Modified resin material for ski helmet goggles and preparation method thereof

Abstract

The present invention discloses a modified resin material for ski helmet goggles and a preparation method thereof, relating to the technical field of organic materials. The present invention discloses a modified resin material for ski helmet goggles, which is obtained by blending a silica-modified acrylate resin, a reactive diluent, a photoinitiator, a leveling agent, and a solvent. The silica-modified acrylate resin is obtained by copolymerizing an acrylate monomer with modified mesoporous silica. The modified mesoporous silica is obtained by subjecting epoxidized mesoporous silica to a series of organic modifications. The modified mesoporous silica prepared in this application, when added to the resin material preparation, effectively imparts excellent hydrophilic and oleophobic properties, high adhesion, and wear resistance to the material, effectively improving the long-term effectiveness of the modified resin material as an anti-fog coating.

Description

Technical Field

[0001] The invention relates to the technical field of organic materials, and in particular to a modified resin material for ski helmet goggles and a preparation method thereof. Background Art

[0002] Ski goggles are essential eye protection for skiing, directly affecting a skier's vision and ultimately their safety. Snow strongly reflects sunlight, and the cold wind during skiing can be very irritating to the eyes. Ski goggles not only protect the eyes but also offer UV protection, anti-glare, and anti-fogging features, ensuring a clear field of vision and protecting the eyes from external hazards. To protect the eyes, ski goggles are often airtight. Atomization is the process by which water changes from vapor to liquid. When moist air comes into contact with a solid object at or below its dew point, it condenses into small, dispersed droplets on the solid surface, creating a fogging phenomenon. During skiing, due to the high temperature inside the goggles and the difficulty of moisture dissipating quickly, the formation of fog on the lenses will go through the stages of droplet growth and droplet nucleation. When the droplet nucleation tends to form independent droplets, the small water droplets formed by condensation adhere to the inner wall. When the contact angle of the droplets is greater than 48.8°, due to the existence of total reflection in the outer circle, the outer circle of the droplets becomes a low-light-transmittance area and the inner circle becomes a high-light-transmittance area. The difference in light transmittance causes the lens to become blurred, affecting its normal operation.

[0003] For the anti-fog treatment of lens substrates, the existing technology generally adopts the external coating method to deposit an anti-fog coating on the surface of the substrate to adjust the affinity between the lens substrate and water droplets; anti-fog coatings can be divided into organic anti-fog coatings and inorganic anti-fog coatings; among them, the main active ingredients of organic anti-fog coatings are some polymers containing hydrophilic functional groups. The polymers prepared from these hydrophilic hydroxyl, carboxyl, sulfonic acid or dihydrogen phosphate monomers have good processability and high transparency in addition to being hydrophilic. They are ideal raw materials for anti-fog coatings. However, due to the inherent hydrophilic characteristics of this type of coating, it is easily soluble in water, resulting in a short anti-fog effect of the coating and easy failure in long-term use in outdoor environments. Moreover, due to the use of the anti-fog coating, a water film is easily formed on the surface of the lens. The water film effectively improves the material's adsorption of hydrocarbons in the air, greatly increasing the occurrence of the lens being contaminated by hydrocarbons in the air, affecting the formation of a continuous water film on the lens surface, resulting in long-term anti-fog effect on the lens. Summary of the Invention

[0004] The purpose of the present invention is to provide a modified resin material for ski helmet goggles and a preparation method thereof, to solve the following technical problems:

[0005] The existing anti-fog coating is a hydrophilic coating, which is easily soluble in water. As a result, the anti-fog effect of the coating is short-lived and easily loses its effectiveness in long-term outdoor use.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing a modified resin material for ski helmet goggles comprises the following steps:

[0008] A1: In a nitrogen atmosphere, add acrylate monomer, modified mesoporous silica, azobisisobutyronitrile, and methanol to a reaction kettle and disperse evenly. Control the temperature at 60-70°C and keep the reaction for 18-24 hours. Add toluene to terminate the reaction and dry to obtain silica-modified acrylate resin.

[0009] A2: According to the raw material ratio, the silica-modified acrylate resin, reactive diluent, photoinitiator, leveling agent and solvent are blended to obtain a modified resin material;

[0010] The preparation method of modified mesoporous silica comprises the following steps:

[0011] S1: Epoxidized mesoporous silica and N,N-dimethylformamide are added to a reaction kettle and dispersed evenly. 2-acrylamido-2-methylpropanesulfonic acid and hydroquinone are added. The temperature is controlled at 65-75°C and the reaction is kept warm for 3-6 hours. Deionized water at 50-60°C is added to terminate the reaction. The reaction is filtered, washed, and dried to obtain component 1. Hydroquinone acts as a free radical inhibitor to effectively prevent the high-temperature polymerization of the acrylamide group of 2-acrylamido-2-methylpropanesulfonic acid.

