Composite material as well as preparation method and application thereof

Abstract

The invention provides a composite material as well as a preparation method and application thereof. The composite material comprises methylene bis-benzotriazolyl tetramethyl butyl phenol nanoparticles and polymethyl methacrylate, wherein the surfaces of the methylene bis-benzotriazolyl tetramethyl butyl phenol nanoparticles are coated with the polymethyl methacrylate, so that a polymethyl methacrylate layer is formed. Through the formed MBBT-PMMA core-shell structure, the contact effect of the methylene bis-benzotriazolyl tetramethyl butyl phenol and the polymethyl methacrylate is improved, the synergistic effect of the methylene bis-benzotriazolyl tetramethyl butyl phenol and the polymethyl methacrylate is fully played, the anti-ultraviolet performance of the composite material is remarkably improved, meanwhile, the core-shell structure endows the composite material with sufficient stability, and the anti-ultraviolet performance of the composite material is improved. The anti-ultraviolet durability of the composite material is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a composite material, a preparation method thereof, and an application thereof. Background Art

[0002] With the intensification of the greenhouse effect, the ozone layer is further damaged, which allows a small part of the short-wave ultraviolet rays that should have been filtered by the ozone layer in sunlight to reach the earth's surface, causing damage to human skin. The ultraviolet rays that can reach the earth's surface are mainly divided into long-wave ultraviolet rays (UVA) and medium-wave ultraviolet rays (UVB). Prolonged exposure to UVB will damage the proteins in the eye lens, causing them to denature and aggregate to form some insoluble turbidity, which will gradually form cataracts over time. While UVB will damage, exfoliate and necrose the epithelial cells of the eyes, thus triggering photokeratitis, similar to the damage caused by welding light to the eyes. At the same time, long-term exposure of the eyes to ultraviolet rays will cause chronic corneal lesions, which will affect the transparency of the cornea and thus affect vision, and will also increase the occurrence probability of other eye diseases. Secondly, the skin around the eyes is usually relatively fragile, and long-term ultraviolet irradiation will not only cause irreversible damage to the skin, but also make the skin age and accelerate the formation of crow's feet at the corners of the eyes. Therefore, it is imperative to protect the eyes and the skin around the eyes.

[0003] The traditional way to protect the eyes from ultraviolet irradiation is to wear a hat or glasses. The hat has a good protective effect on direct ultraviolet rays, but it is powerless against scattered or reflected ultraviolet rays. Therefore, as the last line of defense for the eyes, glasses play a role of a goalkeeper in protecting the eyes from ultraviolet rays. Therefore, improving the ultraviolet protection ability of glasses is of great significance for protecting the eyes.

[0004] Secondly, for glasses wearers, the ease of cleaning of glasses is also an important factor affecting the wearing experience. For some wearers of myopia glasses and presbyopic glasses, long-term use will cause a lot of stains and fingerprints on the glasses lenses. If not cleaned in time, it will lead to a decrease in the light transmittance of the lenses, affecting the user's visual experience, and even causing the wearer's vision to further decline in the long run. Currently, the main lens cleaning methods include ultrasonic cleaning and cleaning fluids, but this requires special equipment and cleaning fluids and cannot clean the glasses anytime and anywhere. Traditional direct water cleaning of the lenses cannot effectively remove stains, and water droplets are likely to remain on the lens surface, which will further affect the light transmittance and the user's visual experience. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems in the prior art to some extent. For this reason, an object of the present invention is to provide a composite material, a preparation method thereof, and an application thereof.

[0006] In the first aspect of the present invention, a composite material is proposed, which comprises: methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles and polymethyl methacrylate, and the polymethyl methacrylate coats the surface of the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles to form a polymethyl methacrylate layer.

