Organic room-temperature phosphorescent material, preparation method and application thereof

Abstract

The application provides an organic room-temperature phosphorescent material, which comprises a host matrix, a guest molecule and a crosslinking agent; the host matrix is PVA, the guest molecule is a polycyclic aromatic compound with a boric acid group, and the crosslinking agent is diphenyl methane diisocyanate. The phosphorescent lifetime of the material is greater than 800 ms, and the naked-eye visible phosphorescent effect is greater than 5 s, so that the material has wide application in the fields of information encryption and substance detection.

Description

Technical Field

[0001] This application relates to the technical field of organic room temperature luminescent materials, specifically to an organic room temperature phosphorescent material, its preparation method, and its application. Background Technology

[0002] Organic room-temperature phosphorescent materials refer to organic compounds or materials that can emit phosphorescence at room temperature. Compared with traditional phosphorescent materials, organic room-temperature phosphorescent materials have advantages such as long service life, good biocompatibility, high brightness, and environmental friendliness, and have broad application prospects in many fields.

[0003] To achieve phosphorescence emission, traditional room-temperature phosphorescent materials often incorporate metal atoms such as iridium and platinum to enhance spin-orbit coupling and improve phosphorescence performance. However, the widespread use of heavy metals inevitably leads to problems such as high production costs, high cytotoxicity, poor processability, and poor stability. Therefore, developing low-cost, high-performance, and environmentally friendly metal-free, purely organic room-temperature phosphorescent materials is of great significance.

[0004] Pure organic phosphorescent materials exhibit luminescence at room temperature, which is easily affected by the environment. Phosphorescence is typically only observed under low-temperature or rigid environmental conditions. Achieving low-temperature conditions in daily life is difficult. Currently, commonly used methods for achieving room-temperature phosphorescence emission include: doping luminescent molecules into a polymer matrix to isolate them from oxygen and moisture while providing a rigid environment to suppress their thermal motion; using crystal engineering to restrict the thermal motion of luminescent molecules through intermolecular interactions, with the crystal lattice effectively preventing the diffusion of oxygen and water; and preparing host-guest materials, where a crystalline host effectively isolates moisture and oxygen and stabilizes triplet excitons, while a host molecule with matching energy levels promotes charge transfer state formation, improves intersystem crossing efficiency, and enhances room-temperature phosphorescence. These methods share the common goal of creating a rigid environment to suppress the thermal motion of luminescent molecules. While these methods ultimately achieve phosphorescence emission, they also have certain drawbacks. For example, once prepared as polymer materials, the luminescent molecules are difficult to separate, and the polymer's morphology is difficult to change after solidification. Preparing crystalline materials requires complex techniques and a demanding crystal growth environment. The preparation of the host material in host-guest doped materials is quite complicated. Summary of the Invention

[0005] To address the aforementioned technical problems, this application proposes an organic room-temperature phosphorescent material, its preparation method, and its application, which has advantages such as simple preparation, long lifespan, full color tunability, and good stability.

[0006] In a first aspect of this application, an organic room temperature phosphorescent material is provided, comprising: a host matrix, a guest molecule, and a crosslinking agent; the host matrix is ​​PVA, the guest molecule is a polycyclic aromatic compound with boric acid groups, and the crosslinking agent is diphenylmethane diisocyanate; the amount of the compound with boric acid groups incorporated is 0.1 to 5 wt% of the weight of the host material.

[0007] Using PVA as the main matrix, arylboronic acid as the guest material, and diphenylmethane diisocyanate as the crosslinking agent, this method employs several techniques. First, PVA contains numerous hydroxyl groups, which can react with boronic acid groups under alkaline conditions to form reversible boronic acid ester bonds. These bonds connect aromatic groups to the PVA matrix, reducing molecular vibrations and suppressing non-radiative transitions, thus enhancing phosphorescence performance. Furthermore, crosslinking the PVA chains with diphenylmethane diisocyanate creates a three-dimensional polymer network framework, further improving the overall rigidity of the material. Compared to other rigid materials used as the matrix, this method offers advantages such as ease of operation, good product stability, lower harm to human health, and greater safety and environmental friendliness. By adjusting the structure and doping ratio of the aromatic groups, a variety of colors, from blue to red, were achieved.

[0008] Preferably, the guest molecule and the host matrix form a borate ester bond, and the host matrix can be reacted with a crosslinking agent to obtain insoluble polymer particles.