[0012] S2: In a nitrogen atmosphere, component 1, 1,1,2,2-tetrahydroperfluorohexyl iodide, sodium bicarbonate, sodium dithionite, and acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 40-50°C. The reaction was kept warm for 6-9 hours, and then washed and dried to obtain component 2.

[0013] S3: In a nitrogen atmosphere, component 2, lithium aluminum hydride, and tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 6-9 hours, and deionized water was added. The mixture was filtered, washed, and dried to obtain component 3.

[0014] S4: In a nitrogen atmosphere, triethylamine, tetrahydrofuran, and triethylamine are added to a reaction kettle and dispersed evenly. Acryloyl chloride is added and reacted at room temperature for 3-6 hours. The pH value is adjusted to 7-8. The mixture is filtered, washed, and dried to obtain modified mesoporous silica.

[0015] As a further embodiment of the present invention, the acrylate monomer is obtained by mixing methyl methacrylate, butyl methacrylate, and hydroxyethyl acrylate in a molar ratio of 1:1-2:2-3; the addition ratio of the acrylate monomer, modified mesoporous silica, azobisisobutyronitrile, and methanol in A1 is 50-80 g: 5-15 g: 1.5-2: 400-1000 mL.

[0016] As a further embodiment of the present invention: the modified resin material in A2 comprises the following raw materials in parts by weight: 50-80 parts of silica-modified acrylate resin, 5-10 parts of reactive diluent, 5-6 parts of photoinitiator, 0.1-2 parts of leveling agent, 1-2 parts of auxiliary agent, and 40-60 parts of solvent;

[0017] The active diluent is one or more of acrylic acid, methacrylic acid, and hydroxyethyl methacrylate mixed in any ratio;

[0018] The photoinitiator is a mixture of benzophenone and 2-hydroxy-2-methyl-1-phenyl-1-propanone in a mass ratio of 2:2-3;

[0019] The leveling agent is any one of BYK-306, BYK-333, and BYK-3700;

[0020] The solvent is either ethanol or isopropanol.

[0021] As a further embodiment of the present invention: A method for preparing epoxidized mesoporous silica comprises the following steps: adding epichlorohydrin, potassium hydroxide, and tetrabutylammonium sulfate into a reaction kettle and uniformly dispersing them, adding mesoporous silica, stirring at room temperature for 12-24 hours, centrifuging, washing, and drying to obtain epoxidized mesoporous silica.

[0022] As a further embodiment of the present invention, the addition ratio of epichlorohydrin, potassium hydroxide, n-tetrabutylammonium sulfate, and mesoporous silica is 1-1.1 g: 0.6-1 g: 0.05-0.1 g: 10 g.

[0023] As a further embodiment of the present invention, the addition ratio of epoxidized mesoporous silica, N,N-dimethylformamide, 2-acrylamido-2-methylpropanesulfonic acid, and hydroquinone in S1 is 10 g: 50-100 mL: 2-3 g: 0.01-0.02 g.

[0024] As a further embodiment of the present invention, the addition ratio of component 1, 1,1,2,2-tetrahydroperfluorohexyl iodide, sodium bicarbonate, sodium dithionite, acetonitrile, and deionized water in S2 is 10 g: 3.7-5.6 g: 0.8-1.2 g: 1.8-2.8 g: 50-100 mL: 25-50 mL.

[0025] As a further solution of the present invention: the addition ratio of component 2, lithium aluminum hydride, tetrahydrofuran, and deionized water in S3 is 10 g: 1-2 g: 50-100 mL: 5-10 mL.

[0026] As a further embodiment of the present invention, the addition ratio of the components triethylamine, tetrahydrofuran, and acryloyl chloride in S4 is 10 g: 1-1.5 g: 50-100 mL: 0.3-0.6 g.

[0027] A modified resin material for ski helmet goggles is made by any of the above-mentioned preparation methods.

