An organic room temperature phosphorescent material with ultra-long phosphorescence life and a preparation method thereof

Abstract

The present invention belongs to the technical field of optical materials, and specifically discloses an organic room temperature phosphorescent material with an ultra-long phosphorescence life and a preparation method thereof, wherein the organic room temperature phosphorescent material comprises a host material and a guest material, wherein: the host material is a rigid polymer, and the guest material is a polycyclic aromatic compound or a derivative thereof that does not contain heavy atoms and heteroatoms. The present invention uses a polycyclic aromatic compound or a derivative thereof that does not contain heavy atoms and heteroatoms as a guest material and a rigid polymer as a host material, thereby obtaining an organic room temperature phosphorescent material with ultra-large Stokes shift and ultra-long phosphorescence life characteristics. At the same time, by adjusting the degree of conjugation of the doped polycyclic aromatic compound and changing the lowest triplet energy level of the guest molecule, the phosphorescence color and life of the material are regulated, and the excellent performance of the maximum phosphorescence emission wavelength>750nm, the longest phosphorescence life>3500ms, and the afterglow visible to the naked eye>65s is achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical materials, and in particular relates to an organic room temperature phosphorescent material with an ultra-long phosphorescence life and a preparation method thereof. Background Art

[0002] Organic luminescence refers to the process in which an excited exciton deactivates from the excited state to the ground state through radiative transition (emission of photons). Among them, fluorescence emission refers to the process in which a singlet exciton emits a photon. Different from fluorescence emission, phosphorescence emission is a process in which a singlet excited exciton first passes through intersystem crossing to a triplet excited state, then returns to the first excited triplet state through internal conversion and vibrational relaxation, and then deactivates by emitting photons. Since this is a slow process (>1μs), phosphorescence has a lifetime of microseconds or even seconds. Because of this characteristic, phosphorescent materials have attracted more and more attention.

[0003] Organic room temperature phosphor materials have attractive application prospects in many high-tech fields such as optical recording, data encryption, sensing, OLED, and bio-imaging due to their simple synthesis, low price, good biocompatibility, and easy functional group modification. Among them, polymer-based organic room temperature phosphorescent materials are considered to be the most promising type of phosphorescent materials for large-scale practical applications because of their advantages such as easy processing, good flexibility, and transparency.

[0004] However, polymer-based organic phosphorescent materials still have some problems, such as weak spin-orbit coupling ability and slow radiation transition rate of triplet excitons, which makes them easily inactivated by the environment. In addition, the polymer-based organic room temperature phosphorescent materials that have been developed still have problems such as complex synthesis, high cost, short phosphorescence lifetime, and single color, which also limit their practical application prospects in various fields.

[0005] With the continuous deepening of research, a variety of strategies have been developed to achieve the construction of polymer-based organic room temperature phosphorescent materials. For non-doped polymer systems, the potential phosphorescent chromophores are mainly positioned in the main chain, side chain, end or bridge of the polymer through copolymerization or homopolymerization; however, this process is usually cumbersome, prone to pollution, and the cost is relatively high. For doped polymer systems, the phosphor and polymer are mixed together mainly through physical blending and intermolecular interactions. Although this strategy currently has obvious advantages in the preparation of polymer-based organic room temperature phosphorescent materials, there are also many problems, such as the small number of available phosphors, the prepared phosphorescent materials are mostly yellow and green with short lifespans, and low phosphorescence quantum yields. Although these strategies can effectively improve the performance of different aspects of phosphorescence, they still need to be further improved.

[0006] Therefore, it is very necessary to explore a strategy for doped polymer-based organic room temperature phosphorescent materials that are simple to synthesize, have a variety of raw material choices, are low in price, and have ultra-long lifetimes and tunable phosphorescent colors. Summary of the invention

[0007] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes an organic room temperature phosphorescent material with ultra-long phosphorescence life and a preparation method thereof, wherein the organic room temperature phosphorescent material has ultra-large Stokes shift and ultra-long phosphorescence life, and has high transparency, various colors, and can be bent and stretched, and has broad application prospects.

[0008] The inventive concept of the present invention is as follows: the organic room temperature phosphorescent material of the present invention is based on the strategy of constructing a charge transfer state to promote intersystem crossing. Since charge transfer is easy to occur between the guest aromatic condensed ring and the main rigid polymer, a charge transfer state is formed; and when the charge is compounded, the charge transfer state can be converted into a guest triplet state, so that the number of guest triplet states is significantly increased, thereby emitting phosphorescence. At the same time, the present invention adjusts the degree of conjugation of the guest polycyclic aromatic compound and changes the lowest triplet energy level of the guest molecule, thereby achieving the regulation of the phosphorescence color and life of the material, and obtaining an organic room temperature phosphorescent material with ultra-large Stokes shift and ultra-long phosphorescence life characteristics, achieving a maximum phosphorescence emission wavelength of >750nm, a maximum phosphorescence life of >3500ms, and a visible afterglow of >65s.

