Organic room-temperature phosphorescent material as well as preparation method and application thereof

Abstract

The invention provides an organic room-temperature phosphorescent material. The organic room-temperature phosphorescent material comprises a host matrix, a guest molecule and a cross-linking agent, the host matrix is PVA, the guest molecule is a polycyclic aromatic compound with a boric acid group, and the cross-linking agent is diphenylmethane diisocyanate. The phosphorescence lifetime of the material is gt; the visible phosphorescence effect gt is achieved by naked eyes; the method has wide application in the fields of information encryption, substance detection and the like.

Description

Technical Field

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

[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 the advantages of long service life, good biocompatibility, high brightness, and green environmental protection, and have broad application prospects in many fields.

[0003] In order to achieve phosphorescent emission, metal atoms such as iridium and platinum are added during the preparation of traditional room temperature phosphorescent materials to enhance spin-orbit coupling and improve the phosphorescent properties of the materials. However, the widespread use of heavy metals inevitably leads to problems such as high production costs, high cytotoxicity, poor processability and stability. Therefore, it is of great significance to develop low-cost, high-performance and environmentally friendly metal-free pure organic room temperature phosphorescent materials.

[0004] The luminescence of pure organic phosphorescent materials at room temperature is easily affected by the environment. Usually, phosphorescence can only be observed under low temperature or rigid environmental conditions. It is difficult to achieve low temperature conditions in daily life. The commonly used methods for achieving room temperature phosphorescence emission are: doping luminescent molecules into polymer matrices, isolating oxygen and moisture from the air while providing a rigid environment to suppress the thermal motion of luminescent molecules; through crystal engineering, using the intermolecular effect to limit the thermal motion of luminescent molecules, and the lattice formed in the crystal can also effectively prevent the diffusion of oxygen and water; preparing host-guest materials, the crystalline host can effectively isolate moisture and oxygen, and stabilize triplet excitons, while the host molecules with matching energy levels can promote the formation of charge transfer states, improve intersystem crossing efficiency, and enhance room temperature phosphorescence. These methods have one thing in common in achieving phosphorescence emission, which is to construct a rigid environment to suppress the thermal motion of luminescent molecules. Although these methods can eventually achieve phosphorescence emission, they also have certain defects. For example, after being prepared into polymer materials, it is difficult for luminescent molecules to be separated again, and it is difficult for polymers to change their morphology after being finalized. The preparation of crystalline materials requires more complex operating techniques and a harsh crystal growth environment. The preparation of the main material in the host-guest doped materials is relatively complicated. Summary of the invention

[0005] In order to solve the above technical problems, the present application proposes an organic room temperature phosphorescent material and a preparation method and application thereof, which has the advantages of simple preparation, long life, full color tunability, good stability, etc.

[0006] In the first aspect of the present application, an organic room temperature phosphorescent material is provided, comprising: a host matrix, a guest molecule and a cross-linking agent; the host matrix is ​​PVA, the guest molecule is a polycyclic aromatic compound with a boronic acid group, and the cross-linking agent is diphenylmethane diisocyanate; the amount of the compound with the boronic acid group incorporated is 0.1~5 wt% of the weight of the host material.

[0007] PVA is used as the main matrix, aromatic boronic acid is used as the guest material, and diphenylmethane diisocyanate is used as the cross-linking agent. First, PVA contains a large number of hydroxyl groups, which can react with boronic acid groups in an alkaline environment to form reversible borate bonds. Through the borate bond, the aromatic group is connected to the PVA main matrix, which can reduce molecular vibration, thereby inhibiting non-radiative transitions and improving phosphorescence performance. And the PVA chain is cross-linked by diphenylmethane diisocyanate to obtain a three-dimensional polymer network framework, further improving the overall rigidity of the material. Compared with other rigid materials as matrices, this method has the advantages of simple operation, good product stability, less harm to the human body, and more safety and environmental protection. By adjusting the structure and doping ratio of the aromatic group, a variety of color emissions from blue to red are achieved.

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

[0009] After the aromatic boronic acid and the PVA aqueous solution are uniformly mixed, ammonia water is added to form an alkaline environment, and then heated, the aromatic boronic acid can react with the PVA chain to form a borate ester bond. Then a cross-linking agent is added to cross-link the PVA chain to obtain insoluble polymer particles. The PVA main matrix in the polymer particles can inhibit the vibration of the molecules, thereby achieving phosphorescence emission.

[0010] Preferably, the general structural formula of the polycyclic aromatic compound with a boronic acid group includes: , , , .