[0028] Beneficial effects of the present invention:

[0029] The present application uses tetrabutylammonium sulfate as a catalyst to cause a ring-opening reaction of epichlorohydrin with an etherification reaction of the hydroxyl groups on the surface of the mesoporous silica, and then a ring-closing reaction occurs under the action of a strong base of potassium hydroxide to obtain epoxidized mesoporous silica. The present application first uses the epoxy groups on the surface of the epoxidized mesoporous silica to undergo a ring-opening reaction with the sulfonic acid groups of 2-acrylamido-2-methylpropanesulfonic acid to obtain component one; and then uses the double bond on component one to undergo free radical addition with 1,1,2,2-tetrahydroperfluorohexyl iodide to obtain component two; then uses lithium aluminum hydride to reduce and deiodine to obtain component three; finally, uses acryloyl chloride to react with the hydroxyl groups of component three to graft the double bond onto the surface of the silica to obtain modified mesoporous silica.

[0030] The present application uses silica-modified acrylate resin as the matrix of the modified resin material coating. The present application modifies mesoporous silica during the preparation process of the acrylate resin to obtain silica-modified acrylate resin. The mesoporous properties of the modified mesoporous silica itself effectively adjust the light transmittance of the coating, and the double bonds grafted on the molecular chains on the surface of the mesoporous silica effectively graft it onto the molecular chains of the acrylate resin substrate, effectively avoiding the problem of short anti-fog duration of the coating due to its water solubility during use. The present invention grafts hydrophilic groups near the surface of mesoporous silica and grafts hydrophobic groups on the surface away from the mesoporous silica, and achieves the hydrophilic-oleophobic properties of the coating by adjusting the density of perfluorinated chains on the surface of the mesoporous silica. The outermost fluorinated layer of the coating has defects of appropriate size to prepare a responsive surface, so that the fluorinated layer can prevent larger oil molecules from penetrating the coating, and can also allow smaller water molecules to rearrange the surface molecules through the fluorinated layer to reach the more hydrophilic hydrophilic layer to form a water film, thereby achieving an anti-fog effect; and the flow of water can also carry away the oil droplets on the surface, achieving a self-cleaning effect; the modified resin material prepared by the present invention is used as a coating and applied to the surface of the goggles to obtain goggles with excellent and long-lasting anti-fog performance. Moreover, with the addition of the modified mesoporous silica prepared by the present invention, the material is given excellent friction resistance and self-cleaning properties, giving ski goggles the advantage of long-lasting anti-fog. DETAILED DESCRIPTION

[0031] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0032] Example 1 The preparation method of modified mesoporous silica comprises the following steps:

[0033] S1: Add 0.3 g of sodium hydroxide and 100 mL of deionized water into a reactor and disperse them evenly. Add 1 g of hexadecyltrimethylammonium bromide, control the temperature at 60°C, add 5 mL of tetraethyl orthosilicate, and keep the reaction warm for 4 h. Filter, dry the solid, and calcine at 550°C for 4 h to obtain mesoporous silica.

[0034] S2: 1 g of epichlorohydrin, 0.6 g of potassium hydroxide, and 0.05 g of tetrabutylammonium sulfate were added to a reaction kettle and dispersed evenly. 10 g of mesoporous silica was added and stirred at room temperature for 12 h. The mixture was centrifuged, washed, and dried to obtain epoxidized mesoporous silica.

[0035] S3: 10 g of epoxidized mesoporous silica and 50 mL of N,N-dimethylformamide were added to a reaction kettle and dispersed evenly. 2 g of 2-acrylamido-2-methylpropanesulfonic acid and 0.01 g of hydroquinone were added. The temperature was controlled at 65°C and the reaction was kept warm for 3 h. The reaction was terminated by adding 50°C deionized water. The mixture was filtered, washed, and dried to obtain component 1.

[0036] S4: In a nitrogen atmosphere, 10 g of component 1, 3.7 g of 1,1,2,2-tetrahydroperfluorohexyl iodide, 0.8 g of sodium bicarbonate, 1.8 g of sodium dithionite, and 25 mL of acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 40°C. The mixture was kept warm for 6 h, washed, and dried to obtain component 2.

[0037] S5: In a nitrogen atmosphere, 10 g of component 2, 1 g of lithium aluminum hydride, and 50 mL of tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 6 h, and 5 mL of deionized water was added. The mixture was filtered, washed, and dried to obtain component 3.

[0038] S6: In a nitrogen atmosphere, 10 g of component three, 1 g of triethylamine, and 50 mL of tetrahydrofuran were added to a reactor and dispersed evenly. 0.3 g of acryloyl chloride was added and reacted at room temperature for 3 h. The pH value was adjusted to 7, and the modified mesoporous silica was obtained by filtration, washing, and drying.

