Organic long-afterglow material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic materials, and discloses an organic long-afterglow material as well as a preparation method and application thereof. The invention discloses application of the compound shown in the formula (I) in an organic long-afterglow material. # imgabs0 #, formula (I); wherein R is selected from deuterium, H, C1-C20 alkyl or C3-C20 cycloalkyl. The compound shown in the formula (I) serves as a guest molecule to be applied to the organic long-afterglow material, the organic long-afterglow material has no afterglow property, a substance containing melamine formaldehyde resin serves as a subject component of the organic long-afterglow material, and after guest doping is conducted, the obtained organic long-afterglow material has stable long-afterglow performance; the organic long-afterglow material can effectively resist the phosphorescence quenching behavior of oxygen to guest molecules, the afterglow color changes from orange to red or dark red after illumination under the aerobic condition, the color change has good reversibility, the afterglow color does not change before and after illumination under the anaerobic condition, and the afterglow color changes from red to red or dark red after illumination under the oxygen-free condition. Therefore, the method can be used for oxygen detection.

Description

Technical Field

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

[0002] Long afterglow materials can continue to emit light after the excitation source stops. This property enables them to effectively eliminate the influence of short-lived background light, thereby significantly improving the clarity and recognizability of the luminescent signal. Therefore, this type of material is widely used in bioimaging, chemical sensing, information encryption, display devices and other fields. Traditionally, long afterglow materials are mainly composed of inorganic components. Inorganic long afterglow materials have excellent performance, but have defects such as high production costs and toxic materials. In contrast, organic room temperature phosphorescent materials have the characteristics of flexible structural design, easy processing and modification, good biocompatibility and dynamic color adjustment, and are gradually replacing traditional long afterglow materials.

[0003] Stimulus-responsive smart long afterglow materials have received widespread attention in recent years. Among them, photoresponsive materials are widely used because of their unique properties and ability to achieve light-induced afterglow color changes. Specifically, (1) photophosphorescent color-changing materials can achieve multi-dimensional regulation of color, time, and space, which makes them have potential application value in the fields of advanced data encryption and multi-color photonic barcode design; (2) they can be used to design multi-color photonic barcodes for advanced data encryption, as well as information storage media with three-dimensional ultra-high information storage capacity, showing good application prospects in the fields of information storage and encryption; (3) they can be used to realize optical waveguides, thereby playing a role in optical communication technology; (4) they can be added to clothing or architectural coatings to enhance beauty and bring fun to life, or used in eyeglass lenses to intelligently adjust photosensitivity and protect eyes from strong light damage; (5) they have ultra-long luminescence lifetime and have potential application value in the fields of luminescent display and sensors; (6) they have good reversibility and cyclic stability, and have long service life and reliability in practical applications; (7) they can be used as smart materials to respond to external light stimulation and achieve intelligent and controllable changes in optical properties; (8) they have time-dependent color-changing phosphorescence, which provides new tools and new opportunities for multi-level encryption and dynamic storage of information.

[0004] In environments such as anaerobic experiments where strict control of gas composition is required, the presence of oxygen may change the reaction path and reaction rate, etc. Visual monitoring of oxygen and qualification testing of anaerobic devices are essential. The light-induced afterglow color change characteristics of photoresponsive materials are one way to achieve visual monitoring of oxygen, but current phosphorescent materials are easily quenched by oxygen, which greatly affects the accuracy of the test results. Summary of the invention

[0005] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, one of the purposes of the present invention is to provide the use of the compound of formula (I) in an organic long afterglow material; the second purpose of the present invention is to provide an organic long afterglow material; the third purpose of the present invention is to provide a method for preparing the organic long afterglow material; the fourth purpose of the present invention is to provide a polymer film; the fifth purpose of the present invention is to provide an organic long afterglow material, or the use of a polymer film.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is: The first aspect of the present invention provides the use of a compound represented by formula (I) in an organic long afterglow material; , formula (I); Wherein, R is selected from deuterium, H, C1-C 20 Alkyl or C3-C 20 Cycloalkyl.

