A method for preparing and applying a fluorine-free glass hydrophobic agent.

Abstract

This invention discloses a method for preparing and applying a fluorine-free glass hydrophobic agent. The specific steps involve first preparing two solvents: Agent A, with a mixture of alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane as the main agent and an alcohol solvent as the diluent; and Agent B, with an acid catalyst and a mixture of water and an alcohol as the diluent. After preparation, Agent A and Agent B are thoroughly stirred to form a homogeneous mixture. Then, Agent B is added dropwise to Agent A. After the addition is complete, the reaction system is sealed and vigorously stirred again until a milky-white, homogeneous micelle system is formed, thus obtaining the target fluorine-free glass hydrophobic agent. The method for preparing the fluorine-free glass hydrophobic agent of this invention is simple. This hydrophobic agent can be directly sprayed onto the surface of a cover glass, and after heat treatment, a high water droplet angle can be achieved, resulting in excellent hydrophobic properties.

Description

Technical Field

[0001] This invention belongs to the field of hydrophobic materials technology, and relates to a method for preparing and applying a fluorine-free glass hydrophobic agent. Background Technology

[0002] The main component of ordinary cover glass is silicon dioxide. The silicon dioxide on its surface adsorbs a certain amount of water molecules from the air, forming hydroxyl groups (-OH). The contact angle between clean cover glass and water is typically maintained at around 20°. This is mainly because the hydroxyl (-OH) groups formed on the glass surface can further form hydrogen bonds with water molecules in the air or on fingers, giving the cover glass good hydrophilicity. These water films spreading on the glass surface significantly increase bacterial adhesion and affect normal visual appearance. Currently, the organic hydrophobic agents used in the glass cover glass industry mainly focus on fluorinated hydrophobic materials. Fluorinated hydrophobic materials are a class of high-performance glass surface treatment materials based on fluorinated compounds. Their core advantage lies in their ability to significantly improve the hydrophobic properties of glass covers. Fluorinated hydrophobic materials typically interact with the hydroxyl (-OH) groups formed on the cover glass surface through chemical bonding, forming a dense and highly hydrophobic fluorinated protective film. Meanwhile, the long-chain carbon-fluorine bonds in the structure of fluorine-based hydrophobic materials also have extremely low surface energy, making them widely used in the surface treatment of cover glass for medical devices. This effectively prevents bacterial adhesion and improves the hygiene standards of medical devices.

[0003] Although fluorinated hydrophobic materials exhibit excellent hydrophobic properties in various cover glass applications—for example, the contact angle between fluorinated cover glass and water can reach over 110°, higher than that of ordinary hydrophobic materials—their practical application still faces some challenges. Firstly, cost is a major limiting factor. The extremely complex synthesis process of fluorinated compounds leads to relatively high production costs, restricting their widespread adoption in low-cost cover glass applications. Secondly, fluorinated hydrophobic materials do not align with the concept of green environmental protection. Summary of the Invention

[0004] Purpose of the invention: The purpose of this invention is to provide a method for preparing and applying a fluorine-free hydrophobic agent for glass, overcoming the problems of existing fluorine-based hydrophobic materials in terms of usage cost, environmental friendliness, and product safety, and promoting the application of fluorine-free hydrophobic materials in the field of cover glass.

[0005] Technical solution: The present invention provides a method for preparing a fluorine-free glass hydrophobic agent, comprising the following steps:

[0006] (1) Using a mixture of alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane as the main agent and alcohol solvent as the diluent, the mixture is stirred thoroughly during the preparation process to form a uniform mixture A;

[0007] (2) Using acid as a catalyst and a mixture of water and alcohol as a diluent, the mixture is stirred thoroughly during preparation to form a homogeneous mixture B;

[0008] (3) Add the agent B obtained in step (2) dropwise to the agent A obtained in step (1). After the addition is complete, seal the system and stir at a speed of 500~600r / min until a milky white uniform micelle system is formed, and the target fluorine-free glass hydrophobic agent can be obtained.

[0009] Further, in step (1), the alkyltrichlorosilane is selected from one of octyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane and octadecyltrichlorosilane; the alcohol solvent is selected from one of methanol, ethanol, isopropanol and n-butanol.

