Dynamic phosphorescent material with high light stability and long service life as well as preparation method and application thereof

Abstract

The invention discloses a dynamic phosphorescent material with high light stability and long service life as well as a preparation method and application thereof, the material has a compound structure as shown in a formula (I): Y1-X-Y2, in the formula (I),-X is selected from the formula (I),-Y1 is selected from any one of the following groups:-OCH3,-OC2H5,-OC3H7,-OC4H9 and-OC5H11, in the formula (I),-X-Y2 is selected from any one of the following groups:-OCH3,-OC2H5,-OC3H7,-OC4H9 and-OC5H11. -Y2 is selected from any one of the following groups: R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are respectively and independently selected from any one of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The light stability of the obtained dynamic phosphorescent material under long-time irradiation can reach 96% at most, the dynamic phosphorescent material has good free radical scavenging capacity, excellent light stability is achieved, and a film prepared from the material has the properties of being high in machinability and colorful and is effectively applied to flexible long-afterglow pattern display.

Description

Technical Field

[0001] The present invention belongs to the technical field of phosphorescent materials, and in particular relates to a dynamic phosphorescent material with high photostability and long life, and a preparation method and application thereof. Background Art

[0002] Room-temperature phosphorescent (RTP) materials have attracted widespread attention due to their unique excited-state properties, tunable luminescence lifetimes, large Stokes shifts, and efficient exciton utilization. These materials have broad application prospects in fields such as information storage encryption, organic light-emitting diodes, bioimaging, and display lighting. In recent years, stimuli-responsive room-temperature phosphorescent materials have attracted much attention due to their unique optical properties. The phosphorescence properties of these materials can be dynamically changed through continuous ultraviolet (UV) light stimulation, pH changes, stress, or thermal stimulation, thereby greatly expanding the design space for functionalized RTP materials. Photoresponsive RTP materials have broad application prospects because they can remotely control their optical properties in a non-invasive manner, have high spatiotemporal precision, and can achieve the dynamic process of phosphorescence without destroying the intrinsic structure of the material.

[0003] Currently, photoresponsive RTP materials can respond specifically to oxygen or the external environment under continuous UV light irradiation, resulting in dynamic changes in color, lifetime, and intensity. However, the stability of phosphorescence emission from these materials under continuous light irradiation is poor, and current methods for regulating phosphorescence stability are relatively limited. Summary of the Invention

[0004] The purpose of the present invention is to solve the above problems and provide a dynamic phosphorescent material with high photostability and long life.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned dynamic phosphorescent material with high photostability and long lifespan.

[0006] Another object of the present invention is to provide a film made of the above-mentioned dynamic phosphorescent material, as well as the application of the material in multi-dimensional information encryption, flexible display, and luminescence-time dependent intelligent coding systems.

[0007] The object of the present invention is achieved in the following ways:

[0008] A dynamic phosphorescent material with high photostability and long lifespan, wherein the compound material has a structure shown in formula (I):

[0009] Y1-X-Y2

[0010] Formula (I)

[0011] In formula (I), the -X- is selected from

[0012] In formula (I), the -Y1 is selected from any one of the following groups:

[0013] ---OCH3, ---OC2H5, ---OC3H7, ---OC4H9, ---OC5H 11 、---OC6H 13 、

[0014]

[0015] In formula (I), the -Y2 is selected from any one of the following groups:

[0016]

[0017] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 are each independently selected from any one of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;

[0018] The above dotted lines represent the insertion sites of the groups and -X-.

[0019] Preferably, the above-mentioned dynamic phosphorescent material with high photostability and long life has a structure shown in formula (I):

[0020] Y1-X-Y2 formula (I)

[0021] In formula (I), the -X- is selected from

[0022] In formula (I), the -Y1 is selected from any one of the following groups:

[0023] ---OCH3,

[0024] The -Y2 is selected from any one of the following groups:

[0025]

[0026] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 Each is independently selected from a hydrogen atom and a bromine atom.