[0039] Example 2 The preparation method of modified mesoporous silica comprises the following steps:

[0040] S1: Add 0.3 g of sodium hydroxide and 100 mL of deionized water into a reactor and disperse them evenly. Add 1 g of hexadecyltrimethylammonium bromide, control the temperature at 60°C, add 5 mL of tetraethyl orthosilicate, and keep the reaction warm for 4 h. Filter, dry the solid, and calcine at 550°C for 4 h to obtain mesoporous silica.

[0041] S2: 1 g of epichlorohydrin, 0.8 g of potassium hydroxide, and 0.08 g of tetrabutylammonium sulfate were added to a reaction kettle and dispersed evenly. 10 g of mesoporous silica was added and stirred at room temperature for 18 h. The mixture was centrifuged, washed, and dried to obtain epoxidized mesoporous silica.

[0042] S3: 10 g of epoxidized mesoporous silica and 70 mL of N,N-dimethylformamide were added to a reaction kettle and dispersed evenly. 2.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 0.01 g of hydroquinone were added. The temperature was controlled at 70°C and the reaction was kept warm for 4.5 h. The reaction was terminated by adding 55°C deionized water. The mixture was filtered, washed, and dried to obtain component 1.

[0043] S4: In a nitrogen atmosphere, 10 g of component 1, 4.5 g of 1,1,2,2-tetrahydroperfluorohexyl iodide, 1 g of sodium bicarbonate, 2.5 g of sodium dithionite, and 40 mL of acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 45°C. The mixture was kept warm for 8 h, washed, and dried to obtain component 2.

[0044] S5: In a nitrogen atmosphere, 10 g of component 2, 1.5 g of lithium aluminum hydride, and 70 mL of tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 8 h, and 7 mL of deionized water was added. The mixture was filtered, washed, and dried to obtain component 3.

[0045] S6: In a nitrogen atmosphere, 10 g of component three, 1.2 g of triethylamine, and 70 mL of tetrahydrofuran were added to a reactor and dispersed evenly. 0.5 g of acryloyl chloride was added and reacted at room temperature for 4.5 h. The pH value was adjusted to 7, and the mixture was filtered, washed, and dried to obtain modified mesoporous silica.

[0046] Example 3 The preparation method of modified mesoporous silica includes the following steps:

[0047] S1: Add 0.3 g of sodium hydroxide and 100 mL of deionized water into a reactor and disperse them evenly. Add 1 g of hexadecyltrimethylammonium bromide, control the temperature at 60°C, add 5 mL of tetraethyl orthosilicate, and keep the reaction warm for 4 h. Filter, dry the solid, and calcine at 550°C for 4 h to obtain mesoporous silica.

[0048] S2: 1-1.1 g of epichlorohydrin, 1 g of potassium hydroxide, and 0.1 g of tetrabutylammonium sulfate were added to a reaction kettle and dispersed evenly. 10 g of mesoporous silica was added and stirred at room temperature for 24 h. The mixture was centrifuged, washed, and dried to obtain epoxidized mesoporous silica.

[0049] S3: 10 g of epoxidized mesoporous silica and 100 mL of N,N-dimethylformamide were added to a reaction kettle and dispersed evenly. 3 g of 2-acrylamido-2-methylpropanesulfonic acid and 0.02 g of hydroquinone were added. The temperature was controlled at 75°C and the reaction was kept warm for 6 h. The reaction was terminated by adding 60°C deionized water. The mixture was filtered, washed, and dried to obtain component 1.

[0050] S4: In a nitrogen atmosphere, 10 g of component 1, 5.6 g of 1,1,2,2-tetrahydroperfluorohexyl iodide, 1.2 g of sodium bicarbonate, 2.8 g of sodium dithionite, and 50 mL of acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 50°C. The reaction was kept at this temperature for 9 h, and then washed and dried to obtain component 2.

[0051] S5: In a nitrogen atmosphere, 10 g of component 2, 2 g of lithium aluminum hydride, and 100 mL of tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 9 h, and 10 mL of deionized water was added. The mixture was filtered, washed, and dried to obtain component 3.

[0052] S6: In a nitrogen atmosphere, 10 g of component three, 1.5 g of triethylamine, and 100 mL of tetrahydrofuran were added to a reactor and dispersed evenly. 0.6 g of acryloyl chloride was added and reacted at room temperature for 6 h. The pH value was adjusted to 7, filtered, washed, and dried to obtain modified mesoporous silica.

[0053] Example 4 A method for preparing a modified resin material for ski helmet goggles comprises the following steps:

[0054] A1: In a nitrogen atmosphere, 10 g of methyl methacrylate, 16 g of butyl methacrylate, 30 g of hydroxyethyl acrylate, 10 g of the modified mesoporous silica prepared in Example 1, 1.5 g of azobisisobutyronitrile, and 400 mL of methanol were added to a reactor and dispersed evenly. The temperature was controlled at 60°C and the reaction was kept warm for 24 h. Toluene was added to terminate the reaction and the mixture was dried to obtain a silica-modified acrylate resin.

[0055] A2: 60 g of silica-modified acrylate resin, 5 g of reactive diluent, 2 g of benzophenone, 3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1 g of leveling agent BYK-306, and 60 g of ethanol were blended to obtain a modified resin material.

[0056] Example 5 A method for preparing a modified resin material for ski helmet goggles comprises the following steps:

[0057] A1: In a nitrogen atmosphere, 10 g of methyl methacrylate, 16 g of butyl methacrylate, 30 g of hydroxyethyl acrylate, 10 g of the modified mesoporous silica prepared in Example 2, 1.5 g of azobisisobutyronitrile, and 400 mL of methanol were added to a reactor and dispersed evenly. The temperature was controlled at 60°C and the reaction was kept warm for 24 h. Toluene was added to terminate the reaction and the mixture was dried to obtain a silica-modified acrylate resin.

[0058] A2: 60 g of silica-modified acrylate resin, 5 g of reactive diluent, 2 g of benzophenone, 3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1 g of leveling agent BYK-306, and 60 g of ethanol were blended to obtain a modified resin material.

[0059] Example 6 A method for preparing a modified resin material for ski helmet goggles comprises the following steps:

[0060] A1: In a nitrogen atmosphere, 10 g of methyl methacrylate, 16 g of butyl methacrylate, 30 g of hydroxyethyl acrylate, 10 g of the modified mesoporous silica prepared in Example 3, 1.5 g of azobisisobutyronitrile, and 400 mL of methanol were added to a reactor and dispersed evenly. The temperature was controlled at 60°C and the reaction was kept warm for 24 h. Toluene was added to terminate the reaction and the mixture was dried to obtain a silica-modified acrylate resin.

[0061] A2: 60 g of silica-modified acrylate resin, 5 g of reactive diluent, 2 g of benzophenone, 3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1 g of leveling agent BYK-306, and 60 g of ethanol were blended to obtain a modified resin material.

[0062] Comparative Example 1 The preparation method of modified mesoporous silica comprises the following steps:

[0063] S1: 1g of epichlorohydrin, 0.8g of potassium hydroxide, and 0.08g of tetrabutylammonium sulfate were added to a reaction kettle and dispersed evenly. 10g of nano-silica was added and stirred at room temperature for 18h. The mixture was centrifuged, washed, and dried to obtain epoxidized silica.

[0064] S2: Add 10 g of epoxidized silica and 70 mL of N,N-dimethylformamide to a reactor and disperse evenly. Add 2.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 0.01 g of hydroquinone. Control the temperature to 70°C and keep the reaction for 4.5 h. Add 55°C deionized water to terminate the reaction. Filter, wash, and dry to obtain component 1.

[0065] S3: In a nitrogen atmosphere, 10 g of component 1, 4.5 g of 1,1,2,2-tetrahydroperfluorohexyl iodide, 1 g of sodium bicarbonate, 2.5 g of sodium dithionite, and 40 mL of acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 45°C. The mixture was kept warm for 8 h, washed, and dried to obtain component 2.

[0066] S4: In a nitrogen atmosphere, 10 g of component 2, 1.5 g of lithium aluminum hydride, and 70 mL of tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 8 h, and 7 mL of deionized water was added. The mixture was filtered, washed, and dried to obtain component 3.

[0067] S5: In a nitrogen atmosphere, 10 g of component three, 1.2 g of triethylamine, and 70 mL of tetrahydrofuran were added to a reactor and dispersed evenly. 0.5 g of acryloyl chloride was added and reacted at room temperature for 4.5 h. The pH value was adjusted to 7, and the mixture was filtered, washed, and dried to obtain modified silica.

[0068] Comparative Example 2 The preparation method of modified mesoporous silica comprises the following steps:

[0069] S1: Add 0.3 g of sodium hydroxide and 100 mL of deionized water into a reactor and disperse them evenly. Add 1 g of hexadecyltrimethylammonium bromide, control the temperature at 60°C, add 5 mL of tetraethyl orthosilicate, and keep the reaction warm for 4 h. Filter, dry the solid, and calcine at 550°C for 4 h to obtain mesoporous silica.

