N-vinyl-5-vinyl uracil compound, preparation method thereof and application of N-vinyl-5-vinyl uracil compound as blue light absorption material
By adding N-vinyl-5-vinyl uracil compound to the polyurethane optical resin material, a blue light protection network is formed, which solves the problem of inaccurate blue light protection in the existing technology, and differentiated absorption of blue light in different bands is achieved, providing efficient protection effects.
Patent Information
- Application Number
- CN202510534285.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-25
- Publication Date
- 2025-08-01
AI Technical Summary
Existing blue light protection technology cannot accurately distinguish short-wave harmful blue light from medium-long wave beneficial blue light, resulting in poor protection effect and may affect visible light transmittance. The stability and cost problems of existing materials during polymerization are prominent.
N-vinyl-5-vinyl uracil compound is used as the anti-blue light additive, and it is uniformly dispersed in the polyurethane optical resin material through a dispersion process to form a blue light protection network to achieve distinction and absorption of blue light in different bands.
It achieves low transmittance to short-wave harmful blue light and high transmittance to medium-long-wave beneficial blue light, providing efficient and accurate blue light protection, avoiding visual damage and maintaining the authenticity of visual objects.
Smart Images
Figure CN120398772A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of light absorbers, and particularly relates to the application of an N-vinyluracil compound as a blue light absorber having a specific absorption at 380-400 nm and a preparation method thereof. Background Art
[0002] With the popularization of electronic devices, the harm of blue light to the eyes has been increasingly concerned. Research shows that high-energy blue light with a wavelength of 400-440 nm can penetrate the lens and reach the retina directly, generating free radicals, leading to the apoptosis of retinal pigment epithelial cells, and then causing vision damage. However, blue light above 460 nm has a positive effect on the regulation of the human biological clock. Therefore, blue light protection materials need to block harmful blue light while retaining the transmittance of beneficial blue light to achieve precise protection.
[0003] The human eye is insensitive to the vision and color discrimination of blue light in the range of 400-440 nm. Moreover, the light waves in this wavelength range have short wavelengths and high energies, which cause great harm to the eyes. The optical lens should maintain a low transmittance for this part of blue light; the medium and long wavelength blue light in the range of 460-500 nm can help the pupil contract and display the color of the object, which is beneficial blue light and causes relatively little harm to the human eye. For this part of blue light, a high transmittance should be maintained to ensure the authenticity of the vision picture. Currently, blue light protection technologies are mainly divided into the absorption method and the reflection method. The absorption method realizes blue light blocking by adding a blue light absorber (such as benzotriazole compounds, etc.) to the material, but there are problems such as difficult dose control, easy migration, and yellowing of the lens. The reflection method realizes blue light reflection through optical coating technology, but it will cause secondary glare damage, and the process is complex and the cost is high. In addition, due to the limitation of the chemical structure stability of some light absorbers and the influence of temperature during the polyurethane polymerization process, the function decreases, the overall blue light protection efficiency is low, or while blocking blue light, some visible light is also lost, resulting in the influence of the visible light transmittance; at the same time, the protection of the short and medium and long wavelength blue spectral regions cannot be distinguished for absorption, and the blue light cannot be precisely protected. Therefore, it is necessary to develop an optical material that can distinguish and absorb blue light in different wavelength bands, so that harmful blue light maintains a low transmittance and beneficial blue light maintains a high transmittance, which is of great significance for promoting the application and development of polyurethane optical materials in the high-end optical protection field. Summary of the Invention
[0004] In view of the above problems of the prior art, the present invention provides an N-vinyluracil compound, the structure of which is shown in Formula A. It can be used as a blue light-absorbing additive for polyurethane optical resin materials. Through a dispersion process, the N-vinyluracil compound and other functional additives are evenly dispersed in the resin, and they cooperate to form a blue light protection network, which has the performance of distinguishing and absorbing blue light in different bands, keeping the short-wave harmful blue light with a low transmittance and the medium- and long-wave beneficial blue light with a high transmittance, and preferably solving the problem of damage to the human eye caused by ultraviolet light and blue light, thereby achieving efficient and accurate blue light protection.
[0005] To achieve the above object, the present invention provides the following technical solutions:
[0006] On the one hand, the present invention provides an N-vinyl-5-vinyluracil compound, the structure of which is shown in Formula A:
[0007]
[0008] On the other hand, the present invention provides the use of the above-mentioned N-vinyl-5-vinyluracil compound as a blue light-absorbing material.
[0009] In the above-mentioned use, preferably, the compound is used as a blue light protection additive for polyurethane optical resin materials.
[0010] In the above-mentioned use, preferably, the blue light protection additive includes N-vinyl-5-vinyluracil, an ultraviolet absorber, a solvent, and an acrylate, and the weight ratio among the four is (1-3):(1-3):(7-15):(10-30).
