Fluorosilicic wetting and leveling agent, its preparation method and application

Abstract

The application belongs to the technical field of leveling agents, and specifically discloses a fluorosilicon wetting leveling agent, a preparation method and application thereof. In the application, dimethylethoxysilane, 1,8-bis(triethoxysilane) octane and polyethyl silicate are subjected to hydrolysis reaction and polymerization reaction to obtain a polymerization liquid; then, the polymerization liquid, double-end side-chain vinyl silicone oil and hydrogen-containing fluorosilicone oil are subjected to a silicon-hydrogen addition reaction to prepare the fluorosilicon wetting leveling agent. The fluorosilicon wetting leveling agent has excellent leveling performance, can effectively reduce surface tension, and can improve the smoothness of a coating film and the stability of paint.

Description

Technical Field

[0001] This invention relates to the field of leveling agent technology, specifically to a fluorosilicone wetting leveling agent, its preparation method, and its application. Background Technology

[0002] Wetting and leveling agents are key additives in coating and ink formulations. Their core function is to reduce the surface tension of the system, eliminate surface defects such as orange peel and pinholes generated during coating application, and enable the coating to spread quickly and evenly on the substrate surface to form a smooth and flat coating film, thereby improving the appearance quality and performance of the coating.

[0003] Currently, wetting and leveling agents on the market are mainly classified into silicone, fluorine, and polyether types. Silicone-based leveling agents offer good leveling and smoothness, but their wetting properties, stain resistance, and temperature resistance are limited. They also exhibit poor spreading performance on low surface energy substrates and are prone to migration and precipitation with long-term use, leading to decreased coating gloss and adhesion. Fluorine-based leveling agents have extremely low surface tension and excellent wetting and stain resistance, but their compatibility with coating systems is poor, easily causing defects such as fisheyes and loss of gloss. Furthermore, their high cost limits their widespread application. Polyether-based leveling agents have good compatibility, but their leveling effect and weather resistance are insufficient, making them unsuitable for high-end coating applications. Summary of the Invention

[0004] This invention provides a fluorosilicone wetting and leveling agent, its preparation method, and its application. The fluorosilicone wetting and leveling agent described in this application has excellent leveling properties, can effectively reduce surface tension, and improve the smoothness and stability of the coating film.

[0005] To achieve the above objectives, the first aspect of this application provides a method for preparing a fluorosilicone wetting and leveling agent, comprising the following steps: (1) Mix dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate evenly, add catalyst, water and ethanol solution, hydrolyze reaction, polymerize reaction, remove solvent to obtain polymer solution; (2) The polymerization liquid, double-ended side chain vinyl silicone oil, hydrofluoric silicone oil and solvent are stirred evenly, and a catalyst and alkynol inhibitor are added. The reaction is carried out and the solvent is removed to obtain fluorosilicone wetting and leveling agent.

[0006] As an embodiment of this application, the vinyl content of the dual-end side-chain vinyl silicone oil is 1.1~1.3wt%, and the viscosity at 25°C is 180~330mPa·s.

[0007] As an embodiment of this application, the mass ratio of dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, and polyethyl silicate is 100:(35~50):(55~70).

[0008] As an embodiment of this application, the mass ratio of the dimethylethoxysilane, catalyst, water, and ethanol solution is 100:(0.1~0.5):(25~35):(25~35).

[0009] As an embodiment of this application, the hydrolysis reaction is carried out at a temperature of 30-50°C for a time of 0.5-5 hours; and / or The polymerization reaction is carried out at a temperature of 60~90℃ for a time of 0.5~5h.

[0010] As an embodiment of this application, the mass ratio of the polymerization liquid, the dual-end side-chain vinyl silicone oil, and the hydrofluoric silicone oil is 100:(50~60):(40~45); and / or The mass ratio of the polymerization liquid, solvent, catalyst, and alkynol inhibitor is 100:(200~500):(0.1~0.5):(0.05~0.2).

[0011] As an embodiment of this application, the alkynol inhibitor is ethynylcyclohexanol.