[0070] S2: 1 g of epichlorohydrin, 0.8 g of potassium hydroxide, and 0.08 g of tetrabutylammonium sulfate were added to a reaction kettle and dispersed evenly. 10 g of mesoporous silica was added and stirred at room temperature for 18 h. The mixture was centrifuged, washed, and dried to obtain epoxidized mesoporous silica.

[0071] S3: 10 g of epoxidized mesoporous silica and 70 mL of N,N-dimethylformamide were added to a reaction kettle and dispersed evenly. 2.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 0.01 g of hydroquinone were added. The temperature was controlled at 70°C and the reaction was kept warm for 4.5 h. The reaction was terminated by adding 55°C deionized water. The mixture was filtered, washed, and dried to obtain component 1.

[0072] S4: In a nitrogen atmosphere, 10 g of component 1, 4.5 g of 1,1,2,2-tetrahydroperfluorohexyl iodide, 1 g of sodium bicarbonate, 2.5 g of sodium dithionite, and 40 mL of acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 45°C. The mixture was kept warm for 8 h, washed, and dried to obtain component 2.

[0073] S5: In a nitrogen atmosphere, 10 g of component 2, 1.5 g of lithium aluminum hydride, and 70 mL of tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 8 h, and 7 mL of deionized water was added. The mixture was filtered, washed, and dried to obtain modified mesoporous silica.

[0074] Comparative Example 3 The preparation method of modified mesoporous silica comprises the following steps:

[0075] S1: Add 0.3 g of sodium hydroxide and 100 mL of deionized water into a reactor and disperse them evenly. Add 1 g of hexadecyltrimethylammonium bromide, control the temperature at 60°C, add 5 mL of tetraethyl orthosilicate, and keep the reaction warm for 4 h. Filter, dry the solid, and calcine at 550°C for 4 h to obtain mesoporous silica.

[0076] S2: 1 g of epichlorohydrin, 0.8 g of potassium hydroxide, and 0.08 g of tetrabutylammonium sulfate were added to a reaction kettle and dispersed evenly. 10 g of mesoporous silica was added and stirred at room temperature for 18 h. The mixture was centrifuged, washed, and dried to obtain epoxidized mesoporous silica.

[0077] S3: Add 10 g of epoxidized mesoporous silica and 70 mL of N,N-dimethylformamide into a reactor and disperse them evenly. Then add 2.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 0.01 g of hydroquinone. Control the temperature to 70°C and keep the reaction warm for 4.5 h. Add 55°C deionized water to terminate the reaction. Filter, wash, and dry to obtain modified mesoporous silica.

[0078] Comparative Example 4 The preparation method of modified mesoporous silica comprises the following steps:

[0079] S1: Add 0.3 g of sodium hydroxide and 100 mL of deionized water into a reactor and disperse them evenly. Add 1 g of hexadecyltrimethylammonium bromide, control the temperature at 60°C, add 5 mL of tetraethyl orthosilicate, and keep the reaction warm for 4 h. Filter, dry the solid, and calcine at 550°C for 4 h to obtain mesoporous silica.

[0080] S2: 1 g of vinyltrimethoxysilane, 30 mL of anhydrous ethanol, and 30 mL of deionized water were added to a reactor and dispersed evenly. 10 g of mesoporous silica was added and the temperature was controlled at 60°C and kept for 5 h to obtain vinyl mesoporous silica.

[0081] S3: In a nitrogen atmosphere, 10 g of vinyl mesoporous silica, 4.5 g of 1,1,2,2-tetrahydroperfluorohexyl iodide, 1 g of sodium bicarbonate, 2.5 g of sodium dithionite, and 40 mL of acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 45°C. The mixture was kept warm for 8 h, washed, and dried to obtain component 2.

[0082] S4: In a nitrogen atmosphere, 10 g of component 2, 1.5 g of lithium aluminum hydride, and 70 mL of tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 8 h, and 7 mL of deionized water was added. The mixture was filtered, washed, and dried to obtain component 3.

[0083] S5: In a nitrogen atmosphere, 10 g of component three, 1.2 g of triethylamine, and 70 mL of tetrahydrofuran were added to a reactor and dispersed evenly. 0.5 g of acryloyl chloride was added and reacted at room temperature for 4.5 h. The pH value was adjusted to 7, and the mixture was filtered, washed, and dried to obtain modified mesoporous silica.