[0009] After uniformly mixing arylboronic acid with an aqueous PVA solution, ammonia is added to create an alkaline environment, followed by heating. The arylboronic acid reacts with the PVA chains to form borate ester bonds. A crosslinking agent is then added to crosslink the PVA chains, resulting in insoluble polymer particles. The PVA matrix within these particles suppresses molecular vibrations, thereby achieving phosphorescence emission.

[0010] Preferably, the general structural formula of polycyclic aromatic compounds containing boric acid groups includes:

[0011] .

[0012] Preferably, the amount of compound containing boric acid groups incorporated is 0.2 to 1.0 wt% of the weight of the main matrix.

[0013] A second aspect of this application provides a method for preparing an organic room-temperature phosphorescent material, comprising the following steps:

[0014] S1. Prepare the host matrix into an aqueous solution, and then add guest molecules to obtain a mixed solution;

[0015] S2. Add ammonia to the mixed solution to create an alkaline environment, and heat in an oil bath for 10–30 min;

[0016] S3. Add a crosslinking agent, react to obtain insoluble polymer particles, filter, rinse and dry to obtain an organic room temperature phosphorescent material.

[0017] Preferably, in S2, the oil bath heating time is 20 min.

[0018] A third aspect of this application provides an application of an organic room temperature phosphorescent material, including: using the organic room temperature phosphorescent material as a characteristic luminescent material in anti-counterfeiting ink; or using the organic room temperature phosphorescent material as a characteristic luminescent material for optical information encoding; or using the organic room temperature phosphorescent material as a surface color material for optoelectronic devices.

[0019] In addition, organic room-temperature phosphorescent materials are used in the measurement of X-ray radiation.

[0020] The beneficial effects of this invention are as follows:

[0021] The organic room-temperature phosphorescent material provided by this invention uses PVA as the main matrix and arylboronic acid as the guest material. After being gently heated sufficiently in an alkaline aqueous solution, the two form reversible borate ester bonds. A crosslinking agent is then added to form a three-dimensional polymer framework, improving the overall rigidity of the material, reducing molecular vibrations, suppressing non-radiative transitions, and enhancing phosphorescence performance. Furthermore, by changing the aryl structure and doping concentration, phosphorescence emission of different colors can be achieved.

[0022] In this application, based on guest molecules with different aryl structures, the room-temperature phosphorescent material provided by this invention exhibits a photoluminescence spectrum ranging from 360 nm to 550 nm under excitation by an ultraviolet light source with a wavelength of 290 nm to 360 nm. The optimal emission peak for photoluminescence occurs between 360 nm and 450 nm, displaying a deep blue to pale blue fluorescence. Even after the ultraviolet light excitation stops, it still exhibits phosphorescence emission visible to the naked eye for >4 s, with a phosphorescence wavelength range of 400 nm to 720 nm and an emission peak between 450 nm and 690 nm. The longest phosphorescence lifetime reaches 854 ms.

[0023] The method for preparing room-temperature phosphorescent materials provided by this invention uses materials that are free of heavy atoms and heavy metals, are safe and non-toxic, and will not harm the human body; the content of the guest component is low, and the cost is low. The preparation process is simple and convenient.

[0024] The room-temperature phosphorescent material provided by this invention has great application value in the fields of information encryption and material detection. Attached Figure Description

[0025] The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and, together with the description, serve to explain the principles of this application. Other embodiments and many anticipated advantages of these embodiments will be readily recognized as they become better understood through reference to the following detailed description. Elements in the drawings are not necessarily to scale. The same reference numerals refer to corresponding similar parts.

[0026] Figure 1 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a 1-naphthaleneboronic acid doping concentration of 0.1% wt.% prepared in Example 1.

[0027] Figure 2 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a 0.5% wt.% doping concentration of 1-naphthaleneboronic acid prepared in Example 2.

[0028] Figure 3 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the 1-naphthoic acid 1% wt.% doped polymer particles prepared in Example 3.

[0029] Figure 4 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the 1-naphthoic acid 3% wt.% doped polymer particles prepared in Example 4.

[0030] Figure 5 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a 0.1% wt.% doping concentration of 4-biphenylboronic acid prepared in Example 5.

[0031] Figure 6 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a 0.5% wt.% doping concentration of 4-biphenylboronic acid prepared in Example 6.

[0032] Figure 7 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the 1% wt.% doped polymer particles of 4-biphenylboronic acid prepared in Example 7.