[0007] According to the above composite material provided by the present invention, methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT) is an excellent organic sunscreen, which can effectively absorb ultraviolet rays in the UVA and UVB bands, providing broad-spectrum and effective ultraviolet protection. Polymethyl methacrylate (PMMA) is a linear thermoplastic polymer with a light transmittance as high as 92%, low density, moderate hardness and excellent weather resistance. The inventors found that if only the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles and polymethyl methacrylate are simply physically mixed, although the anti-ultraviolet performance of the mixed material is improved to a certain extent, the improvement effect is not significant, and the stability is also poor. In the present invention, by coating the polymethyl methacrylate on the surface of the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles to form a polymethyl methacrylate layer, the contact effect between methylene bis-benzotriazolyl tetramethylbutylphenol and polymethyl methacrylate is improved. On the one hand, the synergistic effect of the two is fully exerted, significantly enhancing the anti-ultraviolet performance of the composite material. On the other hand, the core-shell structure endows the composite material with sufficient stability, improving the long-term anti-ultraviolet performance of the composite material. Thus, the composite material has excellent anti-ultraviolet performance, high stability and long-lasting anti-ultraviolet effect.

[0008] In some embodiments of the present invention, the particle size of the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles is 300nm - 700nm. For example, the particle size is 300nm, 400nm, 500nm, 600nm, 700nm, etc., or the range between any two of the above values. Controlling the particle size of the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles within the above range can effectively prevent the phenomenon of pilling after addition, improve the product experience, and also avoid agglomeration due to too small particle size.

[0009] In some embodiments of the present invention, the thickness of the polymethyl methacrylate layer is 200 - 500nm. For example, the thickness is 200nm, 300nm, 400nm, 500nm, etc., or the range between any two of the above values. Controlling the thickness of the polymethyl methacrylate layer within the above range can prevent the uneven wrapping due to too thin thickness, resulting in the release of MBBT, and avoid the influence on the ultraviolet absorption effect of MBBT due to too thick thickness.

[0010] In some embodiments of the present invention, the composite material further comprises polyethylene glycol (PEG), and the polyethylene glycol coats the PMMA layer to form a polyethylene glycol layer. Polyethylene glycol has a higher functional group density and a smaller hydrodynamic volume. The waterproof and antifouling coating prepared from this composite material has a lower surface energy on its surface, making water droplets and stains gather on the lens surface rather than cover it. At the same time, it can effectively prevent the adhesion of fingerprints. In this way, even if there are stains on the lens surface, they can be cleaned with simple rinsing with clean water and no water droplets are left. In addition, the presence of such a waterproof and antifouling coating can also effectively defog. In some special scenarios, such as when sudden large temperature differences cause the lens surface to fog up, it can play an effective defogging effect. The principle is that the low surface energy on the lens surface makes water mist unable to effectively adhere and thus quickly evaporates. Therefore, using PEG to modify the material surface can endow the material with better antifouling ability and can effectively solve the problem of difficult cleaning of water droplets, stains or fingerprint on eyeglasses. At the same time, PEG, this kind of polymer, is sensitive to temperature. The structure of the microgel will change at different temperatures. When the temperature rises, the morphology will shrink and the crosslinking density will increase, making the overall MBBT-PMMA / PEG microgel have stronger ultraviolet absorption and reflection capabilities, which can not only greatly improve the ultraviolet protection ability of eyeglasses, but also greatly extend the service life of eyeglasses.

[0011] Preferably, the thickness of the polyethylene glycol layer is 200nm - 700nm. For example, the thickness is 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, etc., or the range between any two of the above values.

[0012] In some embodiments of the present invention, the polyethylene glycol is formed by the polymerization reaction of oligoethylene glycol methyl ether methacrylate, polyethylene glycol dimethacrylate, and 2-(2-methoxyethoxy)ethyl methacrylate.

[0013] Preferably, the molecular weight of the oligoethylene glycol methyl ether methacrylate is 200 - 400, more preferably 300, and the molecular weight of the polyethylene glycol dimethacrylate is 500 - 600, more preferably 550.

[0014] In some embodiments of the present invention, the oligoethylene glycol methyl ether methacrylate, polyethylene glycol dimethacrylate, and 2-(2-methoxyethoxy)ethyl methacrylate are purified through a neutral alumina chromatographic column to a purity of more than 95%.

[0015] In the second aspect of the present invention, the present invention proposes a method for preparing the above composite material, and the method comprises: (1) Mix and stir to disperse methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles and water to obtain an MBBT nanoparticle dispersion; (2) Add methyl methacrylate and divinylbenzene to the MBBT nanoparticle dispersion and stir to obtain a mixed solution. (3) Heat the mixed solution and then add an initiator to carry out a polymerization reaction to obtain MBBT nanoparticles coated with poly(methyl methacrylate) to form MBBT-PMMA core-shell composite materials.

