failure under mechanical stress. The synergistic combination of polyether silane and phenyl silane is crucial for constructing a rigid-flexible balanced network structure; the absence of either one leads to a significant decrease in the overall performance of the coating.

[0080] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A high-temperature resistant non-stick ceramic coating, characterized in that, The product comprises component A and component B in a mass ratio of 1 to 3:

1. Component A includes the following raw materials in parts by mass: 100 parts inorganic binder, 1 to 30 parts pigment, 10 to 20 parts filler, and 1 to 5 parts dispersant. Component B includes the following components in parts by mass: 0.3 to 2 parts catalyst, 40 to 100 parts silane, 1 to 10 parts non-sticking agent, 2 to 10 parts additive, and 1 to 10 parts solvent. The silane includes polyether silane and phenyl silane, wherein the polyether silane accounts for 20 to 30% of the total mass of silane, and the phenyl silane accounts for 10 to 20% of the total mass of silane.

2. The high-temperature resistant non-stick ceramic coating according to claim 1, characterized in that, The polyether silane is prepared by hydrosilylation of allyl polyether and hydrogen-containing siloxane in a molar ratio of 1:1 to 1.

1.

3. The high-temperature resistant non-stick ceramic coating according to claim 1, characterized in that, The phenylsilane is prepared by hydrosilylation of phenyl vinyl silicone oil and hydrogen-containing siloxane in a mass ratio of 7 to 12:

1.

4. The high-temperature resistant non-stick ceramic coating according to claim 3, characterized in that, The dynamic viscosity of the phenyl vinyl silicone oil is 300–6000 mPa·s.

5. The high-temperature resistant non-stick ceramic coating according to claim 2 or 4, characterized in that, The hydrogen-containing siloxane is selected from at least one of trimethoxysilane, triethoxysilane, methyldimethoxysilane, and ethyldimethoxysilane.

6. The high-temperature resistant non-stick ceramic coating according to claim 1, characterized in that, The silane also includes one or more of the following: tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and γ-(2,3-epoxypropoxy)propyltriethoxysilane.

7. The high-temperature resistant non-stick ceramic coating according to claim 1, characterized in that, The filler contains at least 30-50 wt% modified mesoporous silica, and its preparation method is as follows: Mesoporous silica is impregnated in silicone oil to obtain a carrier filler; Vinyl silicone oil, vinyl silane coupling agent, hydrogen-containing silicone oil, inhibitor and catalyst are mixed to obtain a modified mixture, which is then coated on the surface of the carrier filler and cured by heating. The mass ratio of the vinyl silicone oil, vinyl silane coupling agent, and hydrogen-containing silicone oil is 100:1 to 5:1 to 30, and the amounts of inhibitor and catalyst are 100 to 500 ppm and 5 to 10 ppm, respectively.

8. The high-temperature resistant non-stick ceramic coating according to claim 7, characterized in that, The kinematic viscosity of the vinyl silicone oil is 1000–10000 mm. 2 / s.

9. The high-temperature resistant non-stick ceramic coating according to claim 7, characterized in that, The silicone oil is selected from one or more of dimethyl silicone oil, hydroxyl silicone oil, and amino silicone oil.

10. The method for preparing the high-temperature resistant non-stick ceramic coating according to any one of claims 1 to 9, characterized in that, include: The inorganic binder, pigment, filler and dispersant are mixed according to the mass fractions of component A and stirred evenly to obtain component A; According to the mass fractions of component B, the catalyst, silane, non-sticking agent, additive and solvent are mixed and stirred evenly to obtain component B; Mix component A and component B at a mass ratio of 1 to 3:1 and stir until homogeneous to obtain a high-temperature resistant non-stick ceramic coating.

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