[0084] Comparative Example 5 Comparative Example 5 is compared with Example 5, except that the modified mesoporous silica prepared in Example 1 added in Example 5 is replaced by the modified silica prepared in Comparative Example 1 in equal amounts, and the remaining components and preparation method are completely the same as those in Example 5.

[0085] Comparative Example 6 Compared with Example 5, Comparative Example 6 is only replaced by the modified mesoporous silica prepared in Example 1 in Example 5. The remaining components and preparation method are exactly the same as those in Example 5.

[0086] Comparative Example 7 Compared with Example 5, Comparative Example 7 is only replaced by the modified mesoporous silica prepared in Example 1 in Example 5. The remaining components and preparation method are exactly the same as those in Example 5.

[0087] Comparative Example 8 Compared with Example 5, Comparative Example 8 is only replaced by the modified mesoporous silica prepared in Example 1 in Example 5. The remaining components and preparation method are exactly the same as those in Example 5.

[0088] Performance testing

[0089] Prepare the test sample: The modified resin materials prepared in Examples 4-6 and Comparative Examples 5-8 were applied as coatings on the surface of polycarbonate goggles, dried for 30 seconds, and irradiated with a high-pressure mercury arc lamp (300W / inch) at 1J / cm 2 , coating thickness after curing is 5um;

[0090] (1) Hardness: Tested according to GB / T 6739-1996 “Determination of hardness of paint films by pencil method”. The test results are shown in Table 1.

[0091] (2) Adhesion: Tested according to GB / T 9286-1998 “Scratch test for paint and varnish films”. The test results are shown in Table 1.

[0092] (3) Friction resistance: The test was conducted using a friction tester with a wear tester roller model of CS-10F, a wear load of 250 g, and a wear tester speed of 80 rad / min. The test results are shown in Table 1.

[0093] Table 1: Statistics of performance test data of Examples 4-6 and Comparative Examples 5-8

[0094]

[0095] As can be seen from Table 1, the modified resin material prepared in the present application has good friction resistance and adhesion properties when applied as a coating on the surface of a lens.

[0096] (4) Anti-fog performance: Goggles coated with the modified resins prepared in Examples 4-6 and Comparative Examples 5-8 were placed in a 5°C environment and fumigated with 60°C hot water at a distance of 5 cm from the goggles for 15 seconds. The anti-fog performance level was determined according to Table 2. The test results are shown in Table 3.

[0097] Table 2: Anti-fog performance levels

[0098]

[0099] (5) Water contact angle test: The test was carried out using a JC20000D5 contact angle meter at room temperature. 2.5 μL of ultrapure water and hexadecane were dropped onto the surface of the material, respectively. The contact angles were measured to obtain the static hexadecane contact angle (OCA) and the static water contact angle (WCA). The conversion parameter SP was calculated according to the following formula:

[0100] Conversion parameter SP=OCA-WCA

[0101] Wherein, OCA is the contact angle of hexadecane, °; WCA is the contact angle of decahydrate, °; the test results are shown in Table 3;

[0102] (6) Light transmittance: Tested according to GB / T 2410-2008 “Determination of light transmittance and haze of transparent plastics”, using a color spectrum haze meter for measurement. The test results are shown in Table 3.

[0103] (7) Water resistance: The goggles were immersed in boiling water and the time when the coating turned white and swelled was recorded every 5 minutes. The test results are shown in Table 3.

[0104] Table 3: Statistical table of anti-fog performance test data of Examples 4-6 and Comparative Examples 5-8

[0105]

[0106] As can be seen from Table 3, the modified resin material prepared in the present application, as a coating, imparts good anti-fog and water resistance to the goggles, and has a high conversion parameter SP, imparting hydrophilic-oleophobic properties to the goggles and having a self-cleaning effect.

