Visible light excited organic long afterglow material, three-dimensional structure and preparation method and application thereof

Abstract

This invention discloses a visible light-excited organic long-afterglow material, its three-dimensional structure, preparation method, and applications, relating to the field of organic materials technology. The material comprises a host material and a guest material doped within the host material; the host material is a polar polymer; the guest material is a compound of formula (Ⅰ); the polar polymer is polyvinyl alcohol, polymethyl methacrylate, polyvinylpyrrolidone, or hydroxyethyl polyacrylate. The organic long-afterglow host-guest doped material constructed based on a triarylamine system successfully achieves responsiveness to both ultraviolet and visible light excitation sources, achieving an afterglow lifetime exceeding 1 second under excitation and being excited by a mobile phone flash.

Description

Technical Field

[0001] This invention relates to the field of organic materials technology, specifically to a visible light-excited organic long afterglow material, its three-dimensional structure, preparation method, and application. Background Technology

[0002] Organic long-afterglow materials refer to materials that continue to emit light after the excitation source stops. In recent years, these materials have been widely used in light-emitting displays such as low-light lighting and emergency indicators. They are also used in intelligent transportation, information storage, and other fields. In particular, these materials can achieve biosensing and imaging, as well as multiple data encryption and anti-counterfeiting under "excitation-free" conditions, thus having broad application prospects.

[0003] Traditional organic molecules, after being excited by a light source, typically undergo radiative transitions from the excited state to the ground state, producing only fluorescence, phosphorescence, and delayed fluorescence, which are not suitable for generating long-afterglow luminescence. Long-lived luminescence at room temperature usually refers to phosphorescence, with decay lifetimes mostly in the millisecond or even microsecond range. Pure organic long-afterglow phenomena can usually only be observed under harsh conditions such as ultra-low temperatures, oxygen-free environments, and strong light. Currently, the lifetimes of most defined organic long-afterglow materials are greater than 0.1 s, and related fields are still in the basic research stage. Classified by material composition, they are mainly divided into organic long-afterglow single-component materials and organic long-afterglow doped materials. Currently, the luminescence mechanism of organic long-afterglow single-component materials is generally relatively clear, but these materials exhibit significant non-radiative transitions, which are unfavorable for afterglow generation. In recent years, many similar reports have been made on organic long-afterglow host-guest doped materials. For example, Yang Wenjun's research group proposed achieving ultra-long lifetime (>1 s) and high-efficiency (>36%) room-temperature phosphorescence by doping N-arylcarbazole derivatives containing heteroatoms or heavy halogens into polymethyl methacrylate (PMMA) films. These afterglow polymer films exhibit an ultralong (>20 hours) photoactivated pattern memory effect. Due to their high molecular weight and long molecular chains, polymers provide a rigid and dense environment for guest materials, effectively suppressing molecular rotation and thus contributing to long afterglow luminescence. Furthermore, polymers offer advantages such as ease of processing, flexibility, and low manufacturing costs. Therefore, doping organic molecules into polymer matrices or synthesizing polymers containing heteroatom chromophores has become an ideal strategy for obtaining long afterglow materials. However, currently, most polymer materials exhibit low afterglow luminescence efficiency and short lifetimes at room temperature, and are difficult to process further, such as through 3D printing, severely limiting their practical applications. Summary of the Invention

[0004] To address the shortcomings of the aforementioned background technologies, the main technical problem solved by this invention is that most polymer materials exhibit low afterglow luminescence efficiency and short lifespan at room temperature, and are difficult to process into finer details, such as through 3D printing, severely limiting their practical applications. This invention provides a visible light-excited organic long afterglow material, its three-dimensional structure, its preparation method, and its applications.

[0005] The first objective of this invention is to provide a method for preparing a visible light-excited organic long afterglow material, comprising a host material and a guest material doped in the host material;

[0006] The main material is a polar polymer;

[0007] The object material is a compound of formula (Ⅰ);

[0008]

[0009] In formula (Ⅰ), R1 is dibenzothiophene, dibenzothiophene sulfone, benzothiophene, benzothiophene sulfone, dibenzofuran, benzofuran, carbazole or pyridine;

[0010] R2 and R3 are each independently selected from one of the following groups: hydrogen, methoxy, halogen, hydroxyl, and carboxyl.

[0011] The polar polymer is polyvinyl alcohol, polymethyl methacrylate, polyvinylpyrrolidone, or hydroxyethyl polyacrylate.