[0027] More preferably, the dynamic phosphorescent material with high photostability and long life is Compound 1, Compound 2 or Compound 3, and its structure is shown in the following formula:

[0028]

[0029] The preparation steps of the above compound are as follows:

[0030] 9H-carbazole and n-butyl lithium were added to a reaction flask using tetrahydrofuran as a solvent. After the reaction to obtain a precipitate, the precipitate was reacted with 2,4-dichloro-6-phenyl-1,3,5-triazine. The reaction product was washed with acetone and dried. The dried product, sodium, and methanol were weighed and reacted using tetrahydrofuran as a solvent. After the reaction, compound 1 was obtained by column chromatography.

[0031] Alternatively, 7H-benzo[c]carbazole and n-butyllithium are added to a reaction flask using tetrahydrofuran as a solvent, and a precipitate is obtained by reaction. The precipitate is reacted with 2,4-dichloro-6-phenyl-1,3,5-triazine, and the reaction product is washed with acetone and dried. The dried product, sodium, and methanol are weighed and reacted using tetrahydrofuran as a solvent. After the reaction, compound 2 is obtained by column chromatography.

[0032] Alternatively, 7H-dibenzo[c,g]carbazole and n-butyllithium are added to a reaction flask using tetrahydrofuran as a solvent, and a precipitate is obtained by reaction. The precipitate is reacted with 2,4-dichloro-6-phenyl-1,3,5-triazine, and the reaction product is washed with acetone and dried. The dried product, sodium, and methanol are weighed and reacted using tetrahydrofuran as a solvent. After the reaction is completed, compound 3 is obtained by column chromatography.

[0033] Preferably, the molar ratio of 9H-carbazole, 7H-benzo[c]carbazole or 7H-dibenzo[c,g]carbazole, n-butyllithium, and 2,4-dichloro-6-phenyl-1,3,5-triazine is 1-1.1:1.1-1.3:1-1.1.

[0034] Preferably, the molar ratio of the dried product, sodium, and methanol is in the range of 1-1.1: 1.1-1.2: 1.5-1.8.

[0035] The composite film is prepared by the following method using the above compound materials:

[0036] The compound, polymethyl methacrylate, and butylated hydroxytoluene are weighed and mixed thoroughly with dichloromethane as a solvent, stirred, and ultrasonically treated. The stirred mixture is then slowly poured into a flat-bottomed glass container and allowed to stand at room temperature to completely evaporate the solvent. Finally, the film is demolded from the flat-bottomed glass container under liquid nitrogen to obtain a composite film. The mass ratio of the compound, polymethyl methacrylate, and butylated hydroxytoluene is preferably 1:10:1.8-4. The volume ratio of dichloromethane to compound weight is 0.5 ml / mg. The compound is preferably compound 1, 2, or 3 described above.

[0037] The high light stability long-life dynamic phosphorescent material can be applied in multi-dimensional information encryption, flexible display or light-time-dependent intelligent coding system.

[0038] The application can also prepare an array structure-based smart color developing device based on the above-mentioned film, realize dynamic color regulation under multi-mode light response by independently coding each array site and integrating film samples with differentiated light emission characteristics, and finally realize visual optical information storage and reading function.

[0039] Compared with the prior art, the application has the following beneficial effects:

[0040] (1) The application provides a phosphorescent molecular material, a synthesis method and a high stability long-life dynamic phosphorescent film with simple process and low cost. The application first regulates the light stability of the phosphorescent material, and the light stability can be up to 96% under long-time irradiation.

[0041] (2) The dynamic phosphorescent material prepared by the application has good free radical scavenging capacity, can effectively scavenge active oxygen generated by the reaction of triplet excitons and oxygen by butylated hydroxytoluene, interrupt the photo-oxidation process of phosphorescent molecules initiated by the active oxygen, and thus realize excellent light stability.

[0042] (3) The application prepares an information encryption system based on the high stability phosphorescent film, which can display light emission of different modules under different ultraviolet light irradiation times, so as to display different encrypted information.

[0043] (4) The film synthesized by the application has strong processability and colorful properties, and can be applied to flexible long-afterglow pattern display. BRIEF DESCRIPTION OF DRAWINGS

[0044] Fig. 1(a) is a fluorescence and phosphorescence spectrum of a film prepared based on compound 2;

[0045] Fig. 1(b) is the phosphorescence stability of the film prepared based on compound 2 under continuous light irradiation;

[0046] Fig. 1(c) is the phosphorescence lifetime of the film after light irradiation for 30 s and 10 min;

[0047] Fig. 2(a) is a long-afterglow photo of the film based on compound 2 under different ultraviolet light irradiation times;

[0048] Fig. 2(b) is the phosphorescence intensity under 10 ultraviolet light irradiation cycles, and 1500 s is one light irradiation cycle.