[0012] As an embodiment of this application, the solvent includes at least one selected from toluene, xylene, n-hexane, cyclohexane, tetrahydrofuran, isopropanol, and ethanol; The catalyst mentioned in step (1) includes at least one of p-toluenesulfonic acid and chloroplatinic acid; The catalyst mentioned in step (2) includes at least one of p-toluenesulfonic acid and chloroplatinic acid.

[0013] As an implementation scheme of this application, the reaction temperature in step (2) is 60~90℃ and the time is 0.5~5h.

[0014] The second aspect of this application provides a fluorosilicone wetting and leveling agent, which is prepared by the preparation method described above.

[0015] A third aspect of this application provides the use of a fluorosilicone wetting and leveling agent in the preparation of coatings, inks, or sealants.

[0016] The beneficial effects of this invention are as follows: First, dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, and polyethyl silicate are subjected to hydrolysis and polymerization reactions to obtain a polymer liquid; then, the polymer liquid, double-ended side-chain vinyl silicone oil, and hydrofluoric silicone oil are subjected to a hydrosilylation reaction to prepare a fluorosilicone wetting and leveling agent. The fluorosilicone wetting and leveling agent has excellent leveling properties, can effectively reduce surface tension, improve coating smoothness and coating stability. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0019] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0020] In this invention, there are no particular limitations on the specific dispersion and stirring methods.

[0021] Unless otherwise specified, all reagents or instruments used in this invention are commercially available conventional products. Unless otherwise specified, the raw materials used in each comparative example and the parallel experiments of each embodiment are the same commercially available products.

[0022] The raw materials used in the examples and comparative examples are as follows: Double-ended side-chain vinyl silicone oil-1: Vinyl content is 1.2±0.1wt%, viscosity at 25℃ is 180~250mPa·s, grade JP-02V-200, sourced from Longsheng Sihai New Materials Co., Ltd.

[0023] Double-ended side-chain vinyl silicone oil-2: vinyl content is 1.2±0.1wt%, viscosity at 25℃ is 270~330mPa·s, grade JP-02V-300, sourced from Longsheng Sihai New Materials Co., Ltd.

[0024] Double-ended side-chain vinyl silicone oil-3: vinyl content is 10±0.5wt%, viscosity at 25℃ is 100~200mPa·s, grade JP-02V-150, sourced from Longsheng Sihai New Materials Co., Ltd.

[0025] Double-ended side-chain vinyl silicone oil-4: vinyl content is 1±0.2wt%, viscosity at 25℃ is 950~1100mPa·s, grade JP-01V-1000, sourced from Longsheng Sihai New Materials Co., Ltd.

[0026] Polyethyl silicate: brand name Dynasylan®40, sourced from Evonik.

[0027] Hydrofluoric silicone oil: hydrogen content 0.7wt%, viscosity at 25℃ 30~100mm. 2 / s, grade 25H-08, is from Aiyota Silicone Oil Co., Ltd.

[0028] Hydrogen-containing silicone oil: grade RH202-20L, sourced from Runhe Materials.

[0029] This application provides a method for preparing a fluorosilicone wetting and leveling agent, comprising the following steps: (1) Dimethylethoxysilane (CAS:14857-34-2), 1,8-bis(triethoxysilyl)octane (CAS:52217-60-4), and polyethyl silicate are mixed evenly, and a catalyst, water, and ethanol solution are added. Hydrolysis reaction and polymerization reaction are carried out, and the solvent is removed to obtain a polymer solution. (2) The polymerization liquid, double-ended side chain vinyl silicone oil, hydrofluoric silicone oil and solvent are stirred evenly, and a catalyst and alkynol inhibitor are added. The reaction is carried out and the solvent is removed to obtain fluorosilicone wetting and leveling agent.

[0030] This application first involves hydrolyzing and polymerizing dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, and polyethyl silicate to obtain a polymer solution. Then, the polymer solution, dual-end side-chain vinyl silicone oil, and hydrofluoric silicone oil are subjected to a hydrosilylation reaction to prepare a fluorosilicone wetting and leveling agent. The fluorosilicone wetting and leveling agent has excellent leveling properties, can effectively reduce surface tension, and improve the smoothness and stability of the coating film.