[0007] In some embodiments of the present invention, the compound represented by formula (I) is selected from at least one of the following compounds: , .

[0008] The second aspect of the present invention provides an organic long afterglow material, comprising a main component and guest molecules doped in the main component; the guest molecules include the compound of formula (I) described in the first aspect of the present invention.

[0009] In some embodiments of the present invention, in the organic long afterglow material, the mass fraction of the guest molecule is 0.001%-5%.

[0010] In some embodiments of the present invention, the main component includes melamine formaldehyde resin.

[0011] In the present invention, melamine formaldehyde resin is used as the main component of the organic long afterglow material, and its cross-linked structure can effectively prevent the phosphorescence quenching behavior of oxygen on guest molecules, so that the organic long afterglow material has stable long afterglow performance in the presence of oxygen.

[0012] In some embodiments of the present invention, the organic long afterglow material comprises the following preparation raw materials: a guest molecule solution and a melamine formaldehyde resin prepolymer solution.

[0013] In some embodiments of the present invention, the guest molecule solution includes guest molecules and an organic solvent.

[0014] In some embodiments of the present invention, the organic solvent is selected from one of tetrahydrofuran, methanol, ethanol, acetone, dimethyl sulfoxide, N,N-dimethylformamide, and acetonitrile.

[0015] In some specific embodiments of the present invention, the organic solvent is tetrahydrofuran.

[0016] In some embodiments of the present invention, the concentration of the guest molecules in the guest molecule solution is 1-4 mg / mL.

[0017] In some specific embodiments of the present invention, the concentration of the guest molecule in the guest molecule solution is 1-2 mg / mL In some embodiments of the present invention, the melamine formaldehyde resin prepolymer solution is prepared by heating a melamine and formaldehyde aqueous solution.

[0018] In some embodiments of the present invention, the concentration of the formaldehyde aqueous solution is 30-40 wt %.

[0019] In some specific embodiments of the present invention, the concentration of the formaldehyde aqueous solution is 35-40wt%.

[0020] In some embodiments of the present invention, the solid-to-liquid ratio of the melamine to formaldehyde aqueous solution is (110-130) mg: 1 mL.

[0021] In some specific embodiments of the present invention, the solid-to-liquid ratio of the melamine to formaldehyde aqueous solution is (115-125) mg: 1 mL.

[0022] In some embodiments of the present invention, in the preparation of the melamine formaldehyde resin prepolymer solution, the heating temperature is 80-110°C.

[0023] In some specific embodiments of the present invention, in the preparation of the melamine formaldehyde resin prepolymer solution, the heating temperature is 90-100°C.

[0024] In some embodiments of the present invention, in the preparation of the melamine formaldehyde resin prepolymer solution, the reaction time is 1-4 hours.

[0025] In some specific embodiments of the present invention, in the preparation of the melamine formaldehyde resin prepolymer solution, the reaction time is 1-3 hours.

[0026] In some embodiments of the present invention, the pH value of the melamine formaldehyde resin prepolymer solution is 8-10.

[0027] In some specific embodiments of the present invention, the pH value of the melamine formaldehyde resin prepolymer solution is 8-9.

[0028] In some embodiments of the present invention, the pH value of the melamine formaldehyde resin prepolymer solution is adjusted by adding at least one of amines, alkali metal hydroxides and alkali metal carbonates.

[0029] In some specific embodiments of the present invention, the pH value of the melamine formaldehyde resin prepolymer solution is adjusted by adding at least one of diethylamine, triethylamine, triethanolamine, sodium hydroxide, potassium hydroxide and sodium carbonate.

[0030] The third aspect of the present invention provides a method for preparing the organic long afterglow material according to the second aspect of the present invention, comprising the following steps: The guest molecule solution is mixed with a melamine formaldehyde resin prepolymer solution, and heated to react to obtain the organic long afterglow material.