[0011] Preferably, the compound having a boronic acid group is incorporated in an amount of 0.2-1.0 wt % of the weight of the host matrix.

[0012] In a second aspect of the present application, a method for preparing an organic room temperature phosphorescent material is provided, comprising the following steps: S1. The host matrix is ​​configured into an aqueous solution, and then the guest molecules are added to obtain a mixed solution; S2. Add ammonia water to the mixed solution to form an alkaline environment and heat it in an oil bath for 10 to 30 min; S3. Add a cross-linking agent to react to obtain insoluble polymer particles, filter, rinse and dry to obtain an organic room temperature phosphorescent material.

[0013] Preferably, in S2, the oil bath heating time is 20 min.

[0014] In the third aspect of the present application, an application of an organic room temperature phosphorescent material is provided, 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 an optoelectronic device.

[0015] And, organic room temperature phosphorescent materials are used in the measurement of X-ray radiation.

[0016] The beneficial effects of the present invention are: The organic room temperature phosphorescent material provided by the present invention has PVA as the main matrix and arylboronic acid as the guest material. After the two are heated in an alkaline environment aqueous solution, a reversible borate ester bond is formed. A cross-linking agent is then added to form a three-dimensional polymer framework, thereby improving the overall rigidity of the material, weakening the vibration of the molecules, inhibiting their non-radiative transitions, and improving the phosphorescent luminescence performance. In addition, by changing the aromatic structure and doping concentration, phosphorescent emission of different colors can be achieved.

[0017] In the present application, according to the guest molecules with different aromatic structures, the room temperature phosphorescent material provided by the present invention has a photoluminescence spectrum wavelength range of 360 nm to 550 nm under the excitation of an ultraviolet light source with a wavelength of 290 nm to 360 nm, and the optimal photoluminescence emission peak appears at 360 nm to 450 nm, showing dark blue to light blue fluorescence; after the ultraviolet light source excitation stops, it still has phosphorescence emission visible to the naked eye for more than 4 s, the phosphorescence emission wavelength range is 400 nm to 720 nm, and the emission peak is at 450 nm to 690 nm. The longest phosphorescence lifetime reaches 854 ms.

[0018] The room temperature phosphorescent material preparation method provided by the present invention has the advantages that the material used does not contain heavy atoms and heavy metals, is safe and non-toxic, and will not cause harm to the human body; the guest content is small, the cost is low, and the preparation process is simple and convenient.

[0019] The room temperature phosphorescent material provided by the invention has great application value in the fields of information encryption and material detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated into and constitute a part of this specification. The accompanying drawings illustrate the embodiments and are used together with the description to explain the principles of the present application. It will be easy to recognize other embodiments and many expected advantages of the embodiments because they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale with each other. The same reference numerals refer to corresponding similar parts.

[0021] Figure 1 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles doped with 0.1% wt.% of 1-naphthaleneboronic acid prepared in Example 1; Figure 2 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles doped with 0.5% wt.% of 1-naphthaleneboronic acid prepared in Example 2; Figure 3 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 1% wt.% of 1-naphthaleneboronic acid prepared in Example 3; Figure 4 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 3% wt.% of 1-naphthaleneboronic acid prepared in Example 4; Figure 5 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles doped with 0.1 wt.% of 4-biphenylboronic acid prepared in Example 5; Figure 6 Fluorescence emission spectrum (left) and phosphorescence spectrum (right) of polymer particles with 0.5 wt.% doping concentration of 4-biphenylboronic acid prepared in Example 6; Figure 7 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with 1 wt.% doping concentration of 4-biphenylboronic acid prepared in Example 7; Figure 8 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 3% wt.% of 4-biphenylboronic acid prepared in Example 8; Fig. 9 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles doped with 0.1% wt.% of 1-pyreneboronic acid prepared in Example 9; Fig.10 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles doped with 0.3% wt.% of 1-pyreneboronic acid prepared in Example 10; Fig.11The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 0.5% wt.% of 1-pyreneboronic acid prepared in Example 11; Fig.12 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 1% wt.% of 1-pyreneboronic acid prepared in Example 12; Fig.13 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 1% wt.% of B-[1,1'-binaphthyl]-4-ylboronic acid prepared in Example 13; Fig.14 The fluorescence emission spectrum (left) and phosphorescence spectrum (right) of the polymer particles with a doping concentration of 0.1% wt.% of 4-triphenylamine borate prepared in Example 14; Fig.15 The phosphorescence effect diagram of the organic room temperature phosphorescent material of Examples 1, 5, and 9; Fig.16 is a phosphorescence lifetime diagram of the organic room temperature phosphorescent material of Examples 1-4; Fig.17 is a phosphorescence lifetime diagram of the organic room temperature phosphorescent material of Examples 5-8; Fig.18 is a phosphorescence lifetime diagram of the organic room temperature phosphorescent material of Examples 9-12; Fig.19 is a phosphorescence lifetime diagram of the organic room temperature phosphorescent material of Example 13; Fig. 20 is a phosphorescence lifetime diagram of the organic room temperature phosphorescent material of Example 14; Fig.21 is the TEM image of Example 3; Fig. 22 This is a phosphorescence lifetime diagram of Example 13 after being immersed in six different solvents for two months; Fig.23 The bar graph is a graph showing the phosphorescence lifetime data of Example 13 after being immersed in six different solvents for two months and in an air environment. DETAILED DESCRIPTION