[0010] Further, in step (1), the molar ratio of the alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane is (1~10):1.

[0011] Further, in step (1), the total volume of the alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane is 5 to 10% of the volume of the alcohol solvent.

[0012] Further, in step (2), the acid catalyst is one of hydrochloric acid, nitric acid, acetic acid, phosphoric acid and sulfuric acid; the alcohol solvent is selected from one of methanol, ethanol, isopropanol and n-butanol.

[0013] Further, in step (2), the molar ratio of the amount of water added to the total amount of alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane is (4~15):1.

[0014] Furthermore, in step (2), the volume of water added is 25-50% of the volume of the alcohol solvent.

[0015] Further, in step (2), the amount of acid added is 0.1~0.5 mol of water.

[0016] Furthermore, in step (3), the stirring temperature is 25℃~65℃, and the stirring time is 2 h~12 h.

[0017] Another object of the present invention is to provide an application of the fluorine-free glass hydrophobic agent prepared by the above-mentioned method as a hydrophobic coating for cover glass.

[0018] Furthermore, the application includes the following steps:

[0019] (1) Remove the oily substances from the glass surface, then place it in deionized water, acetone and glycerol solvents and sonicate for 20-30 minutes each, and blow it dry with nitrogen;

[0020] (2) The glass after step (1) is subjected to plasma treatment to introduce polar groups on its surface to achieve a superhydrophilic surface;

[0021] (3) The fluorine-free glass hydrophobic agent prepared by the preparation method is uniformly sprayed onto the glass surface, dried at 70~80℃ for 1~3 hours, and then heat-treated at 120~150℃ for 1~3 hours.

[0022] Principle: A mixed system of alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane is used. The advantages of adding 11-acetoxyundecyltrichlorosilane are: 1. Unlike ordinary alkyltrichlorosilanes, the acetyl group at the end of 11-acetoxyundecyltrichlorosilane is an ester structure, which has better hydrophobicity; 2. The chain length of 11-acetoxyundecyltrichlorosilane is different from that of ordinary alkyltrichlorosilanes. During the friction test, the longer alkyl chain will be rubbed preferentially, while the shorter chain will continue to maintain its hydrophobic effect; 3. The acetyl group at the end of 11-acetoxyundecyltrichlorosilane is a typical electron-withdrawing group. During the friction test, it will release the generated charge and increase the number of friction cycles.

[0023] Beneficial effects: (1) The fluorine-free glass hydrophobic material of the present invention does not use any fluorine-containing substances, and it will not release harmful substances under extreme conditions. The product is pollution-free and safe to use, which is in line with the concept of green environmental protection.

[0024] (2) The raw materials required for the fluorine-free hydrophobic glass material of the present invention are simple and readily available, and the cost of use is lower than that of fluorine-containing hydrophobic materials. The fluorine-free hydrophobic material is easy to prepare and the subsequent spraying operation is simple, making it suitable for large-scale applications.

[0025] (3) After the cover glass is treated with the fluorine-free hydrophobic material of the present invention, the initial contact angle with water can reach more than 105° after testing. After 12,000 standard friction tests, the initial contact angle with water can still reach more than 100°, which meets the actual needs of commercialization. Attached Figure Description

[0026] Figure 1 The contact angle test results are shown for Corning GG3 glass after plasma treatment.

[0027] Figure 2 The image shows the contact angle of Corning GG3 glass treated with the hydrophobic agent prepared in Example 18.

[0028] Figure 3A flowchart of the reaction process for preparing a hydrophobic coating on glass. Detailed Implementation

[0029] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0030] Example 1:

[0031] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0032] Agent A: First, place octyltrichlorosilane (1.1 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (48 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0033] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0034] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0035] Example 2:

[0036] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0037] Agent A: First, place decyltrichlorosilane (1.2 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (52 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0038] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0039] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0040] Example 3:

[0041] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0042] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0043] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0044] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0045] Example 4:

[0046] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0047] Agent A: First, place tetradecyltrichlorosilane (1.5 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (58 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0048] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0049] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0050] Example 5:

[0051] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0052] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0053] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0054] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0055] Example 6:

[0056] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0057] Agent A: First, place octyltrichlorosilane (2.2 g, 9.0 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (68 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0058] Agent B: Next, place deionized water (0.9 g, 54 mmol), 36.5% concentrated hydrochloric acid (4.5 μL, 0.054 mmol), and ethanol (3.6 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0059] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0060] Example 7:

[0061] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0062] Agent A: First, place octyltrichlorosilane (11 g, 45 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (228 ml) in a 500 ml round-bottom flask, seal and stir until homogeneous.