[0031] In some embodiments of the present invention, the heating reaction includes a first-stage heating reaction and a second-stage heating reaction.

[0032] In some embodiments of the present invention, the temperature of the heating reaction is 75-95° C. and the time is 1-3 hours.

[0033] In some specific embodiments of the present invention, the temperature of the first heating reaction is 80-90° C. and the time is 1-2 h.

[0034] In some embodiments of the present invention, the temperature of the second stage heating reaction is 120-140° C. and the time is 0.5-2 h.

[0035] In some specific embodiments of the present invention, the temperature of the second stage heating reaction is 125-135° C., and the time is 1-1.5 h.

[0036] The fourth aspect of the present invention provides a polymer film, wherein the raw materials for preparing the polymer film include the organic long afterglow material described in the second aspect of the present invention.

[0037] In some embodiments of the present invention, the polymer film is made from the organic long afterglow material through a hot pressing process.

[0038] In some embodiments of the present invention, the temperature of the hot pressing process is 140-160°C.

[0039] In some specific embodiments of the present invention, the temperature of the hot pressing process is 145-165°C.

[0040] In some embodiments of the present invention, the pressure of the hot pressing process is 15-20 MPa.

[0041] In some specific embodiments of the present invention, the pressure of the hot pressing process is 15-18 MPa.

[0042] In some embodiments of the present invention, the heat pressing process lasts for 5-15 minutes.

[0043] In some specific embodiments of the present invention, the heat pressing process lasts for 8-12 minutes.

[0044] The fifth aspect of the present invention provides the use of the organic long afterglow material described in the second aspect of the present invention, or the polymer film described in the fourth aspect in oxygen detection.

[0045] In some embodiments of the invention, the use comprises qualification testing of an anaerobic device.

[0046] In some embodiments of the present invention, the applying includes irradiating the organic long afterglow material and / or the polymer film with light.

[0047] In the present invention, the organic long afterglow material and polymer film, under aerobic conditions, after being illuminated, the afterglow color shifts from orange to red or dark red, and under anaerobic conditions, there is no light-induced afterglow color change phenomenon, so it can be used for oxygen detection.

[0048] Compared with the prior art, the present invention has the following beneficial effects: The compound of formula (I) provided by the present invention can be used as a guest molecule in an organic long afterglow material. The compound of formula (I) itself has no afterglow property. A substance including melamine formaldehyde resin is used as the main component of the organic long afterglow material. After being doped with the guest molecule, the obtained organic long afterglow material has stable long afterglow performance. The organic long afterglow material provided by the present invention can effectively resist the phosphorescence quenching behavior of oxygen on guest molecules. Under aerobic conditions, the afterglow color changes after illumination, shifting from orange to red or dark red, and the color change has good reversibility. Under anaerobic conditions, the afterglow color does not change before and after illumination, so it can be used in oxygen detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the compound of formula (1) in Example 1; Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the compound of formula (2) in Example 2; Figure 3 The steady-state luminescence spectra of the solid powders of the compounds of formula (1) and formula (2) in the examples; Figure 4 The luminescence attenuation curve of the solid powder of the compound of formula (1) and formula (2) in the embodiment; Figure 5 The steady-state luminescence spectra of the organic long afterglow materials in Examples 1 and 2; Figure 6 The afterglow luminescence spectra of the organic long afterglow materials in Examples 1 and 2; Figure 7 The afterglow luminescence attenuation curve of the organic long afterglow material in Examples 1 and 2; Figure 8 is the ultraviolet absorption curve of the organic long afterglow material in Example 1 as the illumination time increases; Fig. 9 is the ultraviolet absorption curve of the organic long afterglow material in Example 2 as the illumination time increases; Fig.10 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material in Example 1 before ultraviolet irradiation; Fig.11 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material in Example 1 after ultraviolet irradiation; Fig.12 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material in Example 2 before ultraviolet irradiation; Fig.13 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material after ultraviolet irradiation in Example 2; Fig.14 This is a comparison chart of the afterglow luminescence spectra of the organic long afterglow material in Example 1 before and after irradiation under oxygen-free conditions; Fig.15 This is a comparison chart of the afterglow luminescence spectra of the organic long afterglow material in Example 2 before and after irradiation under oxygen-free conditions; Fig.16 This is a comparison diagram of the afterglow luminescence attenuation curves of the organic long afterglow material in Example 1 before and after illumination; Fig.17 This is a comparison diagram of the afterglow luminescence attenuation curves of the organic long afterglow material before and after illumination in Example 2; Fig.18 This is a diagram of the afterglow color change stability of the organic long afterglow material in Example 1; Fig.19 This is a diagram of the afterglow color change stability of the organic long afterglow material in Example 2; Fig. 20 The CIE chromaticity diagram of the organic long afterglow material in Example 1 within 0-5 minutes of illumination; Fig.21 The CIE chromaticity diagram of the organic long afterglow material in Example 2 within 0-5 minutes of illumination; Fig. 22 These are afterglow photographs of the polymer films prepared in Examples 1 and 2 before and after illumination. DETAILED DESCRIPTION