[0016] According to the preparation method of the composite material provided by the present invention, first, methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles and water are mixed and stirred to disperse, so that the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles are fully dispersed in water; then, methyl methacrylate and divinylbenzene are added to the MBBT nanoparticle dispersion and stirred to make each material fully mixed and uniform. Then, the mixed solution is heated and an initiator is added. Under the action of the initiator, methyl methacrylate and divinylbenzene carry out a polymerization reaction to form a poly(methyl methacrylate) layer on the surface of the MBBT nanoparticles. The MBBT-PMMA core-shell composite material prepared by the above method gives full play to the synergistic effect of both MBBT and PMMA on the one hand, significantly improving the ultraviolet resistance of the composite material. On the other hand, the core-shell layer structure endows the composite material with sufficient stability and improves the long-term ultraviolet resistance of the composite material. Thus, a composite material with excellent and long-lasting ultraviolet resistance can be prepared by this method.

[0017] In some embodiments of the present invention, in step (1), the stirring speed is 500-700 r / min.

[0018] Preferably, the dispersion is carried out by ultrasonic dispersion, and the power of the ultrasonic dispersion is 400W-500W.

[0019] In some embodiments of the present invention, in step (2), the molar ratio of methyl methacrylate to divinylbenzene is (6-9):(200-300).

[0020] In some embodiments of the present invention, in step (2), the stirring speed is 500-700 r / min and the time is 30 min-60 min.

[0021] In some embodiments of the present invention, in step (3), the mixed solution is heated to 70-80 °C. Controlling the temperature of the mixed solution within the above range ensures the effective polymerization of methyl methacrylate and divinylbenzene and forms a poly(methyl methacrylate) layer on the surface of the MBBT nanoparticles.

[0022] In some embodiments of the present invention, in step (3), the initiator includes at least one of potassium persulfate, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, sodium bisulfite, ammonium persulfate, benzoyl peroxide, and azobisisobutyronitrile.

[0023] In some embodiments of the present invention, in step (3), the polymerization reaction time is 2 h - 2.5 h.

[0024] In some embodiments of the present invention, the method further includes: dispersing the MBBT-PMMA core-shell composite material in water, adding 2-(2-methoxyethoxy)ethyl methacrylate, oligoethylene glycol methyl ether methacrylate, and polyethylene glycol dimethacrylate, then heating up, and further adding 2,2'-azobis(2-methylpropionamidine) dihydrochloride to carry out a polymerization reaction to obtain an MBBT-PMMA / PEG composite material.

[0025] Preferably, the molar ratio of 2-(2-methoxyethoxy)ethyl methacrylate, oligoethylene glycol methyl ether methacrylate, and polyethylene glycol dimethacrylate is (200 - 300):(400 - 600):1.

[0026] By forming a PEG layer on the surface of the MBBT-PMMA core-shell composite material, its microgel structure will change with temperature, and the ultraviolet protection ability can be adjusted with temperature. When the external temperature rises, the ultraviolet protection ability will increase accordingly. This structure can also improve the waterproof and anti-fouling ability of the composite material. At the same time, the presence of the PEG layer is also beneficial to improving the stability of the composite material, thereby enhancing the long-term ultraviolet resistance of the composite material. On the other hand, the PEG layer can effectively prevent the attachment of stains on the surface, is easy to clean, does not leave water droplets, and can also effectively defog. In particular, the polyethylene glycol layer prepared from 2-(2-methoxyethoxy)ethyl methacrylate, oligoethylene glycol methyl ether methacrylate, and polyethylene glycol dimethacrylate has a non-linear polyethylene glycol structure, which is more complex, mainly branched or star-shaped. This cross-linked structure can make the MBBT-PMMA core-shell material disperse evenly, prevent agglomeration and release, and at the same time can also make the microgel structure more stable, especially suitable for temperature-responsive structures. Secondly, using non-linear polyethylene glycol can make the overall microgel structure more stable.

[0027] Preferably, the temperature of the polymerization reaction is 60 - 80 °C, and the time is 5 h - 7 h.

[0028] In a third aspect of the present invention, the present invention provides a pair of glasses, which includes lenses, and an anti-ultraviolet coating is formed on at least one side of the lenses. The anti-ultraviolet coating includes the above composite material or the composite material prepared by the above method. Thus, the glasses have excellent and long-lasting anti-ultraviolet performance, good waterproof and anti-fouling ability, and a long service life.

[0029] In some embodiments of the present invention, the thickness of the anti-ultraviolet coating is 0.001 mm - 0.01 mm.

[0030] In some embodiments of the present invention, a titanium nitride coating is formed on the side of the ultraviolet-resistant coating away from the lens. By providing the titanium nitride coating, the wear resistance of the lens is improved, and its service life is extended.

[0031] Preferably, the thickness of the titanium nitride coating is 0.001 mm - 0.01 mm.

[0032] The present invention has at least the following technical effects: (1) In the present invention, by coating polymethyl methacrylate on the surface of methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles to form a polymethyl methacrylate layer, the above-mentioned core-shell layer structure is formed, which improves the contact effect between methylene bis-benzotriazolyl tetramethylbutylphenol and polymethyl methacrylate. On the one hand, the synergistic effect of the two is fully exerted, significantly enhancing the ultraviolet resistance of the composite material. On the other hand, the core-shell layer structure endows the composite material with sufficient stability, enhancing the long-term ultraviolet resistance of the composite material. This composite material has excellent ultraviolet resistance, high stability, and a long-lasting ultraviolet resistance effect.

[0033] (2) In the present invention, by forming a PEG layer on the surface of the MBBT-PMMA core-shell composite material, its microgel structure changes with temperature, and the ultraviolet protection ability is adjusted with temperature. When the external temperature rises, the ultraviolet protection ability increases accordingly. This structure can also improve the waterproof and anti-fouling ability of the composite material. At the same time, the presence of the PEG layer is beneficial to improving the stability of the composite material, thereby enhancing the long-term ultraviolet resistance of the composite material.

[0034] (3) In the present invention, by preparing the MBBT-PMMA / PEG microgel material and coating it on the surface of the spectacle lens, and using polyethylene glycol to modify the material, because polyethylene glycol has a higher functional group density and a smaller hydrodynamic volume, the surface of the prepared waterproof and anti-fouling coating has a lower surface energy, making water droplets and stains gather on the lens surface rather than cover it. At the same time, it can also effectively prevent the adhesion of fingerprints. In this way, even if there are stains on the surface of the prepared lens, it can be cleaned with simple rinsing with clean water and no water droplets will remain. In addition, the presence of the waterproof and anti-fouling coating prepared with the composite material of the present invention can also effectively defog, and can play an effective defogging effect in some special scenarios such as when the lens surface fogs up due to a sudden large temperature difference. Detailed implementation manners

[0035] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present invention. The following describes the present invention with reference to specific embodiments. It should be noted that these embodiments are only descriptive and do not limit the present invention in any way.

[0036] Example 1 This example provides a MBBT-PMMA composite material, and its specific preparation process is as follows: Take 0.3 mmol of MBBT with a particle size of 300 - 500 nm and disperse it in 200 ml of deionized water. Ultrasonically disperse it for 30 minutes at 400 W, stir at a rotation speed of 700 rpm, add 0.012 mmol of methyl methacrylate monomer and 0.4 mmol of divinylbenzene, continue to stir at a speed of 700 rpm for 30 min, then heat up to 70 °C, add 20 ml of potassium persulfate with a concentration of 0.01 mol / L to initiate the reaction. After reacting for 2 h, centrifuge the reaction solution twice to remove the supernatant. The centrifugation speed is 8000 rpm and the centrifugation time is 1 h.

[0037] In the prepared MBBT-PMMA composite material, the thickness of the PMMA layer is 200 - 300 nm.

[0038] This example provides a spectacle lens, and its specific preparation process is as follows: Step 1: Pretreatment of the lens: Immerse the lens in ethanol and ultrasonically clean it for 10 min (power 400 - 500 W). Take it out, wash it with pure water, and then dry the surface with nitrogen. Subsequently, dip a cotton swab in an ethanol solution of 1% γ-aminopropyltriethoxysilane (KH-550) and apply it to both the front and back sides of the lens. After standing for 30 min, slowly dry it with nitrogen.