[0063] Agent B: Next, place deionized water (3.5 g, 198 mmol), 36.5% concentrated hydrochloric acid (16.5 μL, 0.198 mmol), and ethanol (3.6 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0064] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0065] Example 8:

[0066] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0067] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and isopropanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0068] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and isopropanol (2.4 ml) into a 10 ml sample tube, seal and stir until homogeneous.

[0069] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0070] Example 9:

[0071] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0072] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and methanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0073] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and methanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0074] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0075] Example 10:

[0076] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0077] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and n-butanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0078] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and n-butanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0079] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0080] Example 11:

[0081] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0082] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (31 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0083] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0084] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0085] Example 12:

[0086] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0087] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (45 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0088] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0089] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0090] Example 13:

[0091] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0092] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0093] Agent B: Next, place deionized water (0.6 g, 36 mmol), 68% nitric acid (2.4 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0094] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0095] Example 14:

[0096] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0097] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0098] Agent B: Next, place deionized water (0.6 g, 36 mmol), glacial acetic acid (2 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0099] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0100] Example 15:

[0101] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0102] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0103] Agent B: Next, place deionized water (0.6 g, 36 mmol), 85% phosphoric acid (2.2 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0104] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0105] Example 16:

[0106] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0107] Agent A: First, place octadecyltrichlorosilane (1.7 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (62 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0108] Agent B: Next, place deionized water (0.6 g, 36 mmol), concentrated sulfuric acid (1.9 μL, 0.036 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0109] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0110] Example 17:

[0111] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0112] Agent A: First, place tetradecyltrichlorosilane (1.5 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (58 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0113] Agent B: Next, place deionized water (2.4 g, 135 mmol), 36.5% concentrated hydrochloric acid (11 μL, 0.135 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0114] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0115] Example 18:

[0116] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0117] Agent A: First, place tetradecyltrichlorosilane (1.5 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (58 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0118] Agent B: Next, place deionized water (1.6 g, 90 mmol), 36.5% concentrated hydrochloric acid (7.5 μL, 0.09 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0119] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0120] Example 19:

[0121] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0122] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0123] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (2.0 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0124] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0125] Example 20:

[0126] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0127] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0128] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (3 μL, 0.036 mmol), and ethanol (1.2 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0129] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0130] Example 21:

[0131] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0132] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0133] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (9 μL, 0.108 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0134] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0135] Example 22:

[0136] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0137] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0138] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (15 μL, 0.18 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0139] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0140] Example 23:

[0141] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0142] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0143] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (15 μL, 0.18 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0144] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 55°C. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0145] Example 24:

[0146] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0147] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0148] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (15 μL, 0.18 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0149] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 65℃. Continue stirring at this temperature for 2 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0150] Example 25:

[0151] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0152] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0153] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (15 μL, 0.18 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0154] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 8 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0155] Example 26:

[0156] The specific steps for preparing a fluorine-free hydrophobic agent for glass covers are as follows:

[0157] Agent A: First, place dodecyltrichlorosilane (1.4 g, 4.5 mmol), 11-acetoxyundecyltrichlorosilane (1.5 g, 4.5 mmol), and ethanol (54 ml) in a 100 ml round-bottom flask, seal and stir until homogeneous.

[0158] Agent B: Next, place deionized water (0.6 g, 36 mmol), 36.5% concentrated hydrochloric acid (15 μL, 0.18 mmol), and ethanol (2.4 ml) in a 10 ml sample tube, seal and stir until homogeneous.

[0159] Add the well-stirred agent B dropwise slowly to the well-stirred agent A. After the addition is complete, immediately seal the round-bottom flask and set the stirring temperature to 25°C. Continue stirring at this temperature for 12 hours to obtain a milky white fluorine-free glass hydrophobic agent with a lid.