[0011] In the above-mentioned use, preferably, the ultraviolet absorber is at least one of UV-9, UV-21, UV-326, UV-327, UV-328, UV-329, UV-360, and UV-928.
[0012] In the above-mentioned use, preferably, the acrylate compound is selected from at least one of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, polyethylene glycol methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, epoxy acrylate, bisphenol A epoxy acrylate, and ethoxylated bisphenol A diacrylate, etc.
[0013] In the above-mentioned use, preferably, the solvent is selected from at least one of acetonitrile, chloroform, petroleum ether, n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
[0014] On the other hand, the present invention provides a method for preparing N-vinyl-5-vinyluracil as described above, which method comprises the following steps: adding 5-vinyluracil and a solvent with a boiling point higher than 150 °C in a weight ratio of (1-3):(100-300) into a reaction vessel, completely dissolving, then dropping an alkaline aqueous solution to adjust the pH value ≥ 8.0, introducing vinyl chloride gas into the solution, heating to 50-100 °C, dropping a palladium catalyst, continuing the reaction for 5-12 h and then stopping the ventilation, adding water and extracting with dichloromethane, combining the organic phases, drying with anhydrous sodium sulfate, and subjecting the crude product to column chromatography with dichloromethane / methanol to obtain a white powder of N-vinyl-5-vinyluracil compound.
[0015] In the preparation method as described above, preferably, the palladium catalyst is selected from one of palladium acetate, tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium and dibenzylideneacetone palladium, and the amount of the palladium catalyst used is 0.1-0.5 wt% of 5-vinyluracil.
[0016] In the preparation method as described above, preferably, the solvent is selected from at least one of cyclohexanone, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone.
[0017] The preparation method of N-vinyl-5-vinyluracil (compound of formula A) in the present invention is that 5-vinyluracil undergoes deprotonation under alkaline conditions to form uracil anion, and the uracil anion then undergoes nucleophilic substitution reaction with vinyl chloride to vinylate the amino group at the 1-position of the pyrimidine ring, generating N-vinyl-5-vinyluracil (compound of formula A). The specific reaction process and equation are as follows:
[0018] (1) C6H6N2O^2 + OH - ——→ C6H5N2O^2 - + H2O
[0019] (2) C6H5N2O^2 - + CH2=CHCl ——→ C8H8N2O^2 + Cl -
[0020]
[0021] The beneficial effects of the present invention are as follows:
[0022] 1. The N-vinyl-5-vinyluracil compound of the present invention forms a stable N-C bond in the molecule, has a stable molecular structure, can remain stable in the polyurethane polymerization reaction, and has good high-temperature resistance and ultraviolet resistance.
[0023] 2. The π-π conjugate structure on the uracil ring enables it to absorb light of specific wavelengths. The presence of vinyl groups enhances the molecular conjugation effect, which synergistically interacts with conventional UV absorbers, further improving the absorption capacity for high-energy blue light in the range of 400 - 440 nm, while having weak absorption for blue light above 470 nm, allowing it to pass through, which helps regulate the human biological clock, avoid color deviation and visual discomfort, and thus achieve precise regulation and protection of blue light. Description of the Drawings
[0024] Figure 1 Infrared spectrum diagram of the compound prepared in Example 1.
[0025] Figure 2 Spectrum diagram of the light absorber mixture prepared in Example 8 and Comparative Example 1. Detailed Description of the Invention
[0026] The present invention will be further described below through specific examples, but this does not mean any limitation to the protection scope of the present invention.
[0027] Example 1
[0028] 100 g of 5-vinyluracil was added to a reaction vessel containing 25000 g of dimethylformamide solvent. After stirring until completely dissolved, a 36 wt% NaOH solution was added dropwise to adjust the pH value to ≥8.0. Vinyl chloride gas was introduced into the solution, and the mixture was heated to 85 °C for reaction. 0.2 g of bis(dibenzylideneacetone)palladium catalyst was added dropwise within 50 min, and the reaction continued for 8 h before stopping the gas supply. After adding water, extraction was carried out with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was subjected to column chromatography on a dichloromethane / methanol column to obtain 112.3 g of white N-vinyl-5-vinyluracil (Formula A) powder. The yield was 88.2%.
[0029] FT-IR test of infrared spectrum: The product prepared in Example 1 was tested by Fourier transform infrared spectroscopy (FT-IR). From Figure 1 the curve analysis, it can be seen that the N-H stretching vibration peak (broad peak) is at 3240 - 3397 cm-1; the stretching vibration absorption peak of the C-H bond is at 2852 - 3100 cm- 1 ; the stretching vibration absorption peak of the carbonyl group (C=O) on the uracil ring is at 1705 - 1752 cm- 1 ; the stretching vibration absorption peak of the C=C bond is in the region of 1623 - 1682 cm- 1 ; the pyrimidine ring skeletal vibration absorption peak is at 1523 - 1601 cm- 1 ; and the C-N stretching vibration absorption peak is at 1260 - 13650 cm- 1 .