[0012] Preferably, the mass ratio of the object material to the main material is 1:100 to 1,000,000.

[0013] Preferably, the object material is prepared according to the following steps:

[0014] Compound (V), compound (IV), potassium tert-butoxide, tritert-butylphosphine, and palladium catalyst were refluxed at 100°C with toluene as solvent to undergo a Buchwald-Hartwig coupling reaction to yield compound (III); the synthetic route is as follows:

[0015]

[0016] Compound (III), compound (II), potassium tert-butoxide, tritert-butylphosphine, and palladium catalyst were refluxed at 100°C with toluene as solvent to undergo a Buchwald-Hartwig coupling reaction to yield compound (I); the synthetic route is as follows:

[0017]

[0018] In the compounds of formula (I), formula (II), formula (III), formula (IV), and formula (V), R1 is dibenzothiophene, dibenzothiophene sulfone, benzothiophene, benzothiophene sulfone, dibenzofuran, benzofuran, carbazole, or pyridine; R2 and R3 are each independently selected from one of hydrogen, methoxy, halogen, hydroxyl, and carboxyl groups.

[0019] The second objective of this invention is to provide a method for preparing visible light-excited organic long afterglow materials, comprising the following steps:

[0020] The host material and the guest material are weighed separately and placed into a container. A small amount of solvent is added and mixed evenly to obtain a mixed solution. The mixed solution is then drop-coated onto a quartz plate and dried to obtain an organic long afterglow material on the quartz plate.

[0021] The third objective of this invention is to provide a method for preparing visible light-excited organic long afterglow materials, comprising the following steps:

[0022] After weighing the main material and the guest material separately and placing them into a container, add a small amount of solvent, mix evenly, and then heat to evaporate the solvent. Grind the dried material into powder and then hot press it into a film to obtain the organic long afterglow material.

[0023] The fourth objective of this invention is to provide a method for preparing visible light-excited organic long afterglow materials, comprising the following steps:

[0024] After weighing the main material and the guest material separately and placing them into a container, add a small amount of solvent, mix them evenly, and then perform photopolymerization and curing in an ultraviolet oven to obtain the organic long afterglow material.

[0025] The fifth objective of this invention is to provide an application of visible light-excited organic long afterglow materials in 3D printing.

[0026] The sixth objective of this invention is to provide a three-dimensional structure, which is 3D printed using 3D printing ink comprising the above-mentioned visible light-excited organic long afterglow material.

[0027] The seventh objective of this invention is to provide a method for preparing a three-dimensional structure, comprising the following steps:

[0028] Step 1: Use the organic long afterglow material directly as 3D printing ink;

[0029] The monomers of 2-hydroxyethyl acrylate, the monomers of acrylic acid, and the organic long afterglow material were mixed evenly at a mass fraction of 7000:3000:1. Then, 1.5% polyethylene glycol diacrylate and 1.5% photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to form a 3D printing ink.

[0030] Step 2: Print complex three-dimensional structures using the 3D printing ink obtained in Step 1 on a custom high-resolution 3D printing system; the exposure time is 10 seconds, and the thickness of each layer is 50 mm.

[0031] Step 3: After printing, remove the unreacted monomers and crosslinking agents from the surface of the printed 3D structure;

[0032] Step 4: Post-cur the structure in a UV oven to obtain the three-dimensional structure.

[0033] The eighth objective of this invention is to provide an application of visible light-excited organic long afterglow materials in anti-counterfeiting and information encryption.

[0034] Compared with the prior art, the beneficial effects of the present invention are:

[0035] This invention provides a visible light-excited organic long-afterglow material, its preparation method, and its applications. The host material involved in this invention is inexpensive and has good processability. Even a trace amount of guest material doping can demonstrate that the host or guest material alone does not possess visible light-excited long-afterglow properties. Currently, ultraviolet-excited long-afterglow materials are more common in the market. The organic long-afterglow material provided by this invention can be excited by both ultraviolet and visible light. Furthermore, this type of material can be used as a 3D printing ink. This invention can print 3D printed structures that can be excited by visible light, possessing photoresponse-based anti-counterfeiting functions, and can be further applied in fields such as intelligent anti-counterfeiting, information encryption, and data storage, thereby meeting the needs of different user groups. Attached Figure Description

[0036] Figure 1 The room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBASF@SMP material provided in Example 2 of this invention under ultraviolet (365nm) excitation are shown.

[0037] Figure 2 The room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBASF@SMP material provided in Example 2 of this invention under visible light (445nm) excitation.

[0038] Figure 3 The room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBAOF@PMMA material provided in Example 4 of this invention under ultraviolet (365nm) excitation are shown.

[0039] Figure 4 The room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBAOF@PMMA material provided in Example 4 of this invention under visible light (430 nm) excitation.

[0040] Figure 5These are before and after photos of the 3D printed three-dimensional structure illuminated according to Embodiment 11 of the present invention. Detailed Implementation

[0041] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0042] This invention relates to a triarylamine system-based material that can be used to construct organic long-afterglow doped materials. These materials possess advantages such as ease of design and synthesis, good compatibility with different polymer hosts, low production costs, and easily tunable luminescence. More importantly, the organic long-afterglow host-guest doped materials constructed based on the triarylamine system successfully achieved responsiveness to both ultraviolet and visible light excitation sources. Under excitation, they achieved an afterglow lifetime exceeding 1 second and can be excited by the flash of a mobile phone. These materials can be used in anti-counterfeiting printing, encrypted 3D printing, and other processes. Their inherent dual-gating properties reduce the cost of high-performance anti-counterfeiting from the source, thus offering broader application space and market prospects. This invention provides visible light-excited organic long-afterglow materials, along with their preparation methods and applications, which have significant research significance and scientific value. It also promotes the widespread application of visible light-excited organic long-afterglow materials in novel anti-counterfeiting, information encryption, and intelligent 3D printing fields.

[0043] The first aspect of the present invention provides a visible light-excited organic long afterglow material, comprising a host material and a guest material doped in the host material;

[0044] The main material is a polar polymer;

[0045] The object material is a compound of formula (Ⅰ);

[0046]

[0047] In formula (Ⅰ), R1 is dibenzothiophene, dibenzothiophene sulfone, benzothiophene, benzothiophene sulfone, dibenzofuran, benzofuran, carbazole or pyridine;

[0048] R2 and R3 are each independently selected from one of the following groups: hydrogen, methoxy, halogen, hydroxyl, and carboxyl.

[0049] The polar polymer is polyvinyl alcohol, polymethyl methacrylate, polyvinylpyrrolidone, or hydroxyethyl polyacrylate.

[0050] The mass ratio of the object material to the main material is 1:100 to 1,000,000.

[0051] This invention relates to an organic long-afterglow host-guest doped material based on a triarylamine system, which successfully achieves responsiveness to both ultraviolet and visible light excitation sources. Under excitation, it achieves an afterglow lifetime of over 1 second and can be excited by the flash of a mobile phone.

[0052] The object material is prepared according to the following steps:

[0053] Compound (V), compound (IV), potassium tert-butoxide, tritert-butylphosphine, and palladium catalyst were refluxed at 100°C with toluene as solvent to undergo a Buchwald-Hartwig coupling reaction to yield compound (III); the synthetic route is as follows:

[0054]

[0055] Compound (III), compound (II), potassium tert-butoxide, tritert-butylphosphine, and palladium catalyst were refluxed at 100°C with toluene as solvent to undergo a Buchwald-Hartwig coupling reaction to yield compound (I); the synthetic route is as follows:

[0056]

[0057] In one embodiment, the method for synthesizing the guest material of the organic long afterglow material includes:

[0058] Step 1 involves the palladium-catalyzed coupling of a substituted phenyl halide (R2PhBr) and a substituted naphthyl primary amine (R3NhNH2) to prepare an aromatic secondary amine (R2Ph-NH-R3Nh). Specifically, at room temperature, an aryl halide, an aryl primary amine, a strong base potassium tert-butoxide, tritert-butylphosphine, and a palladium catalyst (tris(dibenzylacetone)dipalladium) are added, and the mixture is refluxed at 100°C using toluene as a solvent to undergo a Buchwald-Hartwig coupling reaction to obtain the target aromatic secondary amine (R2Ph-NH-R3Nh).

[0059] Step 2 involves coupling the aryl halide (R1-Br) and the aryl secondary amine (R2Ph-NH-R3Nh) under palladium catalysis to prepare the target compound, an aromatic tertiary amine. Specifically, the aryl halide, the aryl secondary amine, and the strong base potassium tert-butoxide, tritert-butylphosphine, and the palladium catalyst (bis(dibenzylacetone)palladium) are added at room temperature. Toluene is used as the solvent and the mixture is refluxed at 100°C to undergo a Buchwald-Hartwig coupling reaction to obtain the target compound, a triarylamine derivative.

[0060] In compounds of formulas (I), (II), (III), (IV), and (V), the corresponding R1 is dibenzothiophene, dibenzothiophene sulfone, benzothiophene, benzothiophene sulfone, dibenzofuran, benzofuran, carbazole, or pyridine; R2 and R3 are each independently selected from one of hydrogen, methoxy, halogen, hydroxyl, or carboxyl groups.

[0061] A second aspect of this invention provides a method for preparing a visible light-excited organic long afterglow material, comprising the following steps:

[0062] The host material and the guest material are weighed separately and placed into a container. A small amount of solvent is added and mixed evenly to obtain a mixed solution. The mixed solution is then drop-coated onto a quartz plate and dried to obtain an organic long afterglow material on the quartz plate.

[0063] In one embodiment, the host material and guest material are weighed and placed into a beaker, a small amount of solvent is added, and the mixture is stirred thoroughly to ensure that the organic long afterglow guest material and the polymer host material are in full contact. A certain amount of solvent is then dropped onto a quartz plate and allowed to stand and dry to obtain the organic long afterglow material. The solvent is toluene.

[0064] A third aspect of this invention provides a method for preparing a visible light-excited organic long afterglow material, comprising the following steps:

[0065] After weighing the main material and the guest material separately and placing them into a container, add a small amount of solvent, mix evenly, and then heat to evaporate the solvent. Grind the dried material into powder and then hot press it into a film to obtain the organic long afterglow material.

[0066] In one embodiment, the host material and guest material are weighed and placed into a beaker, a small amount of solvent is added, and the mixture is stirred thoroughly to ensure that the organic long afterglow guest material and the polymer host material are in full contact. After heating to evaporate the solvent, the resulting polymer material is ground into powder and then hot-pressed into a film using a hot press to obtain the organic long afterglow material; wherein, the solvent is toluene.

[0067] A fourth aspect of this invention provides a method for preparing a visible light-excited organic long afterglow material, comprising the following steps:

[0068] After weighing the main material and the guest material separately and placing them into a container, add a small amount of solvent, mix them evenly, and then perform photopolymerization and curing in an ultraviolet oven to obtain the organic long afterglow material.

[0069] After weighing the main material and the guest material separately and placing them into a container, a small amount of solvent is added and the mixture is stirred thoroughly. A certain amount of the liquid mixture is then placed in an ultraviolet oven for photopolymerization and curing to obtain the organic long afterglow material. The solvent is toluene.

[0070] The fifth aspect of this invention provides an application of visible light-excited organic long afterglow materials in 3D printing.

[0071] The sixth aspect of the present invention provides a three-dimensional structure, which is 3D printed using 3D printing ink comprising the above-mentioned visible light-excited organic long afterglow material.

[0072] The seventh aspect of this invention provides a method for preparing a three-dimensional structure, comprising the following steps:

[0073] Step 1: Use the organic long afterglow material directly as 3D printing ink;

[0074] Alternatively, the monomers of 2-hydroxyethyl acrylate and acrylic acid are mixed with the organic long afterglow material at a mass fraction of 7000:3000:1, and then 1.5% polyethylene glycol diacrylate and 1.5% photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) are added and stirred thoroughly to form a 3D printing ink.

[0075] Step 2: Print complex three-dimensional structures using the 3D printing ink obtained in Step 1 on a custom high-resolution 3D printing system; the exposure time is 10 seconds, and the thickness of each layer is 50 mm.

[0076] Step 3: After printing, use a rubber suction ball to remove unreacted monomers and crosslinking agents from the surface of the printed 3D structure;

[0077] Step 4: Post-cur the structure in a UV oven to obtain the three-dimensional structure.

[0078] The eighth aspect of this invention provides the application of visible light-excited organic long afterglow materials in anti-counterfeiting and information encryption.

[0079] The organic long-afterglow guest material provided by this invention can be excited by both ultraviolet and visible light. Furthermore, this type of material can be used as a 3D printing ink. Through the above methods, this invention can print 3D printed structures that can be excited by visible light, possessing photoresponse-based anti-counterfeiting capabilities. It can be further applied in fields such as intelligent anti-counterfeiting, information encryption, and data storage, thereby meeting the needs of different user groups.

[0080] It should be noted that, unless otherwise specified, the experimental methods used in this invention are all conventional methods; and the reagents and materials used, unless otherwise specified, are all commercially available.

[0081] Example 1

[0082] The preparation method of organic long afterglow material 3-TBASF@PMMA 3D printing ink includes:

[0083]

[0084] Naphthylamine (2.86 g, 20 mmol), bromobenzene (3.45 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask under an argon atmosphere. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.5 mL of tritert-butylphosphine and 25 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, N-phenyl-2-naphthylamine (3.52 g, yield 80.4%), was obtained.

[0085]

[0086] Under an argon atmosphere, N-phenyl-2-naphthylamine (2.20 g, 10 mmol), 3-bromodibenzothiophene (2.96 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being hexane:dichloromethane = 7:1. 3-TBASF was obtained as a white solid (1.22 g, yield 30.3%).

[0087] 0.3g of 3-TBASF guest material was incorporated into PMMA resin material and mixed evenly. The resulting material was then subjected to photopolymerization treatment in an ultraviolet oven to obtain organic long afterglow 3-TBASF@PMMA.

[0088] Example 2

[0089] The preparation method of organic long afterglow material 4-TBASF@SMP 3D printing ink includes:

[0090]

[0091] Naphthylamine (2.86 g, 20 mmol), bromobenzene (3.45 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask under an argon atmosphere. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.5 mL of tritert-butylphosphine and 25 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, N-phenyl-2-naphthylamine (3.52 g, yield 80.4%), was obtained.

[0092]

[0093] Under an argon atmosphere, N-phenyl-2-naphthylamine (2.20 g, 10 mmol), 4-bromodibenzothiophene (2.96 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being hexane:dichloromethane = 7:1. 4-TBASF was obtained as a white solid (2.48 g, yield 61.5%).

[0094] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 4-TBASF guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 4-TBASF@SMP.

[0095] Example 3

[0096] The preparation method of the organic long afterglow material 3-TBAOF@SMP includes:

[0097]

[0098] Naphthylamine (2.20 g, 10 mmol), bromobenzene (3.45 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask under an argon atmosphere. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.5 mL of tritert-butylphosphine and 25 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, N-phenyl-2-naphthylamine (3.52 g, yield 80.4%), was obtained.

[0099]

[0100] Under an argon atmosphere, N-phenyl-2-naphthylamine (2.20 g, 10 mmol), 3-bromodibenzofuran (2.96 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear solution. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being hexane:dichloromethane = 8:1. 3-TBAOF was obtained as a white solid (1.35 g, yield 35.0%).

[0101] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 3-TBAOF guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 3-TBAOF@SMP.

[0102] Example 4

[0103] The preparation method of the organic long afterglow material 4-TBAOF@PMMA includes:

[0104]

[0105] Naphthylamine (2.20 g, 10 mmol), bromobenzene (3.45 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask under an argon atmosphere. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.5 mL of tritert-butylphosphine and 25 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, N-phenyl-2-naphthylamine (3.52 g, yield 80.4%), was obtained.

[0106]

[0107] Under an argon atmosphere, N-phenyl-2-naphthylamine (2.20 g, 10 mmol), 2-bromodibenzofuran (2.96 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being hexane:dichloromethane = 8:1. 4-TBAOF was obtained as a white solid (1.83 g, yield 47.3%).

[0108] 100g of polymethyl methacrylate (PMMA) and 1g of 4-TBAOF were dissolved together in 500mL of toluene. After thorough stirring and curing, the mixture was heated and ground to obtain a powder material. The powder material was then hot-pressed into a film to make its surface uniform, thus obtaining the organic long afterglow material 4-TBAOF@PMMA.

[0109] Example 5

[0110] The preparation method of organic long-afterglow host-guest material 2-TBAOMeOF@SMP 3D printing ink includes:

[0111]

[0112] Under an argon atmosphere, p-methoxynaphthylamine (3.48 g, 20 mmol), p-methoxybromobenzene (4.11 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask. After adding 80 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 1 mL of tritert-butylphosphine and 50 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, 4,4'-methoxy-N-phenyl-2-naphthylamine (4.20 g, yield 75.3%), was obtained.

[0113]

[0114] Under an argon atmosphere, 4,4'-methoxy-N-phenyl-2-naphthylamine (2.79 g, 10 mmol), 2-bromodibenzofuran (2.96 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being hexane:dichloromethane = 7:1. 2-TBAOMeOF was obtained as a white solid (1.48 g, yield 33.3%).

[0115] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 2-TBAOMeOF guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 2-TBAOMeOF@SMP.

[0116] Example 6

[0117] The preparation method of organic long-afterglow host-guest material 3-TBAOMeOF@SMP 3D printing ink includes:

[0118]

[0119] Under an argon atmosphere, p-methoxynaphthylamine (3.48 g, 20 mmol), p-methoxybromobenzene (4.11 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask. After adding 80 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 1 mL of tritert-butylphosphine and 50 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, 4,4'-methoxy-N-phenyl-2-naphthylamine (4.20 g, yield 75.3%), was obtained.

[0120]

[0121] Under an argon atmosphere, 4,4'-methoxy-N-phenyl-2-naphthylamine (2.79 g, 10 mmol), 3-bromodibenzofuran (2.96 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being n-hexane:dichloromethane = 7:1. 3-TBAOMeOF was obtained as a white solid (2.86 g, yield 64.4%).

[0122] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 3-TBAOMeOF guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 3-TBAOMeOF@SMP.

[0123] Example 7

[0124] The preparation method of organic long-afterglow host-guest material 4-TBAOMeOF@SMP 3D printing ink includes:

[0125]

[0126] Under an argon atmosphere, p-methoxynaphthylamine (3.48 g, 20 mmol), p-methoxybromobenzene (4.11 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask. After adding 80 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 1 mL of tritert-butylphosphine and 50 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, 4,4'-methoxy-N-phenyl-2-naphthylamine (4.20 g, yield 75.3%), was obtained.

[0127]

[0128] Under an argon atmosphere, 4,4'-methoxy-N-phenyl-2-naphthylamine (2.79 g, 10 mmol), 4-bromodibenzofuran (2.96 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being hexane:dichloromethane = 7:1. 4-TBAOMeOF was obtained as a white solid (3.89 g, yield 87.4%).

[0129] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 4-TBAOMeOF guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 4-TBAOMeOF@SMP.

[0130] Example 8:

[0131] The preparation method of 2-TBAOMeOS@SMP 3D printing ink, an organic long-afterglow host-guest material, includes:

[0132]

[0133] Under an argon atmosphere, p-methoxynaphthylamine (3.48 g, 20 mmol), p-methoxybromobenzene (4.11 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask. After adding 80 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 1 mL of tritert-butylphosphine and 50 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, 4,4'-methoxy-N-phenyl-2-naphthylamine (4.20 g, yield 75.3%), was obtained.

[0134]

[0135] Under an argon atmosphere, 4,4'-methoxy-N-phenyl-2-naphthylamine (2.79 g, 10 mmol), 4-bromodibenzothiophene (3.16 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being n-hexane:dichloromethane = 7:1. 2-TBAOMeOS was obtained as a white solid (0.58 g, yield 12.6%).

[0136] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 2-TBAOMeOS guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 2-TBAOMeOS@SMP.

[0137] Example 9

[0138] The preparation method of 3-TBAOMeOS@SMP 3D printing ink, an organic long-afterglow host-guest material, includes:

[0139]

[0140] Under an argon atmosphere, p-methoxynaphthylamine (3.48 g, 20 mmol), p-methoxybromobenzene (4.11 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask. After adding 80 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 1 mL of tritert-butylphosphine and 50 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, 4,4'-methoxy-N-phenyl-2-naphthylamine (4.20 g, yield 75.3%), was obtained.

[0141]

[0142] Under an argon atmosphere, 4,4'-methoxy-N-phenyl-2-naphthylamine (2.79 g, 10 mmol), 3-bromodibenzothiophene (3.16 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered to obtain a clear liquid, and the solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being n-hexane:dichloromethane = 7:1. 3-TBAOMeOS was obtained as a white solid (2.26 g, yield 48.9%).

[0143] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 3-TBAOMeOS guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 3-TBAOMeOS@SMP.

[0144] Example 10

[0145] The preparation method of 4-TBAOMeOS@SMP 3D printing ink, an organic long-afterglow host-guest material, includes:

[0146]

[0147] Under an argon atmosphere, p-methoxynaphthylamine (3.48 g, 20 mmol), p-methoxybromobenzene (4.11 g, 22 mmol), and potassium tert-butoxide (4.48 g, 40 mmol) were added to a 250 mL two-necked flask. After adding 80 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 1 mL of tritert-butylphosphine and 50 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear liquid. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with hexane as the eluent. A white solid, 4,4'-methoxy-N-phenyl-2-naphthylamine (4.20 g, yield 75.3%), was obtained.

[0148]

[0149] Under an argon atmosphere, 4,4'-methoxy-N-phenyl-2-naphthylamine (2.79 g, 10 mmol), 2-bromodibenzothiophene (3.16 g, 12 mmol), and potassium tert-butoxide (3.36 g, 30 mmol) were added to a 250 mL two-necked flask. After adding 50 mL of toluene, the mixture was stirred thoroughly with a magnetic stirrer until homogeneous. Then, 0.3 mL of tritert-butylphosphine and 15 mg of Pd(dba)₂ were added, and the mixture was heated to 100 °C and refluxed for 24 h. The mixture was then cooled to room temperature. Toluene was removed from the reaction solution by vacuum distillation. The reactants were extracted with dichloromethane and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and filtered to obtain a clear solution. The solvent was removed by rotary evaporation. Finally, the solution was purified by silica gel column chromatography, with the eluent being hexane:dichloromethane = 7:1. 4-TBAOMeOS was obtained as a white solid (3.60 g, yield 77.7%).

[0150] 210g of 2-hydroxyethyl acrylate and 90g of acrylic acid were mixed evenly, and then 4.5g of polyethylene glycol diacrylate and 4.5g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxyphosphate (TPO) were added and stirred thoroughly to prepare the 3D printing ink SMP. Then, 0.3g of 4-TBAOMeOS guest material was incorporated into the SMP host material and mixed evenly. The resulting material was then photopolymerized in a UV oven to obtain the organic long-afterglow material 4-TBAOMeOS@SMP.

[0151] Example 11

[0152] Application methods of organic long afterglow materials include:

[0153] Based on the organic long-afterglow material 3-TBASF@SMP prepared in Example 3, a complex mesh-like three-dimensional structure was printed on a custom high-resolution 3D printing system; the exposure time was 10 seconds, and the thickness of each layer was 50 mm. After printing, unreacted monomers and crosslinking agents on the surface of the printed 3D structure were removed using rubber suction balls. Finally, the structure was post-cured in a UV oven.

[0154] To illustrate the relevant properties of the organic long afterglow material provided by this invention, its relevant properties are explained through testing.

[0155] Figure 1 The images show the room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBASF@SMP material provided in Example 2 of this invention under ultraviolet (365 nm) excitation. Figure 1 As can be seen, the 4-TBASF@SMP material exhibits long afterglow properties when excited by ultraviolet light for 5 ms.

[0156] Figure 2 The room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBASF@SMP material provided in Example 2 of this invention under visible light (445 nm) excitation. Figure 2 As can be seen, the 4-TBASF@SMP material exhibits long afterglow properties under visible light excitation with a delay of 5 ms. Combined with... Figure 1 It can be determined that the long afterglow of 4-TBASF@SMP can be excited by both ultraviolet light and visible light.

[0157] Figure 3 The images show the room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBAOF@PMMA material provided in Example 4 of this invention under ultraviolet (365 nm) excitation. Figure 3 As can be seen, the 4-TBAOF@PMMA material exhibits long afterglow properties when excited by ultraviolet light for 5 ms.

[0158] Figure 4 The room-temperature phosphorescence emission spectrum and its delayed spectrum of the 4-TBAOF@PMMA material provided in Example 4 of this invention under visible light (430 nm) excitation. Figure 4 As can be seen, the 4-TBAOF@PMMA material exhibits long afterglow properties under visible light excitation with a delay of 5 ms. Combined with... Figure 3 It can be determined that the long afterglow of 4-TBAOF@PMMA can be excited by both ultraviolet light and visible light.

[0159] Figure 5 These are before-and-after photographs of the 3D-printed three-dimensional structure provided in Embodiment 11 of the present invention, showing the process of illuminating it. Specifically, the material provided in Embodiment 1 is 3D printed into a mesh-like three-dimensional structure, and the photographs are taken before and after illumination. Figure 5 It is understood that the material designed in this invention can be used as 3D printing ink in 3D printing technology.

[0160] In summary, this invention provides a class of visible light-excited organic long-afterglow materials, along with preparation methods and applications based on these materials. This has significant research implications and scientific value, and also promotes the widespread application of visible light-excited organic long-afterglow materials in novel anti-counterfeiting, information encryption, and intelligent 3D printing. The organic long-afterglow materials provided by this invention can be used for 3D printing, and a convenient preparation process is offered. Through the above methods, this invention enables 3D-printed fine structures to possess anti-counterfeiting capabilities that can be activated by visible light or ultraviolet light to produce room-temperature phosphorescence. This has significant research implications and scientific value, and further promotes the widespread application of visible light-excited long-afterglow materials in intelligent anti-counterfeiting, information encryption, and data storage, thereby meeting the needs of different user groups.

[0161] This invention describes preferred embodiments and their effects. However, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to include both the preferred embodiments and all changes and modifications falling within the scope of this invention.

[0162] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A visible light-excited organic long-persistence material, characterized in that, Includes the host material and the guest material doped in the host material; The main material is a polar polymer; The guest material is a compound of formula (Ⅰ); Equation (I) In formula (Ⅰ), R1 is dibenzothiophene or dibenzofuran; R2 and R3 are each independently selected from one of the following groups: hydrogen, methoxy, halogen, hydroxyl, and carboxyl. The polar polymer is polymethyl methacrylate; The mass ratio of the object material to the main material is 1:100~1000000.

2. The organic long-p Persistence material excited by visible light according to claim 1, characterized in that, The object material is prepared according to the following steps: Compound (V), compound (IV), potassium tert-butoxide, tritert-butylphosphine, and palladium catalyst were refluxed at 100°C with toluene as solvent to undergo a Buchwald-Hartwig coupling reaction to yield compound (III); the synthetic route is as follows: Compound (III), compound (II), potassium tert-butoxide, tritert-butylphosphine, and palladium catalyst were refluxed at 100°C with toluene as solvent to undergo a Buchwald-Hartwig coupling reaction to obtain compound (I); the synthetic route is as follows: In the compounds of formula (I), (II), (III), (IV), and (V), R1 is dibenzothiophene or dibenzofuran; R2 and R3 are each independently selected from one of hydrogen, methoxy, halogen, hydroxyl, or carboxyl groups.

3. A method for producing the visible-light-excited organic long-persistence material according to claim 1 or 2, characterized by, Includes the following steps: The host material and the guest material are weighed separately and placed into a container. A small amount of solvent is added and mixed evenly to obtain a mixed solution. The mixed solution is then drop-coated onto a quartz plate and dried to obtain an organic long afterglow material on the quartz plate.

4. A method for producing the visible-light-excited organic long-persistence material according to claim 1 or 2, characterized by, Includes the following steps: After weighing the main material and the guest material separately and placing them into a container, add a small amount of solvent, mix evenly, and then heat to evaporate the solvent. Grind the dried material into powder and then hot press it into a film to obtain the organic long afterglow material.

5. A method for producing the visible light-excited organic long-persistence material according to claim 1 or 2, characterized by, Includes the following steps: After weighing the main material and the guest material separately and placing them into a container, add a small amount of solvent, mix them evenly, and then perform photopolymerization and curing in an ultraviolet oven to obtain the organic long afterglow material.

6. The application of a visible light-excited organic long afterglow material as described in claim 1 or 2 in 3D printing.

7. A three-dimensional structure, characterized by The material is 3D printed using 3D printing ink comprising an organic long afterglow material excited by visible light as described in claim 1 or 2.

8. A method of producing a three-dimensional structure according to claim 7, characterized by, Includes the following steps: Step 1: Use the organic long afterglow material directly as 3D printing ink; Step 2: Print a complex three-dimensional structure using the 3D printing ink obtained in Step 1 on a custom high-resolution 3D printing system; the exposure time is 10 seconds and the thickness of each layer is 50 mm. Step 3: After printing, remove the unreacted monomers and crosslinking agents from the surface of the printed 3D structure; Step 4: Post-cur the structure in a UV oven to obtain the three-dimensional structure.

9. The application of a visible light-excited organic long afterglow material as described in claim 1 or 2 in anti-counterfeiting and information encryption.

Images