[0009] It should be noted that the ultra-large Stokes shift means that the maximum phosphorescence emission wavelength is >350nm; the ultra-long phosphorescence lifetime means that the longest phosphorescence lifetime is >3000ms, and the afterglow visible to the naked eye is >30s.

[0010] To solve the above technical problems, the first aspect of the present invention provides an organic room temperature phosphorescent material, including a host material and a guest material, wherein the host material is a rigid polymer, and the guest material is a polycyclic aromatic compound or a derivative thereof that does not contain heavy atoms and heteroatoms.

[0011] Preferably, the structural formula of the polycyclic aromatic compound or its derivative is selected from any one of the following:

[0012]

[0013] Further preferably, the structural formula of the polycyclic aromatic compound or its derivative is selected from any one of the following:

[0014]

[0015] Preferably, the rigid polymer is selected from at least one of polyvinyl pyrrolidone, polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, polycarbonate, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, epoxy resin, polyurethane, and polylactic acid.

[0016] Further preferably, the rigid polymer is polyvinyl pyrrolidone.

[0017] Preferably, the guest material is incorporated in an amount of 0.01-20 wt % of the host material; further preferably, the guest material is incorporated in an amount of 0.1-10 wt % of the host material; further preferably, the guest material is incorporated in an amount of 0.1-1 wt % of the host material.

[0018] Preferably, the organic room temperature phosphorescent material has a maximum phosphorescence emission wavelength of >750nm, a maximum phosphorescence lifetime of >3500ms, and an afterglow visible to the naked eye of >65s.

[0019] The second aspect of the present invention provides a method for preparing the above-mentioned organic room temperature phosphorescent material, which comprises a solvent volatilization method or a melt cooling method.

[0020] Preferably, the solvent volatilization method comprises the following steps:

[0021] The host material and the guest material are dissolved in an organic solvent to obtain a precursor solution; and the organic solvent is removed to obtain the organic room temperature phosphorescent material.

[0022] Preferably, the organic solvent is removed by natural volatilization, that is, the precursor solution is placed in a ventilated place to remove the organic solvent by free volatilization of the solvent.

[0023] The selection and amount of the organic solvent are determined according to the solubility of the guest material polycyclic aromatic compound and the host material rigid polymer, and are carried out according to the existing technology in the field.

[0024] Preferably, the melt cooling method comprises the following steps:

[0025] The host material and the guest material are mixed, heated and melted to obtain a precursor melt; and cooled to obtain the organic room temperature phosphorescent material.

[0026] The heating temperature can be set to a temperature that allows the main material to become plastic or fluid, and is carried out according to the prior art in the art. For example, when polyvinyl pyrrolidone is selected as the main material, the heating and melting temperature is 190-210°C.

[0027] The third aspect of the present invention provides the application of the above-mentioned organic room temperature phosphorescent material in information storage, anti-counterfeiting coatings, 3D anti-counterfeiting products, data encryption and anti-counterfeiting, special printing technology, programmable labels or biological imaging.

[0028] Preferably, the anti-counterfeiting coating uses the precursor solution prepared by the solvent volatilization method as coating, which is directly used for writing, painting or coating, and after the solvent is completely evaporated, a product with phosphorescent emission can be obtained.

[0029] Preferably, the 3D anti-counterfeiting product can be cast into molds of different shapes, shaped, and modified by using the precursor solution prepared by the solvent volatilization method or the precursor melt prepared by the melt cooling method to obtain a phosphorescent 3D anti-counterfeiting product of a desired shape.

[0030] Preferably, the programmable label includes the organic room temperature phosphorescent material, and writing is completed by irradiating the label with an ultraviolet light mask, using the required pattern or text as information storage. After writing is completed, it is excited with ultraviolet light, and the written information can be read after the ultraviolet light is removed; after heating and annealing, the pattern or text can be written again and recycled.

[0031] Compared with the prior art, the above technical solution of the present invention has at least the following technical effects or advantages:

[0032] (1) The present invention uses a specific polycyclic aromatic compound or its derivatives that do not contain heavy atoms and heteroatoms as the guest material and a rigid polymer as the host material to obtain an organic room temperature phosphorescent material with ultra-large Stokes shift and ultra-long phosphorescence lifetime. At the same time, the present invention adjusts the conjugation degree of the guest polycyclic aromatic compound and changes the lowest triplet energy level of the guest molecule, thereby achieving the regulation of the phosphorescence color and lifetime of the material, achieving the excellent performance of the maximum phosphorescence emission wavelength>750nm, the longest phosphorescence lifetime>3500ms, and the afterglow visible to the naked eye>65s.