[0030] 1H NMR nuclear magnetic resonance hydrogen spectrum analysis: δ = 10.71 - 10.13 (br s, 1H, N-H); 7.82 (s, 1H, C-H); 5.12 - 5.74 (d, 3H, CH2=CH); 5.89 - 6.46 (dd, 3H, CH2=CH).
[0031] Example 2
[0032] 100 g of 5-vinyluracil was added to a reaction vessel containing 25,000 g of dimethyl sulfoxide solvent. After stirring until completely dissolved, a 36 wt% NaOH alkaline solution was added dropwise to adjust the pH value ≥ 8.0. Vinyl chloride gas was introduced into the solution, and the reaction was carried out at 80 °C. 0.2 g of dibenzylideneacetone dipalladium catalyst was added dropwise within 60 min, and the reaction continued for 7.5 h before stopping the gas supply. After adding water, extraction was carried out with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was subjected to column chromatography on dichloromethane / methanol to obtain 110.3 g of white N-vinyl-5-vinyluracil powder. The yield was 87.4%.
[0033] Example 3
[0034] 100 g of 5-vinyluracil was added to a reaction vessel containing 20,000 g of dimethylacetamide solvent. After stirring until completely dissolved, a 36 wt% NaOH alkaline solution was added dropwise to adjust the pH value ≥ 8.0. Vinyl chloride gas was introduced into the solution, and the reaction was carried out at 85 °C. 0.2 g of dibenzylideneacetone dipalladium catalyst was added dropwise within 45 min, and the reaction continued for 8 h before stopping the gas supply. After adding water, extraction was carried out with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was subjected to column chromatography on dichloromethane / methanol to obtain 112.0 g of white N-vinyl-5-vinyluracil powder. The yield was 88.1%.
[0035] Example 4
[0036] 100 g of 5-vinyluracil was added to a reaction vessel containing 22,000 g of dimethylformamide solvent. After stirring until completely dissolved, a 36 wt% NaOH alkaline solution was added dropwise to adjust the pH value ≥ 8.0. Vinyl chloride gas was introduced into the solution, and the reaction was carried out at 75 °C. 0.18 g of dibenzylideneacetone dipalladium catalyst was added dropwise within 55 min, and the reaction continued for 8 h before stopping the gas supply. After adding water, extraction was carried out with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was subjected to column chromatography on dichloromethane / methanol to obtain 107.4 g of white N-vinyl-5-vinyluracil powder. The yield was 86.5%.
[0037] Example 5
[0038] 100 g of 5-vinyluracil was added to a reaction vessel containing 22 kg of dimethylformamide solvent. After stirring until completely dissolved, a 36 wt% NaOH alkaline solution was added dropwise to adjust the pH value to ≥8.0. Vinyl chloride gas was introduced into the solution, and the reaction was carried out at 85 °C. 0.2 g of bis(benzylideneacetone)palladium(0) catalyst was added dropwise within 60 min. After continuing the reaction for 8.5 h, the gas supply was stopped. After adding water, extraction was carried out with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was subjected to column chromatography on a dichloromethane / methanol column to obtain 112.7 g of white N-vinyl-5-vinyluracil powder. The yield was 88.4%.
[0039] Example 6
[0040] 100 g of 5-vinyluracil was added to a reaction vessel containing 22 kg of dimethylformamide solvent. After stirring until completely dissolved, a 36 wt% NaOH alkaline solution was added dropwise to adjust the pH value to ≥8.0. Vinyl chloride gas was introduced into the solution, and the reaction was carried out at 85 °C. 0.15 g of bis(benzylideneacetone)palladium(0) catalyst was added dropwise within 55 min. After continuing the reaction for 8 h, the gas supply was stopped. After adding water, extraction was carried out with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was subjected to column chromatography on a dichloromethane / methanol column to obtain 112.0 g of white N-vinyl-5-vinyluracil powder. The yield was 88.2%.
[0041] Example 7: Aging Resistance Performance Detection of N-Vinyl-5-Vinyluracil Compound
[0042] The aging resistance performance of the N-vinyl-5-vinyluracil compounds prepared in Examples 1-6 was detected respectively. Detection method: The N-vinyl-5-vinyluracil powder prepared in the examples was mixed with glass microspheres and placed in a temperature cycling aging test chamber. Five temperature ranges of -5 °C, 0 °C, 75 °C, 115 °C, and 165 °C were set respectively, and a 72-hour test alternating cycle was set. After taking out, it was put into an aging test chamber for extreme irradiation for 24 hours. The samples after irradiation treatment were dissolved in acetonitrile solvent respectively, and the colorimetric and spectral performance detections were compared with the untreated samples. See Table 1 for details.