[0160] Test example:

[0161] The cover glass surface was treated with a hydrophobic coating, and its contact angle with water and frictional properties were tested. The specific steps are as follows:

[0162] First, the Corning GG3 glass was cut into 50*50 cm pieces and then placed in a soapy water solution, sonicated for 30 minutes to remove surface oils. Next, it was sonicated for 25 minutes each in deionized water, acetone, and glycerol. Finally, the cleaned Corning GG3 white glass was dried with nitrogen in a cleanroom, and then placed horizontally in a plasma cleaner for 30 minutes of surface treatment. This process introduces polar groups such as hydroxyl groups onto the Corning GG3 white glass surface, creating a superhydrophilic surface that facilitates subsequent hydrophobic treatments, such as... Figure 1 The contact angle between the plasma-treated Corning GG3 glass and water is almost 0.

[0163] Next, the fluorine-free hydrophobic material system prepared in Examples 1-26 was uniformly sprayed onto the surface of Corning GG3 white glass. After spraying, it was placed at 75°C for 2 hours to allow the ethanol in the fluorine-free hydrophobic material system to evaporate completely. After drying, the hydrophobically treated Corning GG3 white glass was placed in a vacuum oven and the temperature was set to 140°C for 2 hours. After heat treatment, contact angle and friction tests were performed, and the test results are shown in Table 1.

[0164] Figure 2 The contact angles between Corning GG3 glass treated with the hydrophobic agent obtained in Example 18 and water are shown, with the left contact angle being 109.3° and the right contact angle being 108.7°.

[0165] Table 1:

[0166]

[0167] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing a fluorine-free glass hydrophobic agent, characterized in that, Includes the following steps: (1) Using a mixture of alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane as the main agent and alcohol solvent as the diluent, the mixture is stirred thoroughly during the preparation process to form a uniform mixture A; (2) Using acid as a catalyst and a mixture of water and alcohol as a diluent, the mixture is stirred thoroughly during preparation to form a homogeneous mixture B; (3) Add the agent B obtained in step (2) dropwise to the agent A obtained in step (1). After the addition is complete, seal the system and stir at a speed of 500~600r / min until a milky white uniform micelle system is formed, and the target fluorine-free glass hydrophobic agent can be obtained. (4) Remove the oily substances from the glass surface, then place it in deionized water, acetone and glycerol solvents and sonicate for 20-30 minutes each, and blow it dry with nitrogen. (5) The glass after step (4) is subjected to plasma treatment to introduce polar groups on its surface to achieve a superhydrophilic surface; (6) The fluorine-free glass hydrophobic agent prepared in step (3) is uniformly sprayed onto the glass surface, dried at 70~80℃ for 1~3 hours, and then heat-treated at 120~150℃ for 1~3 hours.

2. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (1), the alkyltrichlorosilane is selected from one of octyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane and octadecyltrichlorosilane; the alcohol solvent is selected from one of methanol, ethanol, isopropanol and n-butanol.

3. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (1), the molar ratio of the alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane is (1~10):

1.

4. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (1), the total volume of the alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane is 5 to 10% of the volume of the alcohol solvent.

5. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (2), the acid catalyst is one of hydrochloric acid, nitric acid, acetic acid, phosphoric acid and sulfuric acid; the alcohol solvent is selected from one of methanol, ethanol, isopropanol and n-butanol.

6. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (2), the molar ratio of the amount of water added to the total amount of alkyltrichlorosilane and 11-acetoxyundecyltrichlorosilane is (4~15):

1.

7. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (2), the volume of water added is 25 to 50% of the volume of the alcohol solvent.

8. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (2), the amount of acid added is 0.1 to 0.5 mol of water.

9. The method for preparing a fluorine-free glass hydrophobic agent according to claim 1, characterized in that, In step (3), the stirring temperature is 25℃~65℃ and the stirring time is 2 h~12 h.

10. The application of the fluorine-free glass hydrophobic agent prepared by the preparation method of any one of claims 1-9 as a hydrophobic coating for cover glass.

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