[0022] In the following detailed description, reference is made to the accompanying drawings, which form a part of the detailed description and are shown by illustrative specific embodiments in which the present application can be practiced. To this end, directional terms, such as "top", "bottom", "left", "right", "up", "down", etc., are used with reference to the orientation of the figures described. Because the components of the embodiments can be positioned in several different orientations, directional terms are used for the purpose of illustration 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 adopted in a limiting sense, and the scope of the present application is defined by the appended claims.

[0023] The embodiments of the present invention and the features in the embodiments may be combined with each other.

[0024] It should be noted that the embodiments listed below are intended to further illustrate the present invention rather than to further limit the present invention.

[0025] The amounts of main raw materials and experimental conditions involved in Examples 1 to 20 are shown in the following table.

[0026] Example 1

[0027] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0028] S2. Weigh 0.5 mg of 1-naphthylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0029] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0030] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0031] Further references 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

[0032] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0033] S2. Weigh 2.5 mg of 1-naphthylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0034] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0035] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0036] Further references 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

[0037] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0038] S2. Weigh 5.0 mg of 1-naphthylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0039] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0040] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0041] Further references 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.

[0042] At the same time, the polymer particles prepared in this example are crushed and dried to obtain Fig. 22 As shown in the TEM image, the polymer particles in this embodiment are spherical and ellipsoidal, and the particle size is about 100-150 nm. Example 4

[0043] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0044] S2. Weigh 15.0 mg of 1-naphthoboric acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by ultrasonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0045] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0046] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0047] Further references 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

[0048] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0049] S2. Weigh 0.5 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0050] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0051] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0052] Further references 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

[0053] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0054] S2. Weigh 1.5 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0055] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0056] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0057] Further references 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

[0058] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0059] S2. Weigh 5.0 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0060] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0061] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0062] Further references 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

[0063] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0064] S2. Weigh 15.0 mg of 4-biphenylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0065] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0066] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0067] Further references 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

[0068] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0069] S2. Weigh 0.5 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0070] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0071] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0072] Further references Fig. 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

[0073] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0074] S2. Weigh 1.5 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution to 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0075] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0076] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0077] Further references Fig.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. Embodiment 11

[0078] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0079] S2. Weigh 2.5 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0080] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0081] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0082] Further references Fig.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

[0083] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0084] S2. Weigh 5.0 mg of 1-pyreneboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0085] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0086] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0087] Further references Fig.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. Embodiment 13

[0088] S1. Preparation of PVA aqueous solution: Weigh 10g of PVA polymer particles, dissolve in 100g of aqueous solution, heat in an oil bath at 100℃ and stir for 5h to obtain 100g*L -1 The PVA solution was cooled to room temperature.

[0089] S2. Weigh 5.0 mg of B-[1,1'-binaphthyl]-4-ylboronic acid as the guest molecule, add 1 ml of ammonia solution, and disperse evenly by ultrasonication. 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 group on the PVA chain to obtain a mixed solution.

[0090] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[0091] 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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0092] Further references Fig.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.

[0093] like Fig.19 As shown, in this embodiment, the phosphorescence lifetime of the polymer particles is 309 ms.

[0094] In addition, in order to better reflect the luminescent properties and phosphorescence lifetime of the polymer particles in this embodiment, the polymer particles in this embodiment were immersed in six different solvents for 2 months and then measured, and the following results were obtained: Fig. 22 , 23 From the images shown, it can be concluded that the luminescence lifetime of the polymer particles after immersion does not change significantly compared with that of the polymer particles in the air, proving that the polymer particles have good stability in a variety of environments. Embodiment 14

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

[0096] S2. Weigh 5.0 mg of 4-boric acid triphenylamine as the guest molecule, add 1 ml of ammonia solution, and disperse it evenly by ultrasonication. Then add the guest molecule solution into 5 ml of PVA solution, heat and stir at 80°C for 20 minutes. The boric acid group reacts with the hydroxyl group on the PVA chain to obtain a mixed solution.