[0107] The above is a detailed description of an embodiment of the present invention. However, the content described is only a preferred embodiment of the present invention and should not be considered to limit the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing a modified resin material for ski helmet goggles, characterized in that: The steps include: A1: In a nitrogen atmosphere, add acrylate monomer, modified mesoporous silica, azobisisobutyronitrile, and methanol to a reaction kettle and disperse evenly. Control the temperature at 60-70°C and keep the reaction for 18-24 hours. Add toluene to terminate the reaction and dry to obtain silica-modified acrylate resin. A2: According to the raw material ratio, the silica-modified acrylate resin, reactive diluent, photoinitiator, leveling agent and solvent are blended to obtain a modified resin material; The preparation method of the modified mesoporous silica comprises the following steps: S1: Add epoxidized mesoporous silica and N,N-dimethylformamide to a reaction kettle and disperse evenly. Add 2-acrylamido-2-methylpropanesulfonic acid and hydroquinone. Control the temperature at 65-75°C and keep the reaction for 3-6 hours. Add 50-60°C deionized water to stop the reaction. Filter, wash, and dry to obtain component 1. S2: In a nitrogen atmosphere, component 1, 1,1,2,2-tetrahydroperfluorohexyl iodide, sodium bicarbonate, sodium dithionite, and acetonitrile were added to a reaction kettle and dispersed evenly. Deionized water was added and the temperature was raised to 40-50°C. The reaction was kept warm for 6-9 hours, and then washed and dried to obtain component 2. S3: In a nitrogen atmosphere, component 2, lithium aluminum hydride, and tetrahydrofuran were added to a reaction kettle and dispersed evenly. The mixture was allowed to stand at room temperature for 6-9 hours, and deionized water was added. The mixture was filtered, washed, and dried to obtain component 3. S4: In a nitrogen atmosphere, triethylamine, tetrahydrofuran, and triethylamine components were added to the reaction vessel and dispersed evenly. Acryloyl chloride was added and reacted at room temperature for 3-6 hours. The pH value was adjusted to 7-8. The modified mesoporous silica was filtered, washed, and dried. The acrylate monomer is obtained by mixing methyl methacrylate, butyl methacrylate, and hydroxyethyl acrylate in a molar ratio of 1:1-2:2-3; the addition ratio of the acrylate monomer, modified mesoporous silica, azobisisobutyronitrile, and methanol in A1 is 50-80g: 5-15g: 1.5-2g: 400-1000mL.

2. The method for preparing a modified resin material for ski helmet goggles according to claim 1, characterized in that: The modified resin material in A2 includes the following raw materials in parts by weight: 50-80 parts of silica-modified acrylate resin, 5-10 parts of reactive diluent, 5-6 parts of photoinitiator, 0.1-2 parts of leveling agent, 1-2 parts of auxiliary agent, and 40-60 parts of solvent; The active diluent is one or more of acrylic acid, methacrylic acid, and hydroxyethyl methacrylate mixed in any ratio; The photoinitiator is a mixture of benzophenone and 2-hydroxy-2-methyl-1-phenyl-1-propanone in a mass ratio of 2:2-3; The leveling agent is any one of BYK-306, BYK-333, and BYK-3700; The solvent is any one of ethanol or isopropanol.

3. The method for preparing a modified resin material for ski helmet goggles according to claim 1, characterized in that: The preparation method of epoxidized mesoporous silica comprises the following steps: adding epichlorohydrin, potassium hydroxide and tetrabutylammonium sulfate into a reaction kettle and dispersing them uniformly, adding mesoporous silica, stirring at room temperature for 12-24 hours, centrifuging, washing and drying to obtain epoxidized mesoporous silica.

4. The method for preparing a modified resin material for ski helmet goggles according to claim 3, characterized in that: The addition ratio of epichlorohydrin, potassium hydroxide, tetrabutylammonium sulfate and mesoporous silica is 1-1.1g: 0.6-1g: 0.05-0.1g: 10g.

5. The method for preparing a modified resin material for ski helmet goggles according to claim 1, characterized in that: The addition ratio of epoxidized mesoporous silica, N,N-dimethylformamide, 2-acrylamido-2-methylpropanesulfonic acid, and hydroquinone in S1 is 10 g: 50-100 mL: 2-3 g: 0.01-0.02 g.

6. The method for preparing a modified resin material for ski helmet goggles according to claim 1, characterized in that: The addition ratio of component 1, 1,1,2,2-tetrahydroperfluorohexyl iodide, sodium bicarbonate, sodium dithionite, acetonitrile, and deionized water in S2 is 10 g: 3.7-5.6 g: 0.8-1.2 g: 1.8-2.8 g: 50-100 mL: 25-50 mL.

7. The method for preparing a modified resin material for ski helmet goggles according to claim 1, characterized in that: The addition ratio of component 2, lithium aluminum hydride, tetrahydrofuran, and deionized water in S3 is 10 g: 1-2 g: 50-100 mL: 5-10 mL.

8. The method for preparing a modified resin material for ski helmet goggles according to claim 1, characterized in that: The addition ratio of components tris, triethylamine, tetrahydrofuran, and acryloyl chloride in S4 is 10 g: 1-1.5 g: 50-100 mL: 0.3-0.6 g.

9. A modified resin material for ski helmet goggles, characterized in that: Prepared by the preparation method according to any one of claims 1 to 8.

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