[0049] Fig. 3(a) is an information encryption system prepared based on the film of compound 2;

[0050] Fig. 3(b) is a high light stability dynamic afterglow writing and erasing device prepared based on the film of compound 2;

[0051] Figure 3(c) Flexible long afterglow display system prepared based on thin films of compounds 1, 2, 3.

[0052] Figure 3(d) Smart color revealing device prepared based on thin films of compounds 1, 2, 3.

[0053] Figure 4 Phosphorescence stability of compound 2, 1% butylated hydroxyl toluene composite thin film under continuous light.

[0054] Figure 5 NMR of compound 1, hydrogen spectrum.

[0055] Figure 6 NMR of compound 1, carbon spectrum.

[0056] Figure 7 NMR of compound 2, hydrogen spectrum.

[0057] Figure 8 NMR of compound 2, carbon spectrum.

[0058] Figure 9 NMR of compound 3, hydrogen spectrum.

[0059] Figure 10 NMR of compound 3, carbon spectrum. DETAILED DESCRIPTION

[0060] The application will now be further described in connection with the following examples, figures and potential applications. These examples are provided to more fully demonstrate the application and are not intended to limit the scope of the application. To those skilled in the art, it will be readily apparent that other useful embodiments of the present application can be realized from the teachings herein.

[0061] Example 1

[0062]

[0063] 9H-carbazole (2 g, 0.012 mol) was added to a reaction flask, followed by the slow addition of 30 mL of tetrahydrofuran (THF). Then, n-butyllithium (5.2 mL, a 2.5 mol / L n-hexane solution) was slowly added at 273 K. The mixture was stirred at 298 K for 4 h, resulting in the formation of a large amount of precipitation. A separate reaction flask was prepared, and 2,4-dichloro-6-phenyl-1,3,5-triazine (2.7 g, 0.012 mol) was added. 30 mL of THF was slowly added, and the previous precipitate was slowly transferred to this reaction flask at 273 K. The mixture was then stirred at 298 K for 4 h. The reaction product was washed three times with acetone and dried to obtain 9-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (2.8 g, 64%). Sodium (0.12 g, 0.005 mol) was added to a reaction flask, followed by the slow addition of methanol (0.18 g, 0.005 mol) and stirring at 298 K for 30 min to obtain a clear sodium methoxide solution. 9-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (1.97 g, 0.005 mol) was added to a reaction flask, followed by the addition of 30 mL of THF and stirring for 30 min. Sodium methoxide was added to the reaction flask and the reaction was continued at 298 K for 30 min. Compound 1 was obtained by column chromatography. 1 HNMR (400MHz, CDCl3, ppm): δ9.09 (d, J = 8.4Hz, 2H), 8.61 (d, J = 2.8Hz, 2H), 8.06 (d, J = 7.6Hz, 2H), 7.64-7.54 (m, 5H), 7.42 (t, J = 7.6Hz), 4.30 (s, 3H). 13 CNMR (100MHz, CDCl3, ppm): δ174.3,171.8,166.0,139.1,135.8,132.9,129.2,128.9,127.2,126.8,123.5,119.8,118.2,55.5.

[0064] Example 2

[0065]