[0097] S3. The mixed solution is cooled to 50°C and then kept warm. 200 mg of diphenylmethane diisocyanate is weighed and added to the mixed solution, and stirring is continued for 20 minutes.

[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, and then filtered with a Buchner funnel, and the uncrosslinked or unreacted PVA chains and alkylboronic acid molecules on the surface of the polymer particles are washed with water, ethanol, and ethyl acetate in sequence, and dried to obtain the room temperature phosphorescent material of the present invention.

[0099] Further references Fig.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.

[0100] In addition, if Fig. 20 As shown, in this embodiment, the phosphorescence lifetime of the polymer particles is 96.9 ms. Embodiment 15

[0101] Based on the polymer particles prepared in Examples 3, 7, 12 and 13, the four polymer particles are arranged into a specific shape and irradiated with an ultraviolet lamp. Due to the photoluminescent properties of the material, a specific luminescent pattern can be observed after the ultraviolet light source is turned off, and different luminescent patterns can be obtained under the excitation of light sources of different wavelengths, thereby completing information encryption. Example 16

[0102] The product of Example 13 was divided into six equal parts and immersed in six common solvents, namely methanol, ethanol, petroleum ether, toluene, ethyl acetate and water, for 2 months, and then filtered, dried and tested for its luminescent properties.

[0103] In addition, in order to better illustrate the present invention, the afterglow (such as Fig.15 As shown in the figure, the polymer particles of Example 1 exhibit light blue fluorescence under 310 nm ultraviolet light source, and emit green afterglow after turning off the ultraviolet light source. Example 5 exhibits light blue fluorescence under 310 nm ultraviolet light source, and emits cyan afterglow after turning off the ultraviolet light source. Example 9 exhibits blue fluorescence under 365 nm ultraviolet light source, and emits red afterglow after turning off the ultraviolet light source.

[0104] Fig.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.

[0105] Fig.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.

[0106] Fig.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.

[0107] Obviously, those skilled in the art can make various modifications and changes to the embodiments of the present application without departing from the spirit and scope of the present application. In this way, if these modifications and changes are within the scope of the claims of the present application and their equivalents, the present application is also intended to cover these modifications and changes. 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 recorded in mutually different dependent claims does not indicate that the combination of these measures cannot be used to profit. Any figure mark in the claims should not be considered to limit the scope.

Claims

1. An organic room temperature phosphorescent material, characterized in that: include: A main matrix, a guest molecule and a cross-linking agent; the main matrix is ​​PVA, the guest molecule is a polycyclic aromatic compound with a boronic acid group, and the cross-linking agent is diphenylmethane diisocyanate; the amount of the compound with a boronic acid group added is 0.1-5wt% of the weight of the main matrix.

2. The organic room temperature phosphorescent material according to claim 1, characterized in that: The host matrix and the guest molecule form borate bonds, and the host matrix reacts with the cross-linking agent to form insoluble polymer particles.

3. The organic room temperature phosphorescent material according to claim 1, characterized in that: The polycyclic aromatic compound with a boronic acid group is selected from one or more of the following structures: 、 、 、 。 4. The organic room temperature phosphorescent material according to claim 1, characterized in that: The compound having a boronic acid group is incorporated in an amount of 0.2-1.0 wt % of the weight of the main matrix.

5. A method for preparing the organic room temperature phosphorescent material according to any one of claims 1 to 4, the method comprising: S1, preparing the host matrix into an aqueous solution, and then adding the guest molecule to obtain a mixed solution; S2, adding ammonia water to the mixed solution to form an alkaline environment, and heating in an oil bath for 10 to 30 minutes; S3, adding the cross-linking agent to the mixed solution to react to obtain insoluble polymer particles, filtering, washing, and drying to obtain an organic room temperature phosphorescent material.

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

7. The organic room temperature phosphorescent material according to any one of claims 1 to 4, characterized in that: The organic room temperature phosphorescent material is applied to the measurement of X-ray radiation.

8. The use of the organic room temperature phosphorescent material according to any one of claims 1 to 4, characterized in that: 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 the organic room temperature phosphorescent material is used as the surface color material of the optoelectronic device.

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