[0031] In this process, dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, and polyethyl silicate undergo hydrolysis and polymerization reactions. Dehydration condensation occurs between the silanol groups, forming Si-O-Si covalent bonds to construct a linear-branched prepolymer. Dimethylethoxysilane provides hydrophobic methyl groups, inhibiting excessive crosslinking and regulating the hardness and flexibility of the prepolymer. 1,8-bis(triethoxysilyl)octane and polyethyl silicate introduce octyl flexible chains and appropriate amounts of silanol groups, improving compatibility with fillers in the coating and enhancing filler dispersibility. The polymerization liquid, dual-end-chain vinyl silicone oil, and hydrofluorosilicone oil undergo hydrosilylation reactions. The fluorocarbon chains in the hydrofluorosilicone oil are uniformly grafted onto the polymer backbone, significantly reducing the surface tension of the leveling agent and imparting excellent wetting properties. Simultaneously, the flexible siloxane segments of the dual-end-chain vinyl silicone oil further optimize the leveling properties of the leveling agent and improve its compatibility with the coating system.

[0032] In some embodiments, the vinyl content of the dual-end side-chain vinyl silicone oil is 1.1 to 1.3 wt%, for example, it can be 1.1 wt%, 1.15 wt%, 1.2 wt%, 1.25 wt%, 1.3 wt%, or any two of these values.

[0033] In some embodiments, the viscosity of the dual-end side-chain vinyl silicone oil at 25°C is 180~330 mPa·s, for example, it can be 180 mPa·s, 200 mPa·s, 220 mPa·s, 240 mPa·s, 250 mPa·s, 260 mPa·s, 280 mPa·s, 300 mPa·s, 320 mPa·s, 330 mPa·s or any two of these values.

[0034] In some embodiments, the mass ratio of dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, and polyethyl silicate is 100:(35~50):(55~70).

[0035] In some embodiments, the mass ratio of the dimethylethoxysilane, catalyst, water, and ethanol solution is 100:(0.1~0.5):(25~35):(25~35).

[0036] In some embodiments, the temperature of the hydrolysis reaction is 30~50°C, for example, it can be 30°C, 32°C, 35°C, 38°C, 40°C, 42°C, 45°C, 48°C, 50°C or any two of these values.

[0037] In some embodiments, the hydrolysis reaction time is 0.5 to 5 hours, for example, it can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or any two of these values.

[0038] In some embodiments, the polymerization reaction temperature is 60~90°C, for example, it can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C or any two of these values.

[0039] In some embodiments, the polymerization reaction time is 0.5 to 5 hours, for example, it can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or any two of these values.

[0040] In some embodiments, the mass ratio of the polymer liquid, the double-ended side-chain vinyl silicone oil, and the hydrofluoric silicone oil is 100:(50~60):(40~45). By controlling the mass ratio of the three components within this range, the leveling agent and the coating have good compatibility, and problems such as fish eyes, loss of gloss, and precipitation do not occur. At the same time, excessive reaction is avoided, and gelation of the system is prevented.

[0041] In some embodiments, the mass ratio of the polymerization liquid, solvent, catalyst, and alkynol inhibitor is 100:(200~500):(0.1~0.5):(0.05~0.2).

[0042] In some embodiments, the alkynol inhibitor is ethynylcyclohexanol.

[0043] In some embodiments, the solvent includes at least one selected from toluene, xylene, n-hexane, cyclohexane, tetrahydrofuran, isopropanol, and ethanol.

[0044] In some embodiments, the catalyst in step (1) includes at least one of p-toluenesulfonic acid and chloroplatinic acid; In some embodiments, the catalyst in step (2) includes at least one of p-toluenesulfonic acid and chloroplatinic acid.

[0045] In some embodiments, the reaction temperature in step (2) is 60~90°C, for example, it can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C or any two of these values.

[0046] In some embodiments, the reaction time in step (2) is 0.5 to 5 hours, for example, it can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or any two of these values.

[0047] In some embodiments, the hydrogen content of the hydrofluoric silicone oil is 0.2 to 0.7 wt%, for example, it can be 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, or any two of these values.