[0066] 7H-Benzo[c]carbazole (2 g, 0.009 mol) was added to a reaction flask, followed by the slow addition of 30 mL of tetrahydrofuran (THF). Then, n-butyllithium (4 mL, a 2.5 mol / L solution in n-hexane) was slowly added at 273 K. The mixture was stirred at 298 K for 4 h, resulting in the formation of a large amount of precipitation. A separate reaction flask was prepared, and 2,4-dichloro-6-phenyl-1,3,5-triazine (2.7 g, 0.012 mol) was added. 30 mL of THF was slowly added, and the precipitate from the previous reaction at 273 K was slowly transferred to this flask. The mixture was stirred at 298 K for 4 h. The reaction product was washed three times with acetone and dried to yield 7-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-7H-benzo[c]carbazole (2.1 g, 57%). Sodium (0.12 g, 0.005 mol) was weighed and added to a reaction flask. Methanol (0.18 g, 0.005 mol) was slowly added and stirred at 298 K for 30 min to obtain a clear sodium methoxide solution. 7-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-7H-benzo[c]carbazole (2 g, 0.005 mol) was weighed and added to a reaction flask. 30 mL of THF was added and stirred for 30 min. Sodium methoxide was added to the reaction flask and the mixture was reacted at 298 K for 30 min. Compound 2 was obtained by column chromatography. 1 H NMR (400MHz, CDCl3, ppm): δ9.23 (d, J = 9.2Hz, 1H), 9.14 (d, J = 8.4Hz, 1H), 8.86 (d, J = 8.4Hz, 1H), 8.64-8. 61(m,3H),8.03(d,J=8Hz,1H),7.97(d,J=9.2Hz,1H),7.75-7.73(m,1H),7.67-7.51(m,6H),4.30(s,3H). 13 C NMR (100MHz, CDCl3, ppm): δ174.2,171.5,165.5,138.7,137.3,135.6,133.1,130.9,129.3, 129.1,128.9,127.9,127.2,127.1,125.8,124.6,123.8,122.0,119.7,117.6,117.4,54.8.

[0067] Example 3

[0068]

[0069] 7H-dibenzo[c,g]carbazole (3 g, 0.013 mol) was added to a reaction flask, followed by the slow addition of 30 mL of tetrahydrofuran (THF). Then, n-butyllithium (5.78 mL, a 2.5 mol / L solution in n-hexane) was slowly added at 273 K. The mixture was stirred at 298 K for 4 h, resulting in the formation of a large amount of precipitation. A separate reaction flask was prepared, and 2,4-dichloro-6-phenyl-1,3,5-triazine (2.7 g, 0.012 mol) was added. 30 mL of THF was slowly added, and the precipitate from the previous reaction at 273 K was slowly transferred to this flask. The mixture was stirred at 298 K for 4 h. The reaction product was washed three times with acetone and dried to yield 7-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-7H-dibenzo[c,g]carbazole (3.1 g, 68%). Sodium (0.12 g, 0.005 mol) was weighed and added to a reaction flask. Methanol (0.18 g, 0.005 mol) was slowly added and stirred at 298 K for 30 min to obtain a clear sodium methoxide solution. 7-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-7H-dibenzo[c,g]carbazole (2.28 g, 0.005 mol) was weighed and added to a reaction flask. 30 mL of THF was added and stirred for 30 min. Sodium methoxide was added to the reaction flask and the reaction was continued at 298 K for 30 min. Compound 3 was obtained by column chromatography. 1 H NMR (400MHz, CDCl3, ppm): δ9.14(d,J=9.2Hz,2H),9.06(d,J=8.4Hz,2H),8.66-8.64(m,2H),8 .05(d,J=8Hz,2H),7.99(d,J=9.2Hz,2H),7.67-7.64(m,3H),7.62-7.56(m,4H),4.31(s,3H). 13 C NMR (100MHz, CDCl3, ppm): δ174.2,171.9,166.3,136.9,135.4,133.1,131.3, 129.2,128.8,128.7,128.0,127.3,126.1,125.2,124.6,121.4,116.6,55.0.

[0070] Example 4

[0071] A composite film was prepared based on compound 1. The specific preparation steps are as follows:

[0072] First, compound 1 (10 mg), polymethyl methacrylate (100 mg), butylated hydroxyl toluene (25.1 mg) were weighed into a transparent sample bottle, dichloromethane (5 mL) was added into the bottle, a magnetic stirrer was added to stir for 30 min and further ultrasonic treatment for 5 min to mix them well. Then the stirred mixture sample was slowly poured into a glass culture dish, and placed at room temperature for 12 h to completely evaporate the solvent. Finally, the sample was demolded from the glass culture dish at 77 K liquid nitrogen to obtain a composite film.

[0073] Example 5

[0074] The preparation method of the composite film of compound 2 is the same as that of Example 4, except that the amount of butylated hydroxyl toluene is 21.8 mg.