[0050] The present invention is further described in detail below by specific examples. The raw materials, reagents or devices used in the examples can be obtained from conventional commercial sources or by prior art methods unless otherwise specified. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

[0051] Example 1 In this embodiment, a compound of formula (1) is prepared, and an organic long afterglow material is prepared using the compound of formula (1) as a guest molecule, and then a polymer film is prepared using the organic long afterglow material as a raw material through a hot pressing process: 1. The synthesis method of the compound of formula (1) is: 1) 4,7-Dibromo-5,6-dinitrobenzene[c][1,2,5]thiadiazole (1.50 g, 3.91 mmol) and tributyl(phenyl)stannane (4.3 g, 11.72 mmol) were added to toluene, and bubbling was continued for 30 min before adding bis(triphenylphosphine)palladium chloride. The reaction was carried out at 120°C for 12 h. The raw materials were basically reacted. Column chromatography was performed using petroleum ether: dichloromethane = 2: 1 to obtain 1.2 g of the intermediate product as a light yellow powder, with a yield of 81.08%.

[0052] The reaction route is shown below: ; 2) The intermediate product was added to 10 mL of a mixed solution of triethyl phosphite and chlorobenzene in a volume ratio of 1:1, and bubbling was performed for 30 min. The mixture was refluxed at 130°C for 10 h. The raw materials were basically reacted. Column chromatography was performed using petroleum ether: ethyl acetate = 1:1 to obtain a yellow powder of the compound of formula (1) with a yield of 50%.

[0053] The reaction route is shown below: .

[0054] 2. The preparation steps of organic long afterglow materials are as follows: S1, weighing 2 mg of the compound of formula (1) and dissolving it in tetrahydrofuran to prepare an organic solution of the compound of formula (1) with a concentration of 1 mg / mL; S2, adding 256 mg of melamine and 2.14 mL of 37 wt % formaldehyde aqueous solution to 0.1 mL of deionized water, and then adding triethanolamine to adjust the pH value of the solution to 8-9, and heating at 95° C. for 2 h to form a clear melamine formaldehyde resin prepolymer solution; S3. Add the organic solution of the compound of formula (1) into the melamine formaldehyde resin prepolymer solution, heat it at 85° C. for 2 h, and then heat it at 130° C. for 1 h. After the solvent is evaporated, a melamine formaldehyde resin-based organic long afterglow material doped with the compound of formula (1) is obtained.

[0055] 3. The preparation steps of polymer film are as follows: The organic long afterglow material was heated and pressurized at 150° C. and 16 MPa for 10 minutes by a hot press to obtain a translucent polymer film.