[0033] Figure 8 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the 4-biphenylboronic acid 3% wt.% doped polymer particles prepared for Example 8;

[0034] Figure 9 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the 1-pyreneboronic acid 0.1% wt.% doped polymer particles prepared for Example 9.

[0035] Figure 10Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of polymer particles with a 0.3% wt.% doping concentration of 1-pyreneboronic acid prepared for Example 10.

[0036] Figure 11 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a 0.5% wt.% doping concentration of 1-pyreneboronic acid prepared in Example 11.

[0037] Figure 12 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the 1-pyreneboronic acid 1% wt.% doped polymer particles prepared for Example 12.

[0038] Figure 13 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of 1% wt.% doped polymer particles of β-[1,1'-binaphthyl]-4-ylboronic acid prepared in Example 13.

[0039] Figure 14 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 0.1% wt.% of 4-boronic acid triphenylamine prepared in Example 14.

[0040] Figure 15 The phosphorescence effect diagrams are for the organic room temperature phosphorescent materials in Examples 1, 5, and 9.

[0041] Figure 16 Phosphorescence lifetime diagrams of the organic room-temperature phosphorescent materials in Examples 1-4;

[0042] Figure 17 Phosphorescence lifetime diagrams for the organic room-temperature phosphorescent materials of Examples 5-8;

[0043] Figure 18 Phosphorescence lifetime diagrams for the organic room-temperature phosphorescent materials of Examples 9-12;

[0044] Figure 19 Phosphorescence lifetime diagram of the organic room temperature phosphorescent material in Example 13;

[0045] Figure 20 Phosphorescence lifetime diagram of the organic room temperature phosphorescent material in Example 14;

[0046] Figure 21 The TEM image is from Example 3;

[0047] Figure 22 This is a phosphorescence lifetime graph of Example 13 after immersion in six different solvents for two months;

[0048] Figure 23 The bar chart shows the phosphorescence lifetime data of Example 13 after immersion in six different solvents for two months and in air. Detailed Implementation

[0049] In the following detailed description, reference is made to the accompanying drawings, which form part of the detailed description and illustrate illustrative specific embodiments in which the present application may be practiced. In this regard, directional terms such as “top,” “bottom,” “left,” “right,” “up,” “down,” etc., are used with reference to the orientation of the described figures. Because components of the embodiments can be positioned in several different orientations, directional terms are used for illustrative purposes and are by no means limiting. It should be understood that other embodiments may be utilized or logical changes may be made without departing from the scope of the present application. Therefore, the following detailed description should not be taken in a limiting sense, and the scope of the present application is defined by the appended claims.

[0050] The embodiments and features described in the present invention can be combined with each other.

[0051] It should be noted that the embodiments listed below are for further illustration of the present invention, and not for further limitation of the present invention.

[0052] The main raw material usage and experimental conditions involved in Examples 1-20 are shown in the table below.

[0053] Example 1

[0054] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0055] S2. Weigh 0.5 mg of 1-naphthoboric acid as the guest molecule, add 1 ml of ammonia solution, and sonicate to disperse evenly. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0056] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0057] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0058] Further reference Figure 1As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 358 nm, and the phosphorescence emission centers are 505 nm and 535 nm. Example 2

[0059] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0060] S2. Weigh 2.5 mg of 1-naphthoboric acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0061] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0062] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0063] Further reference Figure 2 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 358 nm, and the phosphorescence emission centers are 505 nm and 535 nm. Example 3

[0064] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0065] S2. Weigh 5.0 mg of 1-naphthoic acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0066] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0067] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0068] Further reference Figure 3 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 358 nm, and the phosphorescence emission centers are 505 nm and 535 nm.

[0069] Meanwhile, after the polymer particles prepared in this example are crushed and dried, the following results are obtained: Figure 22 The TEM image is shown in the figure. The polymer particles in this embodiment are spherical and ellipsoidal, with a particle size of about 100-150 nm. Example 4

[0070] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0071] S2. Weigh 15.0 mg of 1-naphthoboric acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0072] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0073] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0074] Further reference Figure 4 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 358 nm, and the phosphorescence emission centers are 505 nm and 535 nm. Example 5

[0075] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0076] S2. Weigh 0.5 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and sonicate to disperse evenly. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0077] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0078] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0079] Further reference Figure 5 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 356 nm, and the phosphorescence emission centers are 463 nm and 486 nm. Example 6

[0080] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0081] S2. Weigh 1.5 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and sonicate to disperse evenly. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0082] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0083] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0084] Further reference Figure 6 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 356 nm, and the phosphorescence emission centers are 463 nm and 492 nm. Example 7

[0085] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0086] S2. Weigh 5.0 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0087] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0088] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0089] Further reference Figure 7 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 356 nm, and the phosphorescence emission centers are 463 nm and 492 nm. Example 8

[0090] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0091] S2. Weigh 15.0 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0092] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0093] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0094] Further reference Figure 8 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 356 nm, and the phosphorescence emission centers are 463 nm and 492 nm. Example 9

[0095] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0096] S2. Weigh 0.5 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0097] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0098] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0099] Further reference Figure 9As shown, in this embodiment, the excitation wavelength is 360 nm, the fluorescence emission center is 412 nm, and the main phosphorescence emission center is 612 nm. Example 10

[0100] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0101] S2. Weigh 1.5 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and sonicate to disperse evenly. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0102] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0103] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0104] Further reference Figure 10 As shown, in this embodiment, the excitation wavelength is 360 nm, the fluorescence emission center is 412 nm, and the main phosphorescence emission center is 612 nm. Example 11

[0105] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0106] S2. Weigh 2.5 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0107] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0108] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0109] Further reference Figure 11 As shown, in this embodiment, the excitation wavelength is 360 nm, the fluorescence emission center is 408 nm, and the main phosphorescence emission center is 612 nm. Example 12

[0110] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0111] S2. Weigh 5.0 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0112] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0113] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0114] Further reference Figure 12 As shown, in this embodiment, the excitation wavelength is 360 nm, the fluorescence emission center is 404 nm, and the main phosphorescence emission center is 612 nm. Example 13

[0115] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0116] S2. Weigh 5.0 mg of β-[1,1'-binaphthyl]-4-ylboronic acid as the guest molecule, add 1 ml of ammonia solution, and sonicate to disperse evenly. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid group reacts with the hydroxyl groups on the PVA chain to obtain a mixed solution.

[0117] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0118] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0119] Further reference Figure 13 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 388 nm, and the main phosphorescence emission center is 535 nm.

[0120] like Figure 19 As shown, in this embodiment, the phosphorescence lifetime of the polymer particles is 309 ms.

[0121] Furthermore, to better demonstrate the luminescence performance and phosphorescence lifetime of the polymer particles in this embodiment, the polymer particles in this embodiment were immersed in six different solvents for two months, and then measurements were performed to obtain the following results: Figure 22 , 23 The image shown demonstrates that, compared to polymer particles in air, the luminescence lifetime of the immersed polymer particles did not change significantly, proving that the polymer particles have good stability in various environments. Example 14

[0122] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve them in 100g of aqueous solution, heat and stir in an oil bath at 100℃ for 5 hours to obtain 100g*L of solution. -1 The PVA solution was allowed to cool to room temperature.

[0123] S2. Weigh 5.0 mg of 4-boronic acid triphenylamine as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by sonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 min. The boric acid groups and the hydroxyl groups on the PVA chain react to obtain a mixed solution.

[0124] S3. After the mixed solution has cooled to 50°C in the pot, keep it warm, weigh 200 mg of diphenylmethane diisocyanate and add it to the mixed solution, and continue stirring for 20 min.

[0125] S4. The reaction produces insoluble white polymer particles. The reaction solution is poured into 500 ml of ultrapure water to dilute the unreacted PVA chains. Then, the mixture is filtered using a Buchner funnel, and the surface of the polymer particles is washed sequentially with water, ethanol, and ethyl acetate to remove uncrosslinked or unreacted PVA chains and alkyl boric acid molecules. The mixture is then dried to obtain the room-temperature phosphorescent material described in this invention.

[0126] Further reference Figure 14 As shown, in this embodiment, the excitation wavelength is 300 nm, the fluorescence emission center is 365 nm, and the main phosphorescence emission center is 464 nm.

[0127] In addition, such as Figure 20 As shown, in this embodiment, the phosphorescence lifetime of the polymer particles is 96.9 ms. Example 15

[0128] Based on the polymer particles prepared in Examples 3, 7, 12, and 13, the four polymer particles were arranged into specific shapes and irradiated with ultraviolet lamps. Due to the photoluminescence properties of the materials, specific luminescence patterns could be observed after the ultraviolet light source was turned off, and different luminescence patterns could be obtained under excitation by light sources of different wavelengths, thereby completing information encryption. Example 16

[0129] The product of Example 13 was divided into six equal portions and soaked in six common solvents—methanol, ethanol, petroleum ether, toluene, ethyl acetate, and water—for two months each. The portions were then filtered, dried, and their luminescent properties were tested.

[0130] Furthermore, to better illustrate the present invention, afterglow (e.g., after being subjected to ultraviolet light irradiation and after the light source was turned off) in Examples 1, 4, and 9 was obtained. Figure 15 As shown in the figure, the polymer particles of Example 1 exhibit light blue fluorescence under 310 nm ultraviolet light irradiation, and emit a green afterglow after the ultraviolet light source is turned off. Example 5 exhibits light blue fluorescence under 310 nm ultraviolet light irradiation, and emits a cyan afterglow after the ultraviolet light source is turned off. Example 9 exhibits blue fluorescence under 365 nm ultraviolet light irradiation, and emits a red afterglow after the ultraviolet light source is turned off.

[0131] Figure 16 The phosphorescence lifetimes of the polymer particles of Examples 1-4 are shown, with Example 3 having the longest phosphorescence lifetime of 912 ms.

[0132] Figure 17The phosphorescence lifetimes of the polymer particles of Examples 5-8 are shown, with Example 6 having the longest phosphorescence lifetime of 257.8 ms.

[0133] Figure 18 The phosphorescence lifetimes of the polymer particles of Examples 9-12 are shown, with Example 10 having the longest phosphorescence lifetime of 116.9 ms.

[0134] It is obvious that those skilled in the art can make various modifications and alterations to the embodiments of this application without departing from the spirit and scope of this application. In this way, this application also aims to cover such modifications and alterations if they fall within the scope of the claims and their equivalents. The word "comprising" does not exclude the presence of other elements or steps not listed in the claims. The simple fact that certain measures are described in mutually different dependent claims does not indicate that a combination of these measures cannot be used for profit. Any reference numerals in the claims should not be considered limiting in scope.

Claims

1. An organic room-temperature phosphorescent material, characterized in that, include: The material comprises a host matrix, a guest molecule, and a crosslinking agent; the host matrix is ​​PVA, the guest molecule is a polycyclic aromatic compound with boric acid groups, and the crosslinking agent is diphenylmethane diisocyanate; the amount of the polycyclic aromatic compound with boric acid groups incorporated is 0.1~5 wt% of the weight of the host matrix; the host matrix and the guest molecule form boric acid ester bonds, and the host matrix reacts with the crosslinking agent to form insoluble polymer particles; the particles of the organic room temperature phosphorescent material are spherical or ellipsoidal.

2. The organic room-temperature phosphorescent material according to claim 1, characterized in that, The polycyclic aromatic compound with a boric acid group is selected from one or more of the following structures: ， ， ， 。 3. The organic room-temperature phosphorescent material according to claim 1, characterized in that, The amount of the polycyclic aromatic compound with boric acid groups incorporated is 0.2 to 1.0 wt% of the main matrix.

4. The organic room-temperature phosphorescent material according to claim 1, characterized in that, The organic room-temperature phosphorescent material is used for X-ray radiation measurement.

5. A method for preparing an organic room-temperature phosphorescent material as described in any one of claims 1 to 4, the method comprising: S1. Prepare the host matrix into an aqueous solution, and then add the guest molecules to obtain a primary mixed solution; S2. Add ammonia water to the primary mixed solution to form an alkaline environment, and heat in an oil bath for 10-30 minutes to obtain a secondary mixed solution; S3. Add the crosslinking agent to the secondary mixed solution, react to obtain insoluble polymer particles, filter, rinse and dry to obtain organic room temperature phosphorescent material.

6. The method for preparing the organic room-temperature phosphorescent material according to claim 5, characterized in that, In step S2, the oil bath heating time is 20 minutes.

7. An application of an organic room-temperature phosphorescent material as described in any one of claims 1 to 4, characterized in that: The organic room-temperature phosphorescent material is used as a characteristic luminescent material in the anti-counterfeiting ink; Alternatively, the organic room-temperature phosphorescent material may be used as a characteristic luminescent material for optical information encoding; Alternatively, the organic room-temperature phosphorescent material may be used as the surface color material for optoelectronic devices.

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