[0075] The fluorescence and phosphorescence spectra of the film prepared based on compound 2 show green phosphorescence emission, as shown in Figure 1(a); the phosphorescence stability of the film under continuous light, the phosphorescence intensity is maintained at 96% under 1500 s light, the calculation method is: the highest phosphorescence intensity that can be reached within 1500 s light is 6876 Counts, and the phosphorescence intensity of the film after 1500 s light is 6601 Counts, as shown in Figure 1(b); the phosphorescence lifetime of the film after 30 s and 10 min of light, which proves its lifetime stability, as shown in Figure 1(c). The afterglow photos of the film based on compound 2 under different ultraviolet light irradiation times prove the high stability of its phosphorescence, as shown in Figure 2(a); the phosphorescence intensity under 10 ultraviolet light irradiation cycles, 1500 s is one light irradiation cycle. See Figure 2(b).

[0076] Example 6

[0077] The preparation method of the composite film of compound 3 is the same as that of Example 4, except that the amount of butylated hydroxyl toluene is 19.4 mg.

[0078] Example 7 Information encryption display based on compound 2 composite film

[0079] The composite films with fluorescence and phosphorescence properties are assembled into the required encrypted information at different sites, and different encrypted patterns are displayed under the condition of ultraviolet light being turned on for 30 s and turned off for 15 min, showing the application prospect of time-resolved information encryption materials. The information encryption system based on compound 2 film displays different encrypted information under different light irradiation times, as shown in Figure 3(a);

[0080] Example 8 High light stability afterglow display device based on compound 2 composite film

[0081] Composite films based on Compound 2 were embedded in various display patterns. Upon activation with UV light, the corresponding persistent patterns appeared. These patterns could be effectively erased after being exposed to air for one hour. Furthermore, they maintained high display clarity and brightness even after prolonged erase / write cycles. Figure 3(b) shows a highly light-stable dynamic persistent write / erase device fabricated from a Compound 2 film, which maintains high luminescence intensity even under continuous illumination.

[0082] Example 9: Multi-color afterglow display device based on composite thin film of compounds 1, 2, and 3

[0083] Composite films based on compounds 1, 2, and 3 can exhibit colorful afterglow emissions from blue, green, and orange-red light, respectively. When the corresponding films are formed and integrated into the same display pattern, bright colorful afterglow petals appear after the ultraviolet light is turned off, as shown in Figure 3(c).

[0084] Example 10: Multi-color afterglow display device based on composite thin film of compounds 1, 2, and 3

[0085] Thin films based on compounds 1, 2, and 3 before and after incorporation with butylated hydroxytoluene (BHT) were integrated into a display array in the following order: Compound 3 incorporated with BHT, Compound 1 incorporated with BHT, Compound 2 incorporated with BHT, Compound 3 incorporated with BHT, Compound 1, Compound 2 incorporated with BHT, Compound 2, Compound 2, Compound 1. A time-based light intensity sensor was coupled to the array. Due to differences in the photostability of the composite films after incorporation with BHT, different sites exhibited distinct color development behaviors under varying UV illumination durations. A precise correspondence was established between these and pre-designed digital codes. By analyzing the dynamic mapping between color signals and digital codes, visual optical information storage and readout was achieved. An intelligent encoding system for the phosphorescence-time-variation detection module was also constructed. This system implemented dynamic signal analysis using an experimentally calibrated linear attenuation model and effectively converted it into a corresponding binary signal, ultimately achieving command output. Applications for multidimensional information storage and conversion were demonstrated. Figure 3(d) shows an intelligent colorimetric device fabricated from thin films of compounds 1, 2, and 3, which was applied to multidimensional information storage and command signal display.

[0086] Comparative Example 1: Light stability of composite films based on compound 2 at different contents of butylated hydroxytoluene

[0087] With other conditions unchanged, the composite film preparation method based on Compound 2 was the same as in Example 4, except that the butylated hydroxytoluene content was reduced to 0.06 mg. The resulting film exhibited poor phosphorescence stability under continuous illumination, with the phosphorescence intensity decreasing to 29% after 1500 seconds of illumination. The calculation method was as follows: the maximum phosphorescence intensity achieved within 1500 seconds of illumination was 7449 counts, and the phosphorescence intensity of the film after 1500 seconds of illumination was 2160 counts.