[0056] Example 2 In this embodiment, a compound of formula (2) is prepared, and an organic long afterglow material is prepared using the compound of formula (2) as a guest molecule, and then a polymer film is prepared using the organic long afterglow material as a raw material through a hot pressing process: 1. The synthesis method of the compound of formula (2) is: The compound of formula (1) prepared in Example 1 (0.14 g, 0.45 mmol) and sodium hydride (NaH) (0.12 g, 4.45 mmol) were added to 10 mL of ultra-dry tetrahydrofuran (THF). After hydrogen was removed for 30 min, ethyl bromide (CH3CH2Br) (0.109 g, 4.45 mmol) was added, and the reaction solution was reacted at 66°C for 12 h. The yield was purified by column chromatography using petroleum ether: ethyl acetate = 9: 1 to obtain a solid powder of the compound of formula (2) with a yield of 70%.

[0057] The reaction route is shown below: .

[0058] 2. The preparation steps of organic long afterglow materials are as follows: S1, weighing 2 mg of the compound of formula (2) and dissolving it in tetrahydrofuran to prepare an organic solution of the compound of formula (2) with a concentration of 1 mg / mL; S2, adding 256 mg of melamine and 2.14 mL of 37 wt % formaldehyde aqueous solution to 0.1 mL of deionized water, and then adding triethanolamine to adjust the pH value of the solution to 8-9, and heating at 95° C. for 2 h to form a clear melamine formaldehyde resin prepolymer solution; S3. Add the organic solution of the compound of formula (2) into the melamine formaldehyde resin prepolymer solution, heat it at 85° C. for 2 h, and then heat it at 130° C. for 1 h. After the solvent is evaporated, a melamine formaldehyde resin-based organic long afterglow material doped with the compound of formula (2) is obtained.

[0059] 3. The preparation steps of polymer film are as follows: The organic long afterglow material was heated and pressurized at 150° C. and 16 MPa for 10 minutes by a hot press to obtain a translucent polymer film.

[0060] Characterization and performance testing 1. The pure solid powder (microcrystals) of the compounds of formula (1) and formula (2) prepared independently in the examples were subjected to nuclear magnetic resonance hydrogen spectrum test: Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the compound of formula (1) in Example 1, Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the compound of formula (2) in Example 2, Figure 1 and Figure 2 It can be seen that the compounds of formula (1) and formula (2) synthesized by themselves have the target structures.

[0061] 2. The optical properties of the compounds of formula (1) and formula (2) prepared in Examples 1 and 2, as well as the organic long afterglow materials, were tested to examine the afterglow luminescence spectrum and afterglow lifetime. All tests were performed on an Edinburgh FLS980 steady-state transient fluorescence spectrometer with an integrating sphere: Figure 3 is the steady-state luminescence spectrum of the solid powder of the compound of formula (1) and formula (2) in the embodiment, Figure 3 It can be seen that the compound of formula (1) has a high luminescence intensity only in the wavelength range of 475-650nm, and the compound of formula (2) has a high luminescence intensity only in the wavelength range of 450-600nm, that is, the compounds of formula (1) and formula (2) only emit instantaneous fluorescence and have no afterglow properties.

[0062] Figure 4 is the luminescence attenuation curve of the solid powder of the compound of formula (1) and formula (2) in the embodiment, Figure 4 It can be seen that the duration of luminescence of the solid powders of the compounds of formula (1) and formula (2) after being excited by ultraviolet light is very short, and the fitted lifetime values ​​are 1.73ns and 1.28ns, respectively. That is, the solid powders of the compounds of formula (1) and formula (2) themselves have no afterglow properties, and the luminescence intensity decays rapidly.

[0063] Figure 5 is the steady-state luminescence spectrum of the organic long afterglow material in Examples 1 and 2, Figure 6 is the afterglow luminescence spectrum of the organic long afterglow material in Examples 1 and 2, Figure 5 and Figure 6 It can be seen that the steady-state luminescence of the organic long afterglow materials prepared in Examples 1 and 2 is mainly in the range of 450-600nm, and the delayed luminescence is in the range of 550-750nm.