[0039] Step 2: Add 0.1% hydroxyethyl cellulose to an aqueous solution of 50% isopropanol and ultrasonically disperse it for 20 min (power 400 - 500 W). After it becomes clear, add the pre-dispersed isopropanol solution of MBBT-PMMA with a mass fraction of 5% under magnetic stirring (700 rpm). Stir for 30 min and then ultrasonically treat it for 5 min (power 100 - 150 W). After uniform dispersion, spray the solution on both the front and back sides of the lens with a spray gun (spray gun air pressure 0.35 MPa, nozzle diameter 0.3 mm, spraying distance 12 cm). Spray back and forth 4 - 5 times and then gently blow the surface with nitrogen to accelerate the evaporation of the solvent. Repeat the above spraying and drying steps until the coating thickness on the lens surface reaches about 0.003 mm (detect the film thickness with an instrument such as a profilometer), then place the lens in an oven at 50 °C and bake it for 2 h, and then take it out and cool it to room temperature.

[0040] Step 3: Add 0.5 wt% polyvinylpyrrolidone to a solution of ethanol and water with a titanium nitride content of 1% and a ratio of 1:1. Disperse it by ultrasonic wave (400 - 500 W) for 10 min. After uniform dispersion, continue to spray it on both the front and back sides of the lens cooled in Step 2 with a spray gun. Reduce the spray gun pressure to 0.15 MPa, the spraying distance is 20 cm, and the nozzle diameter remains unchanged. The spraying operation is the same as in Step 2. Stop when the lens thickness reaches 0.001 mm. After spraying, place it in an oven at 50 °C and bake for 1 h, then take it out and cool it to room temperature.

[0041] Example 2 This example provides an MBBT-PMMA composite material, and its specific preparation process is as follows: Take 0.3 mmol of MBBT with a particle size of 400 - 600 nm and disperse it in 200 ml of deionized water. Disperse it by ultrasonic oscillation at 450 W for 30 minutes, stir at a speed of 600 rpm, add 0.015 mmol of methyl methacrylate monomer and 0.5 mmol of divinylbenzene, continue to stir at a speed of 600 rpm for 40 min, then heat up to 75 °C, add 20 ml of potassium persulfate with a concentration of 0.01 mol / L to initiate the reaction. After reacting for 2.5 h, centrifuge the reaction solution twice to remove the supernatant. The centrifugation speed is 8000 rpm and the centrifugation time is 1 h.

[0042] In the prepared MBBT-PMMA composite material, the thickness of the PMMA layer is 300 - 400 nm.

[0043] This example provides a spectacle lens, and its specific preparation process is the same as that of Example 1.

[0044] Example 3 This example provides an MBBT-PMMA composite material, and its specific preparation process is as follows: Take 0.3 mmol of MBBT with a particle size of 500 - 700 nm and disperse it in 200 ml of deionized water. Disperse it by ultrasonic oscillation at 500 W for 30 minutes, stir at a speed of 500 rpm, add 0.018 mmol of methyl methacrylate monomer and 0.6 mmol of divinylbenzene, continue to stir at a speed of 500 rpm for 30 min, then heat up to 80 °C, add 20 ml of potassium persulfate with a concentration of 0.01 mol / L to initiate the reaction. After reacting for 3 h, centrifuge the reaction solution twice to remove the supernatant. The centrifugation speed is 8000 rpm and the centrifugation time is 1 h.

[0045] In the prepared MBBT-PMMA composite material, the thickness of the PMMA layer is 400 - 500 nm.

[0046] This example provides a spectacle lens, and its specific preparation process is the same as that of Example 1.

[0047] Example 4 This example provides an MBBT-PMMA / PEG composite material, and its specific preparation process is as follows: (1) Preparation of the MBBT-PMMA composite material, and its specific preparation process is the same as that in Example 1.

