Organic optical switch material, preparation method thereof and bulk three-dimensional display system
By preparing organic optical switching materials and utilizing the co-excitation of violet and cyan light, the problem of slow response speed of existing materials has been solved, achieving a fast optical switching effect that can be applied to fields such as volumetric 3D display and multi-layered security anti-counterfeiting.
Patent Information
- Application Number
- CN202411101307.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-09
- Publication Date
- 2026-02-10
AI Technical Summary
Existing organic photochromic materials have a slow response speed under single-wavelength light source excitation, making it impossible to achieve a fast-response light switching effect.
Organic optical switching materials were prepared by condensation reaction using 4-methoxysalicylaldehyde and fatty amines. The materials achieved rapid optical switching by co-excitation of violet and cyan light. The molecular structure of the materials was designed to be non-planar to reduce π-π stacking and improve brightness and response speed.
It achieves a rapid light-switching effect under the combined excitation of purple and cyan light. The material has high transparency and good stability, and is suitable for applications such as volumetric 3D display, multi-layer security anti-counterfeiting, and 3D data storage.
Smart Images
Figure CN121494741A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to an organic light switch material and a preparation method thereof, and a volumetric three-dimensional display system comprising the organic light switch material. BACKGROUND
[0002] The volumetric three-dimensional display technology is to construct a series of light-emitting voxel points in the imaging space in a very short time by two light sources, and to realize display by using visual persistence. The volumetric three-dimensional display is a stereoscopic display method of real space imaging, which uses the special visual mechanism of human beings to create a display real object composed of voxel particles instead of molecular particles. In addition to the shape represented by light waves, the real existence of the voxel can also be touched. The volumetric three-dimensional display technology has many advantages such as image reality, full view, multi-angle, multi-person simultaneous observation, real-time interaction, and has broad application prospects. In the field of organic light-emitting material technology, photochromic materials with reversible performance are expected to be used as the medium of volumetric three-dimensional display. Photochromism refers to the change of molecular structure of some compounds under the action of light of certain wavelength and intensity, which leads to the corresponding change of the absorption peak of light, i.e. color change, and this change is generally reversible. Organic photochromic materials are various in types and different in color change mechanism, mainly including: (1) bond homolysis, such as spiropyrans, spirooxazines, etc.; (2) bond homolysis, such as hexaphenyl bisimidazole, etc.; (3) electron transfer tautomerism, such as salicylaldehyde aniline compounds, etc.; (4) cis-trans isomerism, such as thioindigo dyes, azo compounds, etc.; (5) redox reaction, such as fused ring aromatic compounds, etc.; (6) pericyclic reaction, such as captodative acid anhydrides, diarylethene, etc.
[0003] Salicylaldehyde aniline compounds can undergo enol-keto structure tautomerism under the excitation of single-wavelength light source, and can change color, and can recover after visible light stimulation, having a light switch effect, but the switching speed is generally slow and cannot realize fast response. SUMMARY
[0004] In view of this, the first aspect of the present application provides an organic light switch material, and the chemical structural formula is as follows:
[0005] wherein R1, R2 and R3 are independently alkyl with carbon atom number of 1-6.
[0006] The organic light switch material can have the characteristic of intersection light emission under the excitation of purple light and cyan light, and can be used in the display space of volumetric three-dimensional imaging. The organic light switch material applied in the volumetric three-dimensional display has high transparency, good stability and reversibility, and can be used as a fast-response light switch material, and can also be applied in the fields of two-dimensional, multi-safety anti-counterfeiting, three-dimensional data storage, etc.
[0007] A second aspect of this application provides a three-dimensional display system comprising the organic light-switching material as described above.
[0008] A third aspect of this application provides a method for preparing an organic optical switching material, comprising:
[0009] 4-Methoxysalicylaldehyde and aliphatic amines are dissolved in an organic solvent and heated to reflux under stirring to obtain a solution. The solution is then subjected to freeze crystallization, filtration, washing, and recrystallization to obtain the target product.