[0064] Figure 7 is the afterglow luminescence attenuation curve of the organic long afterglow material in Examples 1 and 2, Figure 7It can be seen that the lifetime of the maximum emission peak of the delayed spectrum of the organic long afterglow materials in Examples 1 and 2 can reach millisecond level and be greater than 100ms, and the fitting lifetime values ​​are 0.15s and 0.12s respectively, indicating that the materials have good long afterglow luminescence performance.

[0065] Figure 8 is the ultraviolet absorption curve of the organic long afterglow material in Example 1 as the illumination time increases, Fig. 9 is the ultraviolet absorption curve of the organic long afterglow material in Example 2 as the illumination time increases, Figure 8 and Fig. 9 It can be seen that with the increase of illumination time, the ultraviolet absorption peaks of the organic long afterglow materials in Examples 1 and 2 both show an increasing trend, indicating that the materials have a photochromic phenomenon.

[0066] Fig.10 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material in Example 1 before ultraviolet irradiation are shown in FIG. Fig.11 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material in Example 1 after ultraviolet irradiation are shown in FIG. Fig.10 and Fig.11 It can be seen that under aerobic conditions, after ultraviolet irradiation, the position of the maximum afterglow intensity of the organic long afterglow material in Example 1 shifts from 610nm to 638nm, and the color of the afterglow turns red after irradiation.

[0067] Fig.12 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material in Example 2 before ultraviolet irradiation are shown in FIG. Fig.13 The steady-state luminescence spectrum and afterglow luminescence spectrum of the organic long afterglow material after ultraviolet irradiation in Example 2 are shown in FIG. Fig.12 and Fig.13 It can be seen that under aerobic conditions, after ultraviolet irradiation, the position of the maximum afterglow intensity of the organic long afterglow material in Example 2 shifts from 632nm to 654nm, and the color of the afterglow turns red after irradiation.

[0068] Fig.14 is a comparison chart of the afterglow luminescence spectra of the organic long afterglow material in Example 1 before and after irradiation under oxygen-free conditions, Fig.14 It can be seen that the sample was prepared in an oxygen-free glove box and then hot-pumped for 30 minutes to remove oxygen for testing. The organic long afterglow material in Example 1 did not undergo photophosphorescence discoloration after irradiation for 5 minutes in an oxygen-free environment.

[0069] Fig.15 is a comparison chart of the afterglow luminescence spectra of the organic long afterglow material in Example 2 before and after irradiation under oxygen-free conditions, Fig.15It can be seen that the sample was prepared in an oxygen-free glove box and then hot-pumped for 30 minutes to remove oxygen for testing. The organic long afterglow material in Example 2 did not undergo photophosphorescence discoloration after irradiation for 5 minutes in an oxygen-free environment.

[0070] Depend on Figure 12-Figure 15 It can be seen that the organic long afterglow material provided by the present invention only has the photophosphorescence color change phenomenon under oxygen conditions, which can not only show that the material can effectively resist oxygen quenching, but also show that the material has the potential to be used in oxygen detection.

[0071] Fig.16 is a comparison diagram of the afterglow luminescence attenuation curves of the organic long afterglow material in Example 1 before and after illumination, Fig.16 It can be seen that before illumination, the fitted lifetime value of the maximum emission peak of the delayed spectrum of the organic long afterglow material in Example 1 is 0.16s, and after illumination it is 0.155s. The fitted lifetime values ​​before and after illumination are basically unchanged, indicating that the organic long afterglow material prepared in Example 1 has stable afterglow performance.