[0048] (2) Take the MBBT-PMMA composite material in step (1), disperse it in 200 ml of deionized water, add 0.2 mmol of 2-(2-methoxyethoxy)ethyl methacrylate, 0.4 mmol of oligoethylene glycol methyl ether methacrylate (molecular weight of 300), 0.001 mmol of polyethylene glycol dimethacrylate (molecular weight of 550), then heat up to 65 °C, and then add 20 ml of 1 wt% 2,2'-azobis(2-methylpropionamidine) dihydrochloride to carry out a polymerization reaction, keep the temperature for 1 h, and react for 4 h to obtain the MBBT-PMMA / PEG composite material.

[0049] For the prepared MBBT-PMMA / PEG composite material, the thickness of the PEG layer is 200-400 nm.

[0050] This example provides a spectacle lens. The obtained MBBT-PMMA / PEG composite material is sprayed on the concave and convex surfaces of the spectacle lens by a spraying device, and the unilateral thickness is 0.003 mm. The spraying process is the same as that in Example 1, except that the MBBT-PMMA isopropanol solution in step two is replaced with an MBBT-PMMA / PEG isopropanol solution. And the titanium nitride layer is not sprayed.

[0051] Example 5 This example provides an MBBT-PMMA / PEG composite material, and its specific preparation process is as follows: (1) Preparation of the MBBT-PMMA composite material, and its specific preparation process is the same as that in Example 1.

[0052] (2) Take the MBBT-PMMA composite material in step (1), disperse it in 200 ml of deionized water, add 0.25 mmol of 2-(2-methoxyethoxy)ethyl methacrylate, 0.5 mmol of oligoethylene glycol methyl ether methacrylate (molecular weight of 200), 0.001 mmol of polyethylene glycol dimethacrylate (molecular weight of 500), then heat up to 70 °C, and then add 20 ml of 1 wt% 2,2'-azobis(2-methylpropionamidine) dihydrochloride to carry out a polymerization reaction, keep the temperature for 1 h, and react for 5 h to obtain the MBBT-PMMA / PEG composite material.

[0053] For the prepared MBBT-PMMA / PEG composite material, the thickness of the PEG layer is 300-500 nm This embodiment provides a spectacle lens, and its preparation process is the same as that of Embodiment 4.

[0054] Embodiment 6 This embodiment provides an MBBT-PMMA / PEG composite material, and its specific preparation process is as follows: (1) Preparation of the MBBT-PMMA composite material, and its specific preparation process is the same as that of Embodiment 1.

[0055] (2) Take the MBBT-PMMA composite material in step (1), disperse it in 200 ml of deionized water, add 0.30 mmol of 2-(2-methoxyethoxy)ethyl methacrylate, 0.6 mmol of oligoethylene glycol methyl ether methacrylate (molecular weight 400), 0.001 mmol of polyethylene glycol dimethacrylate (molecular weight 500), then heat up to 60 °C, and then add 20 ml of 1 wt% 2,2'-azobis(2-methylpropionamidine) dihydrochloride to carry out a polymerization reaction, keep the temperature for 1 h, and react for 6 h to obtain the MBBT-PMMA / PEG composite material.

[0056] For the prepared MBBT-PMMA / PEG composite material, the thickness of the PEG layer is 400 - 600 nm.

[0057] This embodiment provides a spectacle lens, and its preparation process is the same as that of Embodiment 4.

[0058] Embodiment 7 This embodiment provides an MBBT-PMMA / PEG composite material, and its specific preparation process is as follows: (1) Preparation of the MBBT-PMMA composite material, and its specific preparation process is the same as that of Embodiment 1.

[0059] (2) Take the MBBT-PMMA composite material in step (1), disperse it in 200 ml of deionized water, add 0.35 mmol of 2-(2-methoxyethoxy)ethyl methacrylate, 0.7 mmol of oligoethylene glycol methyl ether methacrylate (molecular weight 400), 0.001 mmol of polyethylene glycol dimethacrylate (molecular weight 600), then heat up to 80 °C, and then add 20 ml of 1 wt% 2,2'-azobis(2-methylpropionamidine) dihydrochloride to carry out a polymerization reaction, keep the temperature for 1 h, and react for 6 h to obtain the MBBT-PMMA / PEG composite material.

[0060] For the prepared MBBT-PMMA / PEG composite material, the thickness of the PEG layer is 500 - 700 nm.