[0010] This application uses salicylaldehyde and aliphatic amines as raw materials to prepare organic photosensitive materials. The raw material costs are low. Replacing salicylaldehyde introduces a methoxy group at the para-position of the aldehyde group as an electron-donating group, improving the brightness of the organic photosensitive material. The aliphatic amines have branched chains, resulting in a non-planar molecular spatial configuration of the prepared organic photosensitive material. This also reduces the concentration of the organic photosensitive material in plexiglass, decreases intermolecular π-π stacking, reduces fluorescence quenching in the aggregated state, and improves molecular brightness. Attached Figure Description
[0011] Figure 1 The image shows the hydrogen nuclear magnetic spectrum of the organic photo-switching material of Example 1 of this application.
[0012] Figure 2 This is the absorption spectrum of the organic optical switch material of Example 1 of this application.
[0013] Figure 3 This is a schematic diagram illustrating the application of the organic optical switching material in a volumetric three-dimensional display system according to Embodiment 1 of this application.
[0014] Explanation of key component symbols:
[0015] 3D display system 100
[0016] Imaging space 10
[0017] First excitation light 21
[0018] Second excitation light 22 Detailed Implementation
[0019] The embodiments of this application are described below with reference to the accompanying drawings. Unless otherwise specified, the data ranges involved in this application shall include end values.
[0020] This application provides a novel organic optical switch material with the following chemical structural formula:
[0021] R1, R2, and R3 are each independently represented as an alkyl group having 1-6 carbon atoms.
[0022] This organic light-switching material can be used for volumetric 3D displays.
[0023] This organic light switch material can be applied in plexiglass. It can be excited by two light sources of different wavelengths. The intersection of the two light sources can emit orange-yellow fluorescence, and it can recover quickly after being stimulated by visible light, thus having a three-dimensional display effect.
[0024] This organic optical switch material has high transparency, good stability and reversibility. As a fast-response optical switch material, it can also be applied to two-dimensional, multi-layer security anti-counterfeiting, three-dimensional data storage and other fields.
[0025] The above chemical structural formula represents the organic photoswitching material in its natural state. The structure of the organic photoswitching material produced in Example 2 below was characterized using 1H NMR spectroscopy, and the results are as follows: Figure 1 .according to Figure 1 The position (chemical shift) and area (number of hydrogen atoms) of the middle peak can be used to determine the chemical shift of the middle peak. Figure 1 The hydrogen peak in the formula corresponds to the hydrogen-containing functional groups in the molecular structure of the organic optical switch material, verifying that the organic optical switch material with this molecular structure can be formed.
[0026] Please see Figure 2 As can be seen from the absorption spectrum of the organic optical switch material, the organic optical switch material of this application has strong absorption of light in the wavelength region of 225nm-420nm, but weak absorption of light in the wavelength region of 420nm-700nm.
[0027] Based on the principle of excited-state proton transfer, this organic photoelectric switch material can rapidly transform from an enol form (initial state) to a keto isomer when irradiated with violet light with a wavelength of 380 nm to 420 nm. Without irradiation with violet light with a wavelength of 380 nm to 420 nm, the keto isomer will transform into an enol form of the organic photoelectric switch material. That is, the enol form and the keto form interconversion is shown in the following reaction formula.
[0028]
[0029] Another beam of visible light (cyan light with a wavelength of 450nm to 490nm) intersects with violet light with a wavelength of 380nm to 420nm, exciting the ketone isomer to produce laser-induced (orange-yellow fluorescence).
[0030] The organic optical switch material provided in this application embodiment can be converted into an isomer under the irradiation of a first excitation light. The isomer generates laser light under the irradiation of a second excitation light, resulting in a fast overall response speed. It can be applied to various application scenarios, such as two-dimensional display devices, three-dimensional display devices, light-controlled switch elements, or multi-emissivity anti-counterfeiting materials.