[0072] Fig.17 is a comparison diagram of the afterglow luminescence attenuation curves of the organic long afterglow material before and after illumination in Example 2, Fig.17 It can be seen that before illumination, the fitted lifetime value of the maximum emission peak of the delayed spectrum of the organic long afterglow material in Example 2 is 0.123s, and after illumination it is 0.119s. The fitted lifetime values ​​before and after illumination are basically unchanged, indicating that the organic long afterglow material prepared in Example 2 also has stable afterglow performance.

[0073] Fig.18 is the afterglow color stability diagram of the organic long afterglow material in Example 1, Fig.18 It can be seen that the organic long afterglow material in Example 1 has good reversibility when irradiated with light for 5 minutes and heated at 100° C. for 10 seconds.

[0074] Fig.19 is the afterglow color stability diagram of the organic long afterglow material in Example 2, Fig.19 It can be seen that the organic long afterglow material in Example 2 has good reversibility when irradiated with light for 5 minutes and heated at 100° C. for 10 seconds.

[0075] Fig. 20 is the CIE chromaticity diagram of the organic long afterglow material in Example 1 within 0-5 minutes of illumination, Fig.21 is the CIE chromaticity diagram of the organic long afterglow material in Example 2 within 0-5 minutes of illumination, Fig. 20 and Fig.21It can be seen that in the CIE chromaticity diagram of the organic long afterglow materials of Examples 1 and 2, as the illumination time increases, the spectral lines all show a trend of gradually shifting toward the red light direction, indicating that the material will have a red or dark red afterglow after being illuminated, and has the property of photophosphorescence color change.

[0076] Fig. 22 The afterglow photos of the polymer films prepared in Examples 1 and 2 before and after illumination, wherein: Fig. 22 (a) is the polymer film in Example 1 before irradiation, Fig. 22 (b) is the polymer film after being irradiated with light in Example 1. Fig. 22 (c) is the polymer film in Example 2 before irradiation, Fig. 22 (d) is the polymer film after light exposure in Example 2. Fig. 22 It can be seen that under aerobic conditions, the afterglow color of the polymer films in Examples 1 and 2 deepens after illumination, while under anaerobic conditions, the afterglow color of the polymer films does not change before and after illumination, indicating that the material can effectively resist the phosphorescence quenching behavior of oxygen and has the characteristic of light-induced afterglow color change, and can be used for oxygen detection, detection of the qualification of anaerobic devices, etc.

Claims

1. Application of the compound represented by formula (I) in organic long afterglow materials; , formula (Ⅰ); in, R is selected from deuterium, H, C1-C 20 Alkyl or C3-C 20 Cycloalkyl.

2. The use according to claim 1, characterized in that: The compound represented by formula (I) is selected from at least one of the following compounds: 、 。 3. An organic long afterglow material, characterized in that: It comprises a main component and a guest molecule doped in the main component; the guest molecule comprises the compound of formula (I) as claimed in claim 1 or 2.

4. The organic long afterglow material according to claim 3, characterized in that: In the organic long afterglow material, the mass fraction of the guest molecule is 0.001%-5%.

5. The organic long afterglow material according to claim 3, characterized in that: The main component includes melamine formaldehyde resin.

6. The organic long afterglow material according to claim 5, characterized in that: The organic long afterglow material comprises the following preparation raw materials: guest molecule solution and melamine formaldehyde resin prepolymer solution.

7. The organic long afterglow material according to claim 6, characterized in that: In the guest molecule solution, the concentration of the guest molecule is 1-4 mg / mL; And / or, the pH value of the melamine formaldehyde resin prepolymer solution is 8-10.

8. The method for preparing the organic long afterglow material according to claim 6 or 7, characterized in that: The following steps are involved: The guest molecule solution is mixed with a melamine formaldehyde resin prepolymer solution, and heated to react to obtain the organic long afterglow material.

9. A polymer film, characterized in that The raw materials for preparing the polymer film include the organic long afterglow material according to any one of claims 3-7.

10. Use of the organic long afterglow material according to any one of claims 3 to 7, or the polymer film according to claim 9 in oxygen detection.

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