[0048] In some embodiments, the viscosity of the hydrofluoric silicone oil at 25°C is 30~100 mm. 2 / s, for example, could be 30mm 2 / s, 40mm 2 / s, 50mm 2 / s, 60mm 2 / s, 70mm 2 / s, 80mm 2 / s, 90mm 2 / s, 100mm 2 / s or a range consisting of any two of these values.

[0049] In some embodiments, the volume concentration of ethanol in the ethanol solution is 40-80%, for example, it can be 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any two of these values.

[0050] The second aspect of this application provides a fluorosilicone wetting and leveling agent, which is prepared by the preparation method described above.

[0051] A third aspect of this application provides the use of a fluorosilicone wetting and leveling agent in the preparation of coatings, inks, or sealants.

[0052] The present application is further illustrated below with specific embodiments:

[0053] Example 1 A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0054] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:45:60:0.2:30:30.

[0055] (2) Add toluene into the reactor, then add polymerization liquid, double-ended side chain vinyl silicone oil-1, and hydrofluoric silicone oil. Stir at 200 rpm for 20 min, add chloroplatinic acid and ethynylcyclohexanol, heat to 85°C, and react at 85°C for 4 h; heat to 95°C, evacuate to -0.095 MPa, and keep warm for 1 h to obtain fluorosilicone wetting and leveling agent.

[0056] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-1, hydrofluoric silicone oil, toluene chloroplatinic acid, and ethynylcyclohexanol is 100:58:42:250:0.2:0.08.

[0057] Example 2 A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0058] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:35:70:0.2:30:30.

[0059] (2) Add toluene into the reactor, then add polymerization liquid, double-ended side chain vinyl silicone oil-1, and hydrofluoric silicone oil. Stir at 200 rpm for 20 min, add chloroplatinic acid and ethynylcyclohexanol, heat to 85°C, and react at 85°C for 4 h; heat to 95°C, evacuate to -0.095 MPa, and keep warm for 1 h to obtain fluorosilicone wetting and leveling agent.

[0060] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-1, hydrofluoric silicone oil, toluene, chloroplatinic acid, and ethynylcyclohexanol is 100:50:45:250:0.2:0.08.

[0061] Example 3 A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0062] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:50:55:0.2:30:30.

[0063] (2) Add toluene into the reactor, then add polymerization liquid, double-ended side chain vinyl silicone oil-1, and hydrofluoric silicone oil. Stir at 200 rpm for 20 min, add chloroplatinic acid and ethynylcyclohexanol, heat to 85°C, and react at 85°C for 4 h; heat to 95°C, evacuate to -0.095 MPa, and keep warm for 1 h to obtain fluorosilicone wetting and leveling agent.

[0064] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-1, hydrofluoric silicone oil, toluene, chloroplatinic acid, and ethynylcyclohexanol is 100:60:40:250:0.2:0.08.

[0065] Example 4 A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0066] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:45:60:0.2:30:30.

[0067] (2) Toluene was added to the reactor, followed by the polymerization liquid, double-ended side chain vinyl silicone oil-2, and hydrofluoric silicone oil. The mixture was stirred at 200 rpm for 20 min, and chloroplatinic acid and ethynylcyclohexanol were added. The temperature was raised to 85°C and reacted at 85°C for 4 h. The temperature was raised to 95°C, and the vacuum was drawn to -0.095 MPa. The mixture was kept at this temperature for 1 h to obtain the fluorosilicone wetting and leveling agent.

[0068] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-2, hydrofluoric silicone oil, toluene chloroplatinic acid, and ethynylcyclohexanol is 100:58:42:250:0.2:0.08.

[0069] Example 5 A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0070] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:45:60:0.2:30:30.

[0071] (2) Add toluene into the reactor, then add polymerization liquid, double-ended side chain vinyl silicone oil-3, and hydrofluoric silicone oil. Stir at 200 rpm for 20 min, add chloroplatinic acid and ethynylcyclohexanol, heat to 85°C, and react at 85°C for 4 h; heat to 95°C, evacuate to -0.095 MPa, and keep warm for 1 h to obtain fluorosilicone wetting and leveling agent.

[0072] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-3, hydrofluoric silicone oil, toluene chloroplatinic acid, and ethynylcyclohexanol is 100:58:42:250:0.2:0.08.

[0073] Example 6 A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0074] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:45:60:0.2:30:30.

[0075] (2) Toluene was added to the reactor, followed by the polymerization liquid, double-ended side chain vinyl silicone oil-4, and hydrofluoric silicone oil. The mixture was stirred at 200 rpm for 20 min, and chloroplatinic acid and ethynylcyclohexanol were added. The temperature was raised to 85°C and reacted at 85°C for 4 h. The temperature was raised to 95°C, and the vacuum was drawn to -0.095 MPa. The mixture was kept at this temperature for 1 h to obtain the fluorosilicone wetting and leveling agent.

[0076] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-4, hydrofluoric silicone oil, toluene chloroplatinic acid, and ethynylcyclohexanol is 100:58:42:250:0.2:0.08.

[0077] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses an equal amount of hydrogen-containing silicone oil to replace the polymerization liquid, while everything else is the same.

[0078] A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Toluene was added to the reaction vessel, followed by hydrogen-containing silicone oil, double-ended side-chain vinyl silicone oil-1, and hydrogen-fluorinated silicone oil. The mixture was stirred at 200 rpm for 20 min, and then chloroplatinic acid and ethynylcyclohexanol were added. The temperature was raised to 85°C and reacted at 85°C for 4 h. The temperature was raised to 95°C, and the vacuum was drawn to -0.095 MPa. The mixture was kept at this temperature for 1 h to obtain the fluorosilicone wetting and leveling agent.

[0079] The mass ratio of the hydrogen-containing silicone oil, the double-ended side-chain vinyl silicone oil-1, the hydrofluoric silicone oil, the toluenechloroplatinic acid, and the ethynylcyclohexanol is 100:58:42:250:0.2:0.08.

[0080] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the mass ratios of hydrogen-containing silicone oil, double-ended side-chain vinyl silicone oil-1, and hydrogen-fluorinated silicone oil are different, while all other aspects are the same.

[0081] A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0082] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:45:60:0.2:30:30.

[0083] (2) Add toluene into the reactor, then add polymerization liquid, double-ended side chain vinyl silicone oil-1, and hydrofluoric silicone oil. Stir at 200 rpm for 20 min, add chloroplatinic acid and ethynylcyclohexanol, heat to 85°C, and react at 85°C for 4 h; heat to 95°C, evacuate to -0.095 MPa, and keep warm for 1 h to obtain fluorosilicone wetting and leveling agent.

[0084] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-1, hydrofluoric silicone oil, toluene chloroplatinic acid, and ethynylcyclohexanol is 100:20:80:250:0.2:0.08.

[0085] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the mass ratios of hydrogen-containing silicone oil, double-ended side-chain vinyl silicone oil-1, and hydrogen-fluorinated silicone oil are different, while all other aspects are the same.

[0086] A method for preparing a fluorosilicone wetting and leveling agent includes the following steps: (1) Dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate were added to the reactor and nitrogen gas was introduced for protection. The mixture was stirred at 200 rpm for 20 min. Chloroplatinic acid, water and 50 v% ethanol solution were added. The mixture was stirred at 200 rpm for 10 min, then heated to 45 °C for hydrolysis reaction for 2 h, then heated to 75 °C for polymerization reaction for 3 h. The temperature was raised to 95 °C, vacuumed to -0.095 MPa and kept at the temperature for 1 h to obtain the polymerization liquid.

[0087] The mass ratio of the dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, polyethyl silicate, chloroplatinic acid, water, and ethanol solution is 100:45:60:0.2:30:30.

[0088] (2) Add toluene into the reactor, then add polymerization liquid, double-ended side chain vinyl silicone oil-1, and hydrofluoric silicone oil. Stir at 200 rpm for 20 min, add chloroplatinic acid and ethynylcyclohexanol, heat to 85°C, and react at 85°C for 4 h; heat to 95°C, evacuate to -0.095 MPa, and keep warm for 1 h to obtain fluorosilicone wetting and leveling agent.

[0089] The mass ratio of the polymerization liquid, double-ended side-chain vinyl silicone oil-1, hydrofluoric silicone oil, toluene chloroplatinic acid, and ethynylcyclohexanol is 100:80:20:250:0.2:0.08.

[0090] Test case Weigh the raw materials according to the following mass percentage formula: 9% carbon black, 6% ethylene glycol, 0.6% fluorosilicone wetting and leveling agent, 18% water, and the balance acrylic emulsion (Houxian® 5300 acrylic emulsion).

[0091] Water and ethylene glycol were added to a dispersion tank and stirred until homogeneous. Then carbon black was added and stirred until homogeneous again. The remaining substances were then added and stirred until homogeneous to obtain the test coating. The test coating was sprayed onto a substrate, and the dry film thickness was controlled at 50 μm.

[0092] 1. Use a static surface tension meter to test the surface tension. The smaller the reading, the lower the surface tension. The lower the surface tension, the better the wettability.

[0093] 2. Place the coating at 25℃ for 180 days and observe its stability.

[0094] 3. Use an orange peel analyzer to measure the DOI value. The higher the DOI value, the smoother the surface of the coating and the better the leveling performance.

[0095]

[0096] As can be seen from Table 1, the fluorosilicone wetting and leveling agent described in this application has excellent leveling properties, which can effectively reduce surface tension, improve coating smoothness and coating stability.

[0097] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a fluorosilicone wetting and leveling agent, characterized in that, Includes the following steps: (1) Mix dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane and polyethyl silicate evenly, add catalyst, water and ethanol solution, hydrolyze reaction, polymerize reaction, remove solvent to obtain polymer solution; (2) The polymerization liquid, double-ended side chain vinyl silicone oil, hydrofluoric silicone oil and solvent are stirred evenly, and a catalyst and alkynol inhibitor are added. The reaction is carried out and the solvent is removed to obtain fluorosilicone wetting and leveling agent.

2. The method for preparing the fluorosilicone wetting and leveling agent according to claim 1, characterized in that, The vinyl content of the dual-end side-chain vinyl silicone oil is 1.1~1.3wt%, and the viscosity at 25°C is 180~330mPa·s.

3. The method for preparing the fluorosilicone wetting and leveling agent according to claim 1, characterized in that, The mass ratio of dimethylethoxysilane, 1,8-bis(triethoxysilyl)octane, and polyethyl silicate is 100:(35~50):(55~70); and / or The mass ratio of the dimethylethoxysilane, catalyst, water, and ethanol solution is 100:(0.1~0.5):(25~35):(25~35).

4. The method for preparing the fluorosilicone wetting and leveling agent according to claim 1, characterized in that, The hydrolysis reaction is carried out at a temperature of 30-50°C for a time of 0.5-5 hours; and / or The polymerization reaction is carried out at a temperature of 60~90℃ for a time of 0.5~5h.

5. The method for preparing the fluorosilicone wetting and leveling agent according to claim 1, characterized in that, The mass ratio of the polymerization liquid, the dual-end side-chain vinyl silicone oil, and the hydrofluoric silicone oil is 100:(50~60):(40~45); and / or The mass ratio of the polymerization liquid, solvent, catalyst, and alkynol inhibitor is 100:(200~500):(0.1~0.5):(0.05~0.2).

6. The method for preparing the fluorosilicone wetting and leveling agent according to claim 1, characterized in that, The alkynol inhibitor is ethynylcyclohexanol.

7. The method for preparing the fluorosilicone wetting and leveling agent according to claim 1, characterized in that, The solvent includes at least one of toluene, xylene, n-hexane, cyclohexane, tetrahydrofuran, isopropanol, and ethanol; The catalyst mentioned in step (1) includes at least one of p-toluenesulfonic acid and chloroplatinic acid; The catalyst mentioned in step (2) includes at least one of p-toluenesulfonic acid and chloroplatinic acid.

8. The method for preparing the fluorosilicone wetting and leveling agent according to claim 1, characterized in that, The reaction temperature in step (2) is 60~90℃ and the reaction time is 0.5~5h.

9. A fluorosilicone wetting and leveling agent, characterized in that, It is prepared by any of the preparation methods described in claims 1 to 8.

10. The use of the fluorosilicone wetting and leveling agent according to claim 9 in the preparation of coatings, inks or sealants.

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