Claims

1. A dynamic phosphorescent material with high photostability and long life, characterized in that: The material has a structure shown in formula (I): Y1-X-Y2 Formula (I) In formula (I), the -X- is selected from In formula (I), the -Y1 is selected from any one of the following groups: ---OCH3, ---OC2H5, ---OC3H7, ---OC4H9, ---OC5H 11 、---OC6H 13 In formula (I), the -Y2 is selected from any one of the following groups: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 Each is independently selected from any one of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

2. The dynamic phosphorescent material with high photostability and long life according to claim 1, characterized in that: The -X- is selected from In formula (I), the -Y1 is selected from any one of the following groups: ---OCH3、 The -Y2 is selected from any one of the following groups: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 Each is independently selected from a hydrogen atom and a bromine atom.

3. The dynamic phosphorescent material with high photostability and long life according to claim 1, characterized in that: The material structure is shown in the following formula:

4. A method for preparing the dynamic phosphorescent material with high photostability and long life according to claim 3, characterized in that The method comprises the following steps: 9H-carbazole and n-butyl lithium were added to a reaction flask using tetrahydrofuran as a solvent. After the reaction to obtain a precipitate, the precipitate was reacted with 2,4-dichloro-6-phenyl-1,3,5-triazine. The reaction product was washed with acetone and dried. The dried product, sodium, and methanol were weighed and reacted using tetrahydrofuran as a solvent. After the reaction, compound 1 was obtained by column chromatography. Alternatively, 7H-benzo[c]carbazole and n-butyllithium are added to a reaction flask using tetrahydrofuran as a solvent, and a precipitate is obtained by reaction. The precipitate is reacted with 2,4-dichloro-6-phenyl-1,3,5-triazine, and the reaction product is washed with acetone and dried. The dried product, sodium, and methanol are weighed and reacted using tetrahydrofuran as a solvent. After the reaction, compound 2 is obtained by column chromatography. Alternatively, 7H-dibenzo[c,g]carbazole and n-butyllithium are added to a reaction flask using tetrahydrofuran as a solvent, and a precipitate is obtained by reaction. The precipitate is reacted with 2,4-dichloro-6-phenyl-1,3,5-triazine, and the reaction product is washed with acetone and dried. The dried product, sodium, and methanol are weighed and reacted using tetrahydrofuran as a solvent. After the reaction is completed, compound 3 is obtained by column chromatography.

5. The method for preparing a dynamic phosphorescent material with high photostability and long life according to claim 4, characterized in that The molar ratio of 9H-carbazole, 7H-benzo[c]carbazole or 7H-dibenzo[c,g]carbazole, n-butyl lithium and 2,4-dichloro-6-phenyl-1,3,5-triazine is 1-1.1: 1.1-1.3: 1-1.

1.

6. The method for preparing a dynamic phosphorescent material with high photostability and long life according to claim 4, characterized in that The molar ratio of the dried product, sodium and methanol is 1-1.1:1.1-1.2:1.5-1.

8.

7. Use of the dynamic phosphorescent material with high photostability and long lifespan as claimed in claim 1 in multi-dimensional information encryption, flexible display or luminescence-time dependent intelligent coding system.

8. A composite film containing a dynamic phosphorescent material with high photostability and long life, characterized in that The dynamic phosphorescent material according to claim 1 is prepared by the following method: The compound, polymethyl methacrylate, and butylated hydroxytoluene were weighed, and dichloromethane was used as a solvent. The mixture was stirred and ultrasonically treated to mix them evenly. The stirred mixture was then slowly poured into a flat-bottomed glass container and allowed to stand at room temperature to completely evaporate the solvent. Finally, the mold was demolded from the flat-bottomed glass container under liquid nitrogen conditions.

9. The composite film containing a dynamic phosphorescent material with high photostability and long life according to claim 8, characterized in that The mass ratio of the compound 1 or 2 or 3, polymethyl methacrylate and butylated hydroxytoluene is 1:10:1.8-4.

10. An intelligent color display device based on an array structure, characterized in that Comprising the composite film according to claim 8.

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