[0031] The preparation method of this organic optical switch material includes:
[0032] 4-Methoxysalicylaldehyde (A) and aliphatic amine (B) were dissolved in an organic solvent (C) and added to a reaction vessel. The mixture was heated to reflux with stirring and reacted for a certain time, for example, 2 to 4 hours, to obtain a solution. The solution was then cooled and cryogenically crystallized (crystals were precipitated by cooling to a low temperature, such as 0°C). The solution was then filtered, washed, and recrystallized to obtain the target product.
[0033] The organic photoswitching material is the product of the condensation reaction of 4-methoxysalicylaldehyde and aliphatic amine.
[0034] The reaction formula for this preparation method is as follows:
[0035]
[0036] The organic solvent C used in this preparation method is at least one of methanol, ethanol, tetrahydrofuran, 1,4-dioxane, and toluene.
[0037] In this preparation method, the reflux temperature is the boiling point of the compound with the lowest boiling point between the fatty amine (B) and the solvent (C).
[0038] In this preparation method, the molar ratio of 4-methoxysalicylaldehyde (A) to fatty amine (B) is 1:(1-1.2), and the mass ratio of 4-methoxysalicylaldehyde (A) to solvent (C) is 1:(3-5).
[0039] Please see Figure 3 This application also provides a volumetric 3D display system 100, including the aforementioned organic light-switching material. The organic light-switching material is dispersed in plexiglass to form a transparent glass body, which serves as the imaging space 10 for the volumetric 3D display.
[0040] The 3D display system 100 also includes an excitation light source (not shown) for illuminating the imaging space 10. The excitation light source includes a first excitation light 21 and a second excitation light 22. The two light sources intersect at a point in the imaging space 10 to generate luminescent voxel dots. When the excitation light source moves rapidly, multiple intersection points are formed in the imaging space 10, which, as voxels, constitute a 3D stereoscopic image. The first excitation light 21 is violet light with a wavelength of 380nm to 420nm, and the second excitation light 22 is cyan light with a wavelength of 450nm to 490nm.
[0041] The first excitation beam 21 and the second excitation beam 22 intersect at a point in the imaging space 10, generating luminescent voxel dots. By controlling the scanning paths and speeds of the first and second excitation beams 21 and 22 respectively via a computer connected to an optical scanning mirror, the luminescent point at the intersection of the two laser beams is scanned rapidly at a speed exceeding the refresh rate of the human eye, forming an array of multiple voxel dots, thus creating a three-dimensional spatial image within the imaging space 10. The voxel dots generated and disappeared at speeds lower than the limit of human eye resolution using this organic optical switching material, resulting in a fast response speed and enabling dynamic refreshing of the three-dimensional image.
[0042] The specific method for preparing the plexiglass is as follows: Organic photosensitive material, methyl methacrylate, benzoyl peroxide, and a solvent (e.g., dichloromethane) are mixed evenly, poured into a mold, heated, and cured to form plexiglass, thus obtaining plexiglass containing the organic photosensitive material. In some embodiments, the organic photosensitive material can be dissolved in a solvent (e.g., dichloromethane) to obtain a solution of the organic photosensitive material, which is then added to methyl methacrylate and benzoyl peroxide. In the method for preparing the plexiglass, the mass ratio of methyl methacrylate, benzoyl peroxide, dichloromethane, and organic photosensitive material is (5000-10000):(5-10):(50-100):1.
[0043] The method for preparing the vitreous body includes the following heating steps: holding at 70℃~90℃ for 0.5h~1.5h (e.g., holding at 80℃ for 1h), then cooling to 45℃~55℃ and holding for 20h~24h (e.g., cooling to 50℃ and holding for 24h), then heating to 80℃~100℃ and holding for 1.5h~2.5h (e.g., heating to 80℃ and holding for 2h), and finally cooling to room temperature.
[0044] This application uses salicylaldehyde and aliphatic amines as raw materials to prepare organic photosensitive materials, which are inexpensive. Replacing salicylaldehyde introduces a methoxy group at the para-position of the aldehyde group as an electron-donating group, thereby improving the brightness of the organic photosensitive material. The aliphatic amines have branched chains, which makes the molecular spatial configuration of the prepared organic photosensitive material non-planar, and at the same time reduces the concentration of the organic photosensitive material in plexiglass, reduces the π-π stacking between molecules, reduces the fluorescence quenching phenomenon of molecular aggregates, and improves the brightness of the molecules. Compared with salicylaldehyde aniline acetals, salicylaldehyde acetals have a faster recovery speed and better switching effect because the nitrogen atom of the aniline molecule has a conjugation effect with the benzene ring. When the light source excites the salicylaldehyde aniline acetal, the enol-keto structure interconversion occurs, and the visible light stimulation recovery speed is generally slow. However, salicylaldehyde acetals do not have the conjugation effect between the nitrogen atom and the benzene ring.
[0045] The preparation of organic optical switching materials will be specifically described below through Examples 1 to 3.
[0046] Example 1
[0047] The specific preparation method of organic optical switching materials is as follows:
[0048] Weigh 1.52 g of 4-methoxysalicylaldehyde, 0.87 g of tert-butylamine, and 7.5 g of tetrahydrofuran and add them to a reaction vessel. Stir and heat to 45 °C, keep the reaction temperature for 2 h, cool to -10 °C, freeze to crystallize, filter, wash with cold ethanol, and dry to obtain organic photo-switching material.
[0049] The glass containing the organic optical switching material is prepared as follows:
[0050] Weigh 5 mg of the organic photo-switching material from Example 1 and 50 mg of benzoyl peroxide, add them to 0.5 g of dichloromethane, dissolve them, then add them to 50 g of methyl methacrylate solution, mix well, pour into a mold, heat to 80°C and keep at that temperature for 1 h, cool to 50°C and keep at that temperature for 24 h, then heat to 80°C and keep at that temperature for 2 h, cool to room temperature, remove the cured material from the mold, and obtain a glass containing the organic photo-switching material.
[0051] Applications of volumetric 3D display:
[0052] A 405nm light source was selected as the wavelength of the photochromic light source, and a 450nm light source was selected as the wavelength of the excitation light source of the photochromic isomer. The two beams of light converged inside the glass containing organic light-switching material to form voxel dots. The scanning path and scanning speed of the two light sources were controlled by a computer to achieve a three-dimensional display effect.
[0053] Example 2
[0054] The specific preparation method of organic optical switching materials is as follows:
[0055] Weigh 1.52 g of 4-methoxysalicylaldehyde, 1.04 g of tert-amylamine, and 7.5 g of ethanol and add them to a reaction vessel. Stir and heat to 77°C, keep the reaction temperature for 2 h, cool to -10°C, freeze to crystallize, filter, wash with cold ethanol, and dry to obtain the organic photo-switching material.
[0056] The glass containing the organic optical switching material is prepared as follows:
[0057] Weigh 5 mg of the organic photo-switching material from Example 2 and 50 mg of benzoyl peroxide, add them to 0.5 g of dichloromethane, dissolve them, then add them to 50 g of methyl methacrylate solution, mix them evenly, pour them into a mold, heat to 80°C and keep for 1 h, cool to 50°C and keep for 24 h, then heat to 80°C and keep for 2 h, cool to room temperature, remove the cured material from the mold, and obtain a glass containing the organic photo-switching material.
[0058] Applications of volumetric 3D display:
[0059] A 405nm light source was selected as the wavelength of the photochromic light source, and 488nm was selected as the wavelength of the excitation light source of the photochromic isomer. The two beams of light converged inside the glass containing organic photo-switching material to form voxel dots. The scanning path and scanning speed of the two light sources were controlled by computer to achieve a three-dimensional display effect.
[0060] Example 3
[0061] The specific preparation method of organic optical switching materials is as follows:
[0062] Weigh 1.52 g of 4-methoxysalicylaldehyde, 1.71 g of 2-methyl-2-octylamine, and 7.5 g of 1,4-dioxane and add them to a reaction vessel. Stir and heat to 101 °C, maintain the temperature for 2 h, cool to -10 °C, freeze to crystallize, filter, wash with cold ethanol, and dry to obtain the organic photo-switching material.
[0063] The glass containing the organic optical switching material is prepared as follows:
[0064] Weigh 5 mg of the organic photo-switching material from Example 3 and 25 mg of benzoyl peroxide, add them to 0.5 g of dichloromethane, dissolve them, then add them to 25 g of methyl methacrylate solution, mix them evenly, pour them into a mold, heat to 80°C and keep for 1 h, cool to 50°C and keep for 24 h, then heat to 80°C and keep for 2 h, cool to room temperature, remove the cured material from the mold, and obtain a glass containing the organic photo-switching material.
[0065] Applications of volumetric 3D display:
[0066] A 395nm light source was selected as the wavelength of the photochromic light source, and a 488nm light source was selected as the wavelength of the excitation light source of the photochromic isomer. The two beams of light converged inside the glass containing organic photo-switching material to form voxel dots. The scanning path and scanning speed of the two light sources were controlled by a computer to achieve a three-dimensional display effect.
[0067] The above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit it. Although this application has been described in detail with reference to the above preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions to the technical solutions of this application should not depart from the spirit and scope of the technical solutions of this application.
Claims
1. An organic optical switching material, characterized in that, The chemical structural formula of the organic optical switch material is: R1, R2, and R3 are each independently represented as an alkyl group having 1-6 carbon atoms.
2. The organic optical switching material according to claim 1, characterized in that, The organic optical switch material absorbs light with wavelengths of 250nm to 350nm.
3. The organic optical switching material according to claim 1, characterized in that, The organic photosensitive material can be transformed from an enol form to a keto isomer when irradiated with violet light with a wavelength of 380 nm to 420 nm; and when not irradiated with violet light, the keto isomer will transform into the enol form of the organic photosensitive material.
4. A volumetric three-dimensional display system, characterized in that, Including the organic optical switch material as described in any one of claims 1 to 3.
5. The volumetric three-dimensional display system according to claim 4, characterized in that, The organic optical switching material is dispersed in glass to form a transparent glass body, which serves as the imaging space of the volumetric 3D display system. The volumetric 3D display system also includes an excitation light source, which emits excitation light to illuminate the imaging space. The excitation light includes a first excitation light and a second excitation light.
6. The volumetric three-dimensional display system according to claim 5, characterized in that, The first excitation light has a wavelength of 380nm to 420nm (violet light), and the second excitation light has a wavelength of 450nm to 490nm (cyan light).
7. The volumetric three-dimensional display system according to claim 5, characterized in that, The method for preparing the glass body includes: mixing the organic photo-switching material, methyl methacrylate, benzoyl peroxide, and dichloromethane evenly, pouring the mixture into a mold, heating, and curing to form the glass body.
8. The volumetric three-dimensional display system according to claim 7, characterized in that, The mass ratio of the methyl methacrylate, the benzoyl peroxide, the dichloromethane, and the organic photo-switching material is (5000-10000):(5-10):(50-100):
1.
9. A method for preparing an organic optical switching material, characterized in that, include: 4-Methoxysalicylaldehyde and aliphatic amines are dissolved in an organic solvent and heated to reflux under stirring to obtain a solution. The solution is then subjected to freeze crystallization, filtration, washing, and recrystallization to obtain the target product.
10. The method for preparing the organic optical switching material according to claim 9, characterized in that, The organic solvent is at least one selected from methanol, ethanol, tetrahydrofuran, 1,4-dioxane, and toluene; and / or The reflux temperature is the boiling point temperature of the compound with the lowest boiling point among the fatty amine and the solvent; and / or In the reaction raw materials, the molar ratio of 4-methoxysalicylaldehyde to the fatty amine is 1:(1-1.2), and the mass ratio of 4-methoxysalicylaldehyde to the solvent is 1:(3-5).