[0061] This embodiment provides a spectacle lens, and its preparation process is the same as that of Embodiment 4.

[0062] Comparative Example 1 This Comparative Example 1 provides a physical mixture of MBBT and PMMA, and its specific preparation process is as follows: Take 200 ml of deionized water, stir at a rotation speed of 600 rpm, add 0.015 mmol of methyl methacrylate monomer and 0.5 mmol of divinylbenzene, continue to stir at a speed of 600 rpm for 30 min, then heat up to 70 °C, add 20 ml of potassium persulfate with a concentration of 0.01 mol / L to initiate the reaction. After reacting for 2.5 h, take 0.3 mmol of MBBT with a particle size of 400 - 600 nm and disperse it by ultrasonic wave (power 450 W) to be evenly dispersed. Centrifuge the mixed solution twice to remove the supernatant. The centrifuge rotation speed is 8000 rpm and the centrifuge time is 1 h to prepare a physical mixture of MBBT and PMMA.

[0063] This example provides a spectacle lens, and its preparation process is the same as that of Example 1, with the difference that in step two, the MBBT - PMMA isopropanol solution is replaced by a physical mixture of MBBT and PMMA in isopropanol solution. The thickness of the unilateral coating of the lens is 0.003 mm.

[0064] Comparative Example 2 Disperse titanium dioxide with a particle size of 400 - 600 nm in ethanol, and spray it onto the front and back sides of the spectacle lens using a spray gun. The spraying conditions are the same as those in Example 1, and the subsequent drying and titanium nitride spraying operations are the same as those in Example 1.

[0065] The thickness of the unilateral titanium dioxide layer is 0.003 mm, and then continue to spray titanium nitride. The spraying conditions are the same as those in Example 1, and the subsequent drying and titanium nitride spraying operations are the same as those in Example 1. The thickness of the obtained titanium nitride layer is 0.001 mm.

[0066] Comparative Example 3 Using a spraying device, only spray titanium nitride on the surface of the spectacle lens. The spraying conditions are the same as those in Example 1, and the subsequent drying and titanium nitride spraying operations are the same as those in Example 1. The thickness of the obtained titanium nitride layer is 0.001 mm.

[0067] Test the performance of the spectacle lenses prepared in the examples and comparative examples. The specific method is as follows: (1) Ultraviolet transmission test Measure the ultraviolet transmittance of the spectacle lenses in the examples and comparative examples according to the GB 39552.1 - 2020 standard. The ultraviolet transmittance of both the examples and comparative examples is lower than 10%, and among them, the ultraviolet transmittance of the examples is even lower than 4%.

[0068] (2) Ultraviolet protection experiment Using pigskin to simulate human skin, the LUYOR-3410 LED portable ultraviolet lamp is used as the light source to irradiate the pigskin through the lens. The irradiated area is 1 cm 2 , with a power of 15 W. Taking the time when the smallest visible erythema (MED) just appears on the surface of the pigskin as the cut-off time, tests are carried out at 25 °C and 40 °C respectively. Using the ultraviolet lamp to irradiate the pigskin through the unsprayed lens as the blank group. The test results are shown in Table 1.

[0069] Table 1

[0070] As can be seen from Table 1, the minimum time for the appearance of erythema on the pigskin in the examples is significantly longer than that in the comparative examples, indicating that the composite material of the present application has excellent ultraviolet resistance. At the same time, as can be seen from Table 1, the minimum erythema time at 40 °C in Examples 4-7 is longer than that at 25 °C, indicating that the spectacle lenses of the present invention can more effectively resist ultraviolet rays at high temperatures.

[0071] (3) Ultraviolet resistance durability test At 40 °C, the LUYOR-3410 LED portable ultraviolet lamp is used as the light source to irradiate the lenses prepared in the comparative examples and examples, with a power of 15 W. Irradiate at 40 °C for 2 h, and conduct the ultraviolet protection experiment again after 100 cycles. The results are shown in Table 2.

[0072] Table 2

[0073] As can be seen from Table 2, after the ultraviolet cyclic irradiation of the lenses in the examples, compared with the data in Table 1, the decrease in the minimum erythema time in the examples is smaller, while the time in the comparative examples decreases significantly, indicating that the composite material of the present invention has long-term ultraviolet resistance.

[0074] (4) Lens anti-fouling performance test Place the lenses of the comparative examples and examples in a closed box containing 2 g of talcum powder, take them out after vibrating for one minute, gently blow the surface dust with nitrogen, and rate the residual dust (evaluation level from 1 to 5), 1 = completely clean, 5 = serious residue. The specific results are shown in Table 3.

[0075] Table 3

[0076] Subsequently, wipe the surface of the lens with a cotton cloth containing 0.1% sodium dodecyl sulfate, wipe back and forth 5 times, and rate the residual stains (evaluation level from 1 to 5), 1 = completely clean, 5 = serious residue. The specific results are shown in Table 4.

[0077] Table 4

[0078] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A composite material, characterized in that, Comprising: Methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles and polymethyl methacrylate, wherein the polymethyl methacrylate coats the surface of the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles to form a polymethyl methacrylate layer.

2. The composite material according to claim 1, wherein, The particle size of the methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles is 300 nm to 700 nm.

3. The composite material according to claim 1, wherein The thickness of the polymethyl methacrylate layer is 200 nm to 500 nm.

4. The composite material according to any one of claims 1-3, characterized in that Also included is polyethylene glycol, which coats the polymethyl methacrylate layer to form a polyethylene glycol layer; Preferably, the thickness of the polyethylene glycol layer is 200 nm to 700 nm; Preferably, the polyethylene glycol is formed by the polymerization reaction of oligoethylene glycol methyl ether methacrylate, polyethylene glycol dimethacrylate, and 2-(2-methoxyethoxy)ethyl methacrylate; More preferably, the molecular weight of the oligoethylene glycol methyl ether methacrylate is 200 - 400, and the molecular weight of the polyethylene glycol dimethacrylate is 500 - 600.

5. A method for preparing the composite material according to any one of claims 1-4, characterized in that, Comprising: (1) Mix and stir to disperse methylene bis-benzotriazolyl tetramethylbutylphenol nanoparticles and water to obtain an MBBT nanoparticle dispersion; (2) Add methyl methacrylate and divinylbenzene to the MBBT nanoparticle dispersion and stir to obtain a mixture; (3) Heat the mixture and add an initiator to carry out a polymerization reaction to obtain polymethyl methacrylate-coated MBBT nanoparticles to form an MBBT-PMMA core-shell composite material.

6. The method according to claim 5, wherein In step (1), the stirring speed is 500 - 700 r / min; Preferably, the dispersion is carried out by ultrasonic dispersion, and the power of the ultrasonic dispersion is 400 W - 500 W.

7. The method according to claim 5, wherein In step (3), the mixture is heated to 70 - 80 °C; And / or, the initiator includes at least one of potassium persulfate, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, sodium bisulfite, ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile; And / or, the polymerization reaction time is 2 h - 2.5 h; And / or, in step (2), the stirring speed is 500 - 700 r / min and the time is 30 min - 60 min.

8. The method according to any one of claims 5 to 7, characterized in that, Also included: Disperse the MBBT-PMMA core-shell composite material in water, add 2-(2-methoxyethoxy)ethyl methacrylate, oligoethylene glycol methyl ether methacrylate, and polyethylene glycol dimethacrylate, then heat up, and then add 2,2'-azobis(2-methylpropionamidine) dihydrochloride to carry out a polymerization reaction to obtain an MBBT-PMMA / PEG composite material; Preferably, the temperature of the polymerization reaction is 60 - 80 °C and the time is 5 h - 7 h.

9. A pair of glasses, characterized in that, Comprising a lens, an anti-ultraviolet coating is formed on at least one side of the lens, and the anti-ultraviolet coating includes the composite material according to any one of claims 1 - 4 and / or the composite material prepared by the method according to any one of claims 5 - 8.

10. The glasses according to claim 9, characterized in that, The thickness of the anti-ultraviolet coating is 0.001 mm - 0.01 mm; And / or, a titanium nitride coating is formed on the side of the anti-ultraviolet coating away from the lens; Preferably, the thickness of the titanium nitride coating is 0.001 mm - 0.01 mm.

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