[0043] Table 1 Comparison of Aging Resistance of Example Samples and Untreated Samples
[0044]
[0045] Conclusion: Through naked-eye observation, the color of the untreated sample was transparent light yellow, and there was no color difference change compared with the irradiated sample; through the comparison of spectral detection data, it was found that the spectral curves completely overlapped, and there were no changes in the detection samples of Examples 1-6, indicating that the stability and anti-aging performance of the N-vinyl-5-vinyluracil compound can meet the requirements of the anti-blue light function.
[0046] Comparative Example 1: Preparation of a light absorber mixed solution
[0047] Dissolve 0.1 g of ultraviolet absorber UV-21 (UV) in 1.2 g of acetonitrile (ACN) solvent, and add 5 g of methyl acrylate monomer (ACR) thereto to form a light absorber mixture.
[0048] Example 8: Light absorber mixed solution containing N-vinyl-5-vinyluracil
[0049] Dissolve 0.1 g of N-vinyl-5-vinyluracil compound and 0.1 g of ultraviolet absorber UV-21 in 1.2 g of acetonitrile solvent, and add 5 g of methyl acrylate monomer thereto to form a light absorber mixture.
[0050] Example 9: Optical property detection experiment of N-vinyl-5-vinyluracil
[0051] Perform optical property detection on the light absorber mixed solutions prepared in Example 8 and Comparative Example 1 respectively. For the transmittance detection, use a UV-8000 type ultraviolet-visible spectrophotometer produced by Shanghai Yuanxi Instrument Co., Ltd. Coat the mixed solution directly on the prism of the ultraviolet-visible spectrophotometer to measure the spectral transmittance. The detection results are listed in Table 2 and Figure 2 .
[0052] Table 2 Spectral transmittance of the sample in Example at different wavelength bands
[0053]
[0054] From the above detection results, it can be known that: the light absorber mixture composed of N-vinyl-5-vinyluracil compounds with specific absorption wavelengths manufactured by the present invention has a transmittance of ≤0.01 in the ultraviolet spectral region, a transmittance of ≤3.4 in the short-wave blue light region of 385 - 445 nm, a transmittance of ≥72 in the long-wave blue light region of 475 - 500 nm, and a transmittance of ≥88 in the visible spectral region above 550 nm. It has the performance of differentiating and absorbing blue light in different bands, can achieve precise regulation and protection of blue light, and can better solve the problem of damage to the human eye caused by ultraviolet light and blue light.
Claims
1. An N-vinyl-5-vinyluracil compound, characterized in that, Its structure is as shown in Formula A:
2. Use of the N-vinyl-5-vinyluracil compound as claimed in claim 1 as a blue light absorbing material.
3. The application according to claim 2, wherein The compound is used as a blue light blocking additive for polyurethane optical resin materials.
4. The application according to claim 3, wherein The blue light blocking additive comprises N-vinyl-5-vinyluracil, an ultraviolet absorber, a solvent and an acrylate, and the weight ratio among the four is (1-3):(1-3):(7-15):(10-30).
5. The application according to claim 4, characterized in that The ultraviolet absorber is at least one of UV-9, UV-21, UV-326, UV-327, UV-328, UV-329, UV-360 and UV-928.
6. The application according to claim 4, wherein The acrylate compound is selected from at least one of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, polyethylene glycol methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, epoxy acrylate, bisphenol A epoxy acrylate and ethoxylated bisphenol A diacrylate, etc.
7. The application according to claim 4, characterized in that, The solvent is selected from at least one of acetonitrile, chloroform, petroleum ether, n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
8. The preparation method of N-vinyl-5-vinyluracil according to claim 1, characterized in that, The method comprises the following steps: adding 5-vinyluracil and a solvent with a boiling point higher than 150 °C into a reaction vessel according to a weight ratio of (1-3):(100-300), completely dissolving, dropping an alkaline aqueous solution, adjusting the pH value ≥ 8.0, introducing vinyl chloride gas into the solution, heating at 50-100 °C, dropping a palladium catalyst, continuing the reaction for 5-12 h and then stopping the ventilation, adding water and extracting with dichloromethane, combining the organic phases, drying with anhydrous sodium sulfate, and subjecting the crude product to column chromatography with dichloromethane / methanol to obtain a white powder of the N-vinyl-5-vinyluracil compound.
9. The preparation method according to claim 8, characterized in that, The palladium catalyst is selected from one of palladium acetate, tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium and dibenzylideneacetone palladium, and the dosage of the palladium catalyst is 0.1-0.5 wt% of 5-vinyluracil.
10. The preparation method according to claim 8 or 9, characterized in that, The solvent is selected from at least one of cyclohexanone, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone.