An organic long-afterglow material, a preparation method and application thereof

Abstract

The application discloses an organic long-afterglow material and a preparation method and application thereof, and application of a compound of formula 1 in a photo-activated organic long-afterglow material. The compound of formula 1 is used as a guest component of the photo-activated long-afterglow material, has high efficiency in generating triplet excitons, and has strong ability in transferring triplet exciton energy to oxygen molecules. The long-afterglow material prepared by doping the compound of formula 1 in an epoxy polymer has a short photo-activation process, and the material after activation can be restored to a state without long-afterglow emission by heating at 90-120 DEG C for 6-45 min and cooling to room temperature, thus effectively overcoming the defects of long activation time and difficulty in restoring to an unactivated state of the current photo-activated long-afterglow material. The prepared material not only has the reversible photo-activated long-afterglow luminescence characteristics, but also has long afterglow luminescence lifetime, high efficiency, adjustable color and good stability after activation, and therefore, the material has strong practicability in the fields of anti-counterfeiting, data encryption, optical printing and the like.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and in particular to an organic long afterglow material and a preparation method and application thereof. Background Art

[0002] Long-afterglow materials continue to emit light even after the excitation source ceases, effectively eliminating the effects of short-lived background light and significantly improving the signal-to-noise ratio of the luminescence signal. Traditional long-afterglow luminescent materials are primarily inorganic or organometallic materials containing precious metals or rare earth elements. However, these materials suffer from high preparation costs and high toxicity. In contrast, purely organic URTP materials offer advantages such as low toxicity, ease of synthesis, and low cost, addressing the shortcomings of traditional long-afterglow materials. Consequently, they have attracted widespread attention from researchers and are being applied in biological tissue imaging, anti-counterfeiting, information encryption, and light-emitting devices.

[0003] Currently, strategies for achieving long-lasting organic luminescence at room temperature primarily include: 1. Providing a rigid environment for organic molecules through crystal engineering and forcing them to form specialized molecular aggregates; 2. Polymerizing organic molecules into polymers; and 3. Incorporating organic molecules into a solid matrix that isolates oxygen and restricts molecular motion through a host-guest doping approach. Among these, doping organic molecules (guests) into a polymer matrix (host) is simpler and faster, and the long-lasting luminescence properties of the material can be tuned by varying parameters such as the chemical structure and doping concentration of the organic molecules and the molecular weight of the polymer matrix. Organic long-lasting luminescence materials prepared using this method also offer advantages such as good processability, flexibility, and ease of large-scale production. However, these materials generally suffer from low afterglow efficiency and short lifetimes. This is attributed to factors such as low intersystem crossing efficiency of the organic molecules, low triplet excited state stability, and insufficient protection and confinement of the guest molecules by the selected polymer matrix. In addition, since the matrix used is mostly linear polymers with polar side groups, such as polylactic acid (PLA), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), etc., the long afterglow performance of the material is greatly affected by water vapor and oxygen in the air and has poor stability.

[0004] The above problems seriously restrict the practical application of polymer-based organic long-lasting glow materials. Therefore, the design and preparation of polymer-based luminescent materials with high afterglow efficiency, long life and good stability at room temperature has important theoretical and practical significance for the development and application of organic long-lasting glow materials. Summary of the Invention

[0005] The present invention aims to address at least one of the aforementioned technical problems existing in the prior art. To this end, the present invention provides an organic long-afterglow material, its preparation method, and its application. This organic long-afterglow material overcomes the problems of prior art light-activated long-afterglow materials, such as long activation time and difficulty in returning to an unactivated state.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] The first aspect of the present invention provides the use of a compound of formula 1 in a light-activated organic long afterglow material:

[0008]

[0009] Among them, R1 is deuterium, H, C1~C 20 Alkyl, C3~C 20 Cycloalkyl.

[0010] In some embodiments of the present invention, R1 is deuterium, H, C1-C 12 Alkyl, C3~C 12 Cycloalkyl.

[0011] In some embodiments of the present invention, R1 is deuterium, H, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, or biphenyl.

[0012] In some embodiments of the present invention, the compound of Formula 1 is selected from at least one of the following compounds:

[0013]

[0014] In a second aspect of the present invention, a light-activated organic long afterglow material is provided, comprising a host component and a guest component doped in the host component, wherein the guest component comprises the compound of formula 1.

[0015] In some embodiments of the present invention, the main component includes an epoxy polymer.

[0016] In some embodiments of the present invention, the epoxy polymer is formed by polymerization of bisphenol A diglycidyl ether and a curing agent.

[0017] In some embodiments of the present invention, in the light-activated organic long afterglow material, the molar ratio of bisphenol A diglycidyl ether, the guest component, and the curing agent is 1: (0.0001-0.05): (0.5-2).

[0018] In some embodiments of the present invention, the curing agent includes at least one of 1,3-propylenediamine, diethylenetriamine, and triethylenetetramine.

[0019] The light-activated organic long afterglow material of the present invention does not have the property of ultra-long-life phosphorescence emission in its initial state. After a short period of light activation, its phosphorescence lifetime is significantly prolonged and its efficiency is greatly improved, thereby producing long-life and high-efficiency afterglow luminescence. After heat treatment, it can be restored to a state without ultra-long-life phosphorescence emission, that is, it has reversible light-activated organic long afterglow luminescence characteristics. Aromatic organic compounds containing heteroatoms can undergo π-π* transitions, have strong spin-orbit coupling, and have high intersystem crossing efficiency. At the same time, epoxy resin has a covalently cross-linked three-dimensional network structure, which can isolate oxygen and water vapor and restrict molecular motion, greatly improving the stability of the triplet excitons of the guest molecules and reducing their non-radiative transition rate. The synergistic effect of the host and the guest enables the prepared polymer-based luminescent material to produce organic long afterglow with long lifetime, high quantum yield, and good performance stability.

[0020] In some embodiments of the present invention, the doping includes physical doping.

[0021] In some embodiments of the present invention, the mass fraction of the guest molecule is 0.001% to 5%, such as 0.1% to 1%. Depending on the chemical structure of the doped guest molecule, the afterglow quantum yield, afterglow lifetime and other properties of the organic long afterglow material can be regulated.

[0022] In the present invention, during light activation, the energy of triplet excitons generated by guest molecules can be effectively transferred to residual oxygen molecules in the epoxy polymer, converting them into singlet oxygen. The highly active singlet oxygen then reacts with the epoxy polymer matrix, thereby eliminating the quenching effect of oxygen molecules in the polymer on triplet excitons generated by the guest molecules. Since the guest molecules of the present invention have a high efficiency in generating triplet excitons and a strong ability to transfer triplet exciton energy to oxygen molecules, the photoactivation process of the material can be completed in only 30 to 120 seconds.

[0023] In the present invention, after being activated by light, the organic long-afterglow material is heated at 90-120°C (e.g., 100°C) in an oxygen atmosphere for 6-45 minutes (e.g., 10-45 minutes) and then cooled to room temperature to restore the material to a state without ultra-long-lifetime phosphorescence emission. During heating, the movement of the epoxy polymer molecular chains intensifies, allowing oxygen to enter the polymer. After cooling to room temperature, the newly entered oxygen molecules quench the triplet excitons generated by the guest molecules, preventing the material from producing long-afterglow luminescence.

[0024] In some embodiments of the present invention, the method for preparing the light-activated organic long afterglow material comprises the following steps:

[0025] Bisphenol A diglycidyl ether, a guest component, and a curing agent are mixed and stirred, and then cured to obtain the light-activated organic long afterglow material.

[0026] In some embodiments of the present invention, the curing temperature is 20-120°C, such as 80-100°C.

[0027] In some embodiments of the present invention, the curing time is 0.5 to 48 hours, such as 1 to 3 hours.

[0028] The third aspect of the present invention provides the use of the compound of Formula 1 and / or the light-activated organic long afterglow material in data encryption and / or anti-counterfeiting and / or functional ink and / or road marking.

[0029] The fourth aspect of the present invention provides a compound of formula 2,

[0030]

[0031] Among them, R2 is C1~C 20 Alkyl, C3~C 20 Cycloalkyl.

[0032] In some embodiments of the present invention, R2 is deuterium, H, C1-C 12 Alkyl, C3~C 12 Cycloalkyl.

[0033] In some embodiments of the present invention, R2 is deuterium, H, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, or biphenyl.

[0034] In some embodiments of the present invention, the compound of formula 2 is selected from at least one of the following compounds:

[0035]

[0036] The fifth aspect of the present invention provides a method for preparing the compound of formula 2, comprising the following steps: 5H-benzo[a]benzo[4,5]thieno[3,2-c]carbazole ( ) and a halogenated alkane to produce a compound of formula 2;

[0037] The halogenated alkane is selected from halogenated C1-C 20 Alkanes, halogenated C3~C 20 Cycloalkanes.

[0038] In some embodiments of the present invention, the molar ratio of 5H-benzo[a]benzo[4,5]thieno[3,2-c]carbazole to halogenated alkane is 1:(3-6), such as 1:(4-5), (1:4.5).

[0039] In some embodiments of the present invention, the halogen group in the halogenated alkane is selected from any one of F, Cl, Br, and I, such as Br.

[0040] In some embodiments of the present invention, the reaction comprises a substitution reaction.

[0041] In some embodiments of the present invention, the reaction temperature is 20-100°C; such as 30-80°C, 40-70°C, or 60°C.

[0042] In some embodiments of the present invention, the reaction time is 4 to 36 hours, such as 8 to 16 hours, 10 to 14 hours, or 12 hours.

[0043] In some embodiments of the present invention, the solvent used in the reaction includes any one of tetrahydrofuran, dichloromethane, and 1,4-dioxane.

[0044] In some embodiments of the present invention, the reaction is carried out under alkaline conditions, and the alkaline conditions are adjusted to at least one of sodium hydride (NaH), sodium tert-butoxide (t-BuONa), and potassium tert-butoxide (t-BuOK).

[0045] In some embodiments of the present invention, the reaction is carried out in an inert atmosphere, such as an argon atmosphere.

[0046] In some embodiments of the present invention, the method for preparing the compound of formula 2 further comprises purifying the reaction product, wherein the purification comprises separation and purification, reprecipitation, filtration, and drying.

[0047] In some embodiments of the present invention, the separation and purification comprises separation and purification using silica gel column chromatography.

[0048] In some embodiments of the present invention, when the silica gel column chromatography is used for separation and purification, the eluent used includes a mixed solution of a medium-polarity solvent and a low-polarity solvent in a volume ratio of (1-3):3; for example, a mixed solution of a medium-polarity solvent and a low-polarity solvent in a volume ratio of 1:3.

[0049] In some embodiments of the present invention, the polar solvent includes at least one of dichloromethane, chloroform, ethyl acetate, and tetrahydrofuran.

[0050] In some embodiments of the present invention, the low-polarity solvent includes at least one of petroleum ether, cyclohexane, and hexane; for example, the low-polarity solvent is n-hexane.

[0051] The beneficial effects of the present invention are:

[0052] The compound of Formula 1 of the present invention can be used in photoactivated long-afterglow materials. As a guest component in photoactivated long-afterglow materials, it has high efficiency in generating triplet excitons and a strong ability to transfer triplet exciton energy to oxygen molecules. The long-afterglow material prepared by doping it in an epoxy polymer has a short photoactivation process, and the activated material can be restored to a state without long-afterglow emission by heating it at 90-120°C for 6-45 minutes and cooling it to room temperature. This effectively overcomes the shortcomings of current photoactivated long-afterglow materials, such as the long activation time required and the difficulty in restoring it to an unactivated state. The prepared material not only exhibits reversible photoactivated long-afterglow luminescence properties, but also exhibits a long lifetime, high efficiency, adjustable color, and good stability after activation. Therefore, the material has strong practical applications in fields such as anti-counterfeiting, data encryption, and optical printing. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the compound of formula I of the present invention.

[0054] Figure 2 It is the hydrogen nuclear magnetic resonance spectrum of the compound of formula II of the present invention.

[0055] Figure 3 It is the hydrogen nuclear magnetic resonance spectrum of the compound of formula III of the present invention.

[0056] Figure 4 It is the hydrogen nuclear magnetic resonance spectrum of the compound of formula IV of the present invention.

[0057] Figure 5 is the hydrogen nuclear magnetic resonance spectrum of the compound of formula V of the present invention.

[0058] Figure 6 A diagram showing the relationship between illumination time and afterglow intensity of the long afterglow materials prepared in Examples 5 to 9 of the present invention.

[0059] Figure 7 The graph is a graph of fluorescence emission decay curves of the compound of formula I (a), the compound of formula II (b), the compound of formula III (c), the compound of formula IV (d), and the compound of formula V (e) of the present invention.

[0060] Figure 8 The photoluminescence spectra of the compound of formula I (a), the compound of formula II (b), the compound of formula III (c), the compound of formula IV (d), and the compound of formula V (e) of the present invention are shown.

[0061] Figure 9 This is a graph showing emission attenuation curves of polymer materials with different doping concentrations of the guest molecules of the present invention, namely, compound I (a), compound II (b), compound III (c), compound IV (d), and compound V (e).

[0062] Figure 10 This is a cyclic diagram of the photoactivated long afterglow luminescence and deactivation process of the polymer material of Example 9 of the present invention.

[0063] Figure 11 This is a graph showing the emission attenuation curves of the polymer material of Example 9 of the present invention after multiple cycles.

[0064] Figure 12 This is a diagram showing the anti-counterfeiting application of the polymer material in Example 9 of the present invention. DETAILED DESCRIPTION

[0065] The present invention is further described in detail below using specific examples. Unless otherwise specified, the raw materials, reagents, and apparatus used in the examples and comparative examples are available from conventional commercial sources or by conventional methods. Unless otherwise specified, all experimental or testing methods are conventional in the art.

[0066] Example 1

[0067] This example prepares the compound of formula II, and the specific process is as follows:

[0068]

[0069] Under an argon atmosphere, 5H-benzo[a]benzo[4,5]thieno[3,2-c]carbazole (0.20 g, 0.62 mmol) and sodium tert-butoxide (0.24 g, 2.48 mmol) were added sequentially to 20 mL of ultra-dry tetrahydrofuran. After stirring at room temperature for 30 minutes, iodomethane (1.00 mL) was added and the mixture was refluxed under condensation for 12 hours before quenching the reaction. After cooling the reaction solution to room temperature, the solvent was removed by rotary evaporation to obtain a crude product. The crude product was purified by silica gel column chromatography using a mixture of dichloromethane (DCM) and petroleum ether (PE) (v / v 2:1) as the developing solvent and reprecipitated from dichloromethane (DCM) / n-hexane to obtain a white powder (yield: 91.2%).

[0070] 1H NMR(600MHz,Chloroform-d)δ9.20–9.16(m,1H),8.85–8.79(m,2H),8.36(dt,J=7.8,0.9Hz,1H),8.07(ddd,J=7. 8,1.3,0.6Hz,1H),7.73(ddd,J=8.3,6.8,1.3Hz,1H),7.66–7.52(m,4H),7.49–7.41(m,2H),4.40(s,3H).ESI-MS m / z:[M]+calcd for C23H15NS+,338.0988; found,338.0998.

[0071] Example 2

[0072] This example prepares the compound of formula III, and the specific process is as follows:

[0073]

[0074] Under an argon atmosphere, 5H-benzo[a]benzo[4,5]thieno[3,2-c]carbazole (0.20 g, 0.62 mmol) and sodium hydride (0.59 g, 2.48 mmol) were added sequentially to 20 mL of ultra-dry tetrahydrofuran. After stirring at room temperature for 30 minutes, ethyl bromide (1.00 mL) was added and the mixture was refluxed under condensation for 12 hours before quenching the reaction. After cooling the reaction solution to room temperature, the solvent was removed by rotary evaporation to obtain a crude product. The crude product was purified by silica gel column chromatography using a mixture of dichloromethane (DCM) and petroleum ether (PE) (v / v 2:1) as the developing solvent and reprecipitated from dichloromethane (DCM) and n-hexane to obtain a white powder (yield: 83.7%).

[0075] 1 H NMR(600MHz,Chloroform-d)δ9.34–9.24(d,J=8.4Hz,1H),8.95–8.87(d,J=8.2Hz,1H),8 .79–8.71(m,1H),8.47–8.42(d,J=7.8Hz,1H),8.17–8.07(dd,J=7.8,1.1Hz,1H),7.84–7. 80(ddd,J=8.2,6.8,1.2Hz,1H),7.77–7.73(ddd,J=8.2,6.7,1.2Hz,1H),7.70–7.59(m,3 H),7.54–7.48(t,J=7.4Hz,2H),5.02–4.94(q,J=7.3Hz,2H),1.82–1.73(t,J=7.3Hz,3H).

[0076] 13 C NMR (151MHz, CDCl3) δ140.19,134.04,125.62,124.91,124.80,124.62,124.39,123.71, 123.23,122.98,122.35,121.54,121.24,120.38,113.75,109.15,41.01,15.16.ESI-MS m / z:[M]+calcd for C24H17NS+,352.10817; found,352.11581.

[0077] Example 3

[0078] This example prepares the compound of formula IV, and the specific process is as follows:

[0079]

[0080] Under an argon atmosphere, 5H-benzo[a]benzo[4,5]thieno[3,2-c]carbazole (0.20 g, 0.62 mmol) and sodium hydride (0.59 g, 2.48 mmol) were added sequentially to 20 mL of ultra-dry tetrahydrofuran. After stirring at room temperature for 30 minutes, n-propyl bromide (0.69 g, 5.61 mmol) was added and the mixture was refluxed for 12 hours before quenching the reaction. After cooling the reaction mixture to room temperature, the solvent was removed by rotary evaporation to obtain a crude product. The crude product was purified by silica gel column chromatography using a mixture of dichloromethane (DCM) and petroleum ether (PE) (v / v 2:1) as the developing solvent and reprecipitated from dichloromethane (DCM) and n-hexane to obtain a white powder (yield: 77.7%).

[0081] 1 H NMR(600MHz,Chloroformd)δ9.33–9.24(m,1H),8.93–8.85(d,J=8.3Hz,1H),8.77–8.64 (m,1H),8.51–8.38(m,1H),8.18–8.09(m,1H),7.83–7.79(ddd,J=8.3,6.8,1.3Hz,1H),7 .76–7.72(ddd,J=8.3,6.8,1.3Hz,1H),7.70–7.58(m,3H),7.54–7.47(dtd,J=7.8,6.7, 1.0Hz, 2H), 4.89–4.79 (m, 2H), 2.28–2.15 (h, J = 7.5Hz, 2H), 1.22–1.14 (t, J = 7.4Hz, 3H).

[0082] 13C NMR (151MHz, CDCl3) δ140.71,134.10,125.59,124.91,124.74,124.63,124.35 ,122.94,122.18,121.62,121.19,120.33,109.48,47.81,23.30,11.42.ESI-MS m / z:[M]+calcd for C25H19NS+,366.12382; found,366.13138.

[0083] Example 4

[0084] This example prepares the compound of formula V, and the specific process is as follows:

[0085]

[0086] Under an argon atmosphere, 5H-benzo[a]benzo[4,5]thieno[3,2-c]carbazole (0.20 g, 0.62 mmol) and sodium hydride (0.59 g, 2.48 mmol) were added sequentially to 20 mL of ultra-dry tetrahydrofuran. After stirring at room temperature for 30 minutes, butyl bromide (0.65 g, 4.74 mmol) was added and the mixture was refluxed for 12 hours before quenching the reaction. After cooling the reaction mixture to room temperature, the solvent was removed by rotary evaporation to obtain a crude product. The crude product was purified by silica gel column chromatography using a mixture of dichloromethane (DCM) and petroleum ether (PE) (v / v 2:1) as the developing solvent. The product was then reprecipitated from dichloromethane (DCM) and n-hexane to obtain a white powder (yield: 74.6%).

[0087] 1 H NMR(600MHz,Chloroformd)δ9.31–9.26(d,J=8.3Hz,1H),8.93–8.87(d,J=8.2Hz,1H),8.73–8.70(m,1H) ,8.47–8.42(d,J=7.7Hz,1H),8.14–8.10(m,1H),7.84–7.78(ddd,J=8.4,6.7,1.3Hz,1H),7.75–7.71(ddd ,J=8.3,6.7,1.2Hz,1H),7.69–7.62(m,2H),7.62–7.58(ddd,J=8.2,6.9,1.1Hz,1H),7.53–7.47(m,2H), 4.91–4.84(t,J=7.9Hz,2H),2.18–2.12(m,2H),1.66–1.58(q,J=7.5Hz,2H),1.11–1.07(t,J=7.4Hz,3H).

[0088] 13 C NMR (151MHz, CDCl3) δ140.65,134.10,125.59,124.91,124.73,124.63,124.32,123.72,12 3.23,123.00,122.22,121.63,121.20,120.32,109.44,46.11,32.06,20.34,13.93.ESI-MS m / z:[M]+calcd for C26H21NS+,380.13947; found.380.14694.

[0089] Example 5

[0090] This embodiment prepares a light-activated organic long-lasting glow material, and the specific process is as follows:

[0091] A compound of formula I (5H-benzo[a]benzo[4,5]thieno[3,2-c]carbazole) (0.50 mg, 0.0015 mmol), bisphenol A diglycidyl ether (1000.00 mg, 2.93 mmol) and 1,3-propylenediamine were placed in a 1.5 mL transparent sample tube; the mixture was sonicated at room temperature until clear and transparent, injected into a mold, and cured at 90° C. for 2 hours to obtain a polymer material with a molar fraction of the compound of formula I of 0.05%.

[0092] Example 6

[0093] This embodiment prepares a light-activated organic long-lasting glow material, and the specific process is as follows:

[0094] The compound of formula II prepared in Example 1 (5-methyl-benzo[a]benzo[4,5]thieno[3,2-c]carbazole) (0.50 mg, 0.0015 mmol), bisphenol A diglycidyl ether (1000.00 mg, 2.93 mmol) and 1,3-propylenediamine were placed in a 1.5 mL transparent sample tube; the above mixture was ultrasonicated at room temperature until clear and transparent, injected into a mold, and cured at 90° C. for 2 hours to obtain a polymer material with a molar fraction of the compound of formula II of 0.05%.

[0095] Example 7

[0096] This embodiment prepares a light-activated organic long-lasting glow material, and the specific process is as follows:

[0097] The compound of formula III prepared in Example 2 (5-ethyl-benzo[a]benzo[4,5]thieno[3,2-c]carbazole) (0.50 mg, 0.0015 mmol), bisphenol A diglycidyl ether (1000.00 mg, 2.93 mmol) and 1,3-propylenediamine were placed in a 1.5 mL transparent sample tube; the mixture was sonicated at room temperature until clear and transparent, injected into a mold, and cured at 90° C. for 2 hours to obtain a polymer material with a molar fraction of the compound of formula III of 0.05%.

[0098] Example 8

[0099] This embodiment prepares a light-activated organic long-lasting glow material, and the specific process is as follows:

[0100] The compound of formula IV (5-n-propyl-benzo[a]benzo[4,5]thieno[3,2-c]carbazole) prepared in Example 3 (0.50 mg, 0.0014 mmol), bisphenol A diglycidyl ether (1000.00 mg, 2.93 mmol) and 1,3-propylenediamine were placed in a 1.5 mL transparent sample tube; the above mixture was ultrasonicated at room temperature until clear and transparent, injected into a mold, and cured at 90° C. for 2 hours to obtain a polymer material with a molar fraction of the compound of formula IV of 0.05%.

[0101] Example 9

[0102] This embodiment prepares a light-activated organic long-lasting glow material, and the specific process is as follows:

[0103] The compound of formula V (5-n-butyl-benzo[a]benzo[4,5]thieno[3,2-c]carbazole) (0.50 mg, 0.0014 mmol) prepared in Example 4, bisphenol A diglycidyl ether (1000.00 mg, 2.93 mmol) and 1,3-propylenediamine were placed in a 1.5 mL transparent sample tube; the above mixture was sonicated at room temperature until clear and transparent, injected into a mold, and cured at 90° C. for 2 hours to obtain a polymer material with a molar fraction of the compound of formula V of 0.05%.

[0104] According to the preparation methods of Examples 5 to 9, the amounts of the compounds of Formula I to Formula V were adaptively adjusted so that the molar fractions of the compounds of Formula I to Formula V in the polymer material were 0.01%, 0.1%, 0.5%, and 1.0%, respectively.

[0105] Test example

[0106] Figures 1 to 5 The H NMR spectra shown confirm the structures of the compounds of Formulas I, II, III, IV, and V and the purity of the samples.

[0107] The materials prepared in Examples 5-9 were subjected to performance testing, primarily examining their photoactivation performance and long-lasting luminescence performance. Luminescence performance tests were conducted on an Edinburgh FLS980 steady-state transient fluorescence spectrometer with an integrating sphere and an Ocean Optics QE65 Pro CCD fiber spectrometer. The test results are shown in Table 1 below.

[0108] Table 1

[0109]

[0110]

[0111] The relationship diagram between the illumination time and afterglow intensity of the polymer materials in Examples 5 to 9, the steady-state spectrum before and after light activation, the delayed spectrum after light activation, the room temperature phosphorescence decay curve before and after light activation, the luminescence and afterglow photos before and after activation under 365nm ultraviolet light, the photoactivated long afterglow luminescence and its deactivation process cycle, the anti-counterfeiting application demonstration, etc. are shown in the figures respectively.

[0112] Depend on Figures 6-7 It can be seen that the long afterglow materials prepared in Examples 5 to 9 do not have the property of ultra-long-life phosphorescent emission in the powder state, and their lifetimes are all below 10ms. Figures 8-9 After activation with 330nm UV light for 90 to 720 seconds, the prepared materials all produced significant long-lasting luminescence, with afterglow lifetimes reaching up to 0.87 seconds and efficiencies reaching up to 53.3%. Furthermore, the wavelength, lifetime, and efficiency of the long-lasting luminescence can be tuned by varying the doped guest molecules.

[0113] Depend on Figures 10-11 It can be seen that the organic long-afterglow material prepared in Example 9, after being activated by light, can be restored to a state without long-afterglow luminescence by heating in an air atmosphere at 90-120°C for 6-45 minutes and then cooling to room temperature. Furthermore, the activation and deactivation process can be repeated multiple times. After 10 cycles, the polymer film still maintained a lifespan comparable to that of the initial activation, still at 0.85 seconds.

[0114] Depend on Figure 12 It can be seen that by utilizing the reversible light-activated long-afterglow luminescence characteristics of the material prepared in Example 9, the desired afterglow luminescence pattern can be clearly printed on the material using light. Moreover, different patterns can be easily reprinted or different information can be written after thermal erasure (deactivation), thereby realizing optical printing and erasing functions. It should be noted that the pattern is invisible under ambient light and only appears in the form of afterglow luminescence after ultraviolet light excitation and removal of the excitation source. These results show that the prepared long-afterglow material has strong practicality in the fields of optical printing, anti-counterfeiting, information encryption, etc.

[0115] In summary, in the embodiments of the present invention, using compounds of Formula I to Formula V as guests and epoxy resin as the host, the polymer luminescent material prepared by physical doping can emit afterglow with long lifetime, high quantum yield, and good stability in air at room temperature. The unique long afterglow luminescence properties of the prepared material can also be used to achieve functions such as anti-counterfeiting and information encryption. Thus, the prepared epoxy resin-based material doped with heteroatom-containing aromatic organic compounds has advantages such as long afterglow luminescence lifetime, high quantum yield, and good performance stability, and can be used in fields such as anti-counterfeiting, information encryption, functional inks, and road marking.

[0116] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A light-activated organic long-afterglow material, characterized in that: The invention comprises a host component and a guest component doped in the host component, wherein the guest component comprises a compound of formula 1: The compound of formula 1 is selected from at least one of the following compounds: 、 ; The main component includes epoxy polymer; the epoxy polymer is formed by polymerization of bisphenol A diglycidyl ether and a curing agent; The mass fraction of the guest molecule is 0.1% to 1%.

2. The light-activated organic long afterglow material according to claim 1, characterized in that: The preparation method of the light-activated organic long afterglow material comprises the following steps: mixing and stirring bisphenol A diglycidyl ether, a guest component and a curing agent, and curing to obtain the light-activated organic long afterglow material.

3. The light-activated organic long afterglow material according to claim 2, characterized in that: The curing temperature is 20-120°C.

4. The light-activated organic long afterglow material according to claim 2, wherein: The curing time is 0.5 to 48 hours.

5. Use of the light-activated organic long afterglow material according to any one of claims 1 to 4 in data encryption and / or anti-counterfeiting and / or functional inks and / or road markings.

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