[0033] (2) The present invention adopts a solution volatilization method or a melt cooling method to prepare an organic room temperature phosphorescent material. The host and guest materials used are widely available, low in price, and have good biocompatibility. The preparation process is simple and convenient, easy to operate, short in time, and does not require the use of expensive instruments. The prepared phosphorescent material has excellent luminescent properties, high transparency, various colors, and can be bent and stretched. It can be widely used in information storage, anti-counterfeiting coatings, 3D anti-counterfeiting products, data encryption and anti-counterfeiting, special printing technology, programmable labels, biological imaging and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the benzo[c]phenanthrene / PVP material prepared in Example 1;

[0035] Figure 2 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the Qu / PVP material prepared in Example 2;

[0036] Figure 3 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the fluoranthene / PVP material prepared in Example 3;

[0037] Figure 4 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the pyrene / PVP material prepared in Example 4;

[0038] Figure 5 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the benzo[A]anthracene / PVP material prepared in Example 5;

[0039] Figure 6 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the chrysanthemum / PVP material prepared in Example 6;

[0040] Figure 7 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the dibenzo(a,h)anthracene / PVP material prepared in Example 7;

[0041] Figure 8 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the dibenzo[g,p]fused dinaphthalene / PVP material prepared in Example 8;

[0042] Fig. 9 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the benzo(g,h,i)perylene / PVP material prepared in Example 9;

[0043] Fig.10 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the coronene / PVP material prepared in Example 10;

[0044] Fig.11 Phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in Examples 1-10;

[0045] Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in Examples 1-10;

[0046] Fig.13 This is an example diagram of the application of the organic room temperature phosphorescent anti-counterfeiting coating in a quartz plate prepared in Example 11;

[0047] Fig.14 This is an example diagram of the application of the organic room temperature phosphorescent anti-counterfeiting coating prepared in Example 11 on white paper;

[0048] Fig.15This is a physical picture of the organic room temperature phosphorescent 3D anti-counterfeiting product prepared in Example 12;

[0049] Fig.16 This is an application example diagram of a programmable label with phosphorescent properties prepared in Example 13;

[0050] Fig.17 The fluorescence emission spectrum of the anthracene / PVP material prepared in Comparative Example 1;

[0051] Fig.18 The pyrene / PMMA material and fluorescence emission spectrum prepared in Comparative Example 2. DETAILED DESCRIPTION

[0052] The present invention is described in detail below in conjunction with the examples, so that the technical personnel of the relevant technical field can understand the present invention. It is necessary to point out here that the examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. The non-essential improvements and adjustments made to the present invention by the skilled person in the relevant field according to the above invention content should still belong to the scope of protection of the present invention. At the same time, the raw materials mentioned below that are not described in detail are all commercially available products; the process steps or preparation methods that are not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0053] Example 1

[0054] A preparation method of a benzo[c]phenanthrene / PVP material comprises the following steps:

[0055] Wherein: the guest material is benzo[c]phenanthrene, and its structural formula is shown in the following formula 1:

[0056] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0057] (1) Weigh an appropriate amount of sample according to a mass ratio of benzo[c]phenanthrene to polyvinyl pyrrolidone of 1:100, and dissolve the weighed benzo[c]phenanthrene and polyvinyl pyrrolidone in dichloromethane, so that the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0058] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a green organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0059] Figure 1 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the benzo[c]phenanthrene / PVP material prepared in this example, the excitation light wavelength is 365nm; Fig.11The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0060] Example 2

[0061] A preparation method of a polyvinylpyrrolidone (PVP) material comprises the following steps:

[0062] Wherein: the object material is quenched, and its structural formula is shown in Formula 2 below:

[0063] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0064] (1) Weigh an appropriate amount of sample at a mass ratio of chrysene to polyvinyl pyrrolidone of 1:100, dissolve the weighed chrysene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0065] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a yellow-green organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0066] Figure 2 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the Qu / PVP material prepared in this example, the excitation light wavelength is 365nm; Fig.11 The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0067] Example 3

[0068] A preparation method of fluoranthene / PVP material comprises the following steps:

[0069] Wherein: the guest material is fluoranthene, and its structural formula is shown in Formula 3 below:

[0070] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0071] (1) Weigh an appropriate amount of sample at a mass ratio of fluoranthene to main polyvinyl pyrrolidone of 1:100, dissolve the weighed fluoranthene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0072] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a yellow organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0073] Figure 3 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the fluoranthene / PVP material prepared in this example, the excitation light wavelength is 365nm; Fig.11 The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0074] Example 4

[0075] A preparation method of pyrene / PVP material comprises the following steps:

[0076] Wherein: the guest material is pyrene, and its structural formula is shown in Formula 4 below:

[0077] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0078] (1) Weigh an appropriate amount of sample at a mass ratio of pyrene to main polyvinyl pyrrolidone of 1:100, dissolve the weighed pyrene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0079] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a red organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0080] Figure 4 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the pyrene / PVP material prepared in this example, the excitation light wavelength is 365nm; Fig.11 The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0081] Example 5

[0082] A preparation method of a benzo[A]anthracene / PVP material comprises the following steps:

[0083] Wherein: the guest material is benzo[A]anthracene, and its structural formula is shown in Formula 5 below:

[0084] Polyvinylpyrrolidone (PVP) is the main polymer material.

[0085] (1) Weigh an appropriate amount of the sample according to the mass ratio of benzo[a]anthracene to the main polyvinylpyrrolidone of 1:100. Dissolve the weighed benzo[a]anthracene and polyvinylpyrrolidone in dichloromethane. The concentration of polyvinylpyrrolidone in the obtained precursor solution is 100 mg / mL;

[0086] (2) Drop the precursor solution on a quartz plate. After the dichloromethane has completely evaporated, cover the surface of the material with another quartz plate at 100 °C. After irradiating with ultraviolet light for 30 s (to consume the residual oxygen in the material), a wine-red organic room-temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0087] Figure 5 This is the fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the benzo[a]anthracene / PVP material prepared in this example. The excitation light wavelength is 365 nm; Fig.11 This shows the phosphorescence effect diagram of the organic room-temperature phosphorescent material prepared in this example; Fig.12 This shows the phosphorescence lifetime diagram of the organic room-temperature phosphorescent material prepared in this example.

[0088] Example 6

[0089] The preparation of a picene / PVP material includes the following steps:

[0090] Among them: The guest material is picene, and its structural formula is as shown in Formula 6 below:

[0091] Polyvinylpyrrolidone (PVP) is the main polymer material.

[0092] (1) Weigh an appropriate amount of the sample according to the mass ratio of picene to the main polyvinylpyrrolidone of 1:100. Dissolve the weighed picene and polyvinylpyrrolidone in diethyl ether. The concentration of polyvinylpyrrolidone in the obtained precursor solution is 100 mg / mL;

[0093] (2) Drop the precursor solution on a quartz plate. After the diethyl ether has completely evaporated, cover the surface of the material with another quartz plate at 100 °C. After irradiating with ultraviolet light for 30 s (to consume the residual oxygen in the material), a green organic room-temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0094] Figure 6 This is the fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the picene / PVP material prepared in this example. The excitation light wavelength is 370 nm; Fig.11 This shows the phosphorescence effect diagram of the organic room-temperature phosphorescent material prepared in this example; Fig.12The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0095] Example 7

[0096] A preparation method of a dibenzo(a,h)anthracene / PVP material comprises the following steps:

[0097] Wherein: the guest material is dibenzo(a,h)anthracene, and its structural formula is shown in Formula 7 below:

[0098] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0099] (1) Weigh an appropriate amount of sample at a mass ratio of dibenzo(a,h)anthracene to main polyvinyl pyrrolidone of 1:100, dissolve the weighed dibenzo(a,h)anthracene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0100] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a brown organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0101] Figure 7 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the dibenzo(a,h)anthracene / PVP material prepared in this example, the excitation light wavelength is 370nm; Fig.11 The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0102] Example 8

[0103] A preparation method of a dibenzo[g,p]fused dinaphthalene / PVP material comprises the following steps:

[0104] Wherein: the guest material is dibenzo[g,p]fused dinaphthalene, and its structural formula is shown in Formula 8 below:

[0105] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0106] (1) Weigh an appropriate amount of sample according to the mass ratio of dibenzo[g,p]-fused dinaphthalene to main polyvinyl pyrrolidone of 1:100, dissolve the weighed dibenzo[g,p]-fused dinaphthalene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0107] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a red organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0108] Figure 8 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the dibenzo[g,p]fused dinaphthalene / PVP material prepared in this example, the excitation light wavelength is 380nm; Fig.11 The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0109] Example 9

[0110] A preparation method of benzo(g,h,i)perylene / PVP material comprises the following steps:

[0111] Wherein: the guest material is benzo(g,h,i)perylene, and its structural formula is shown in Formula 9 below:

[0112]

[0113] , polyvinyl pyrrolidone (PVP) is the main polymer material.

[0114] (1) Weigh an appropriate amount of sample according to the mass ratio of benzo(g,h,i)perylene to the main polyvinyl pyrrolidone of 1:100, dissolve the weighed benzo(g,h,i)perylene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0115] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a wine-red organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0116] Fig. 9 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the benzo(g,h,i)perylene / PVP material prepared in this example, the excitation light wavelength is 380nm; Fig.11 The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0117] Example 10

[0118] A preparation method of a coronene / PVP material comprises the following steps:

[0119] Wherein: the guest material is coronene, and its structural formula is shown in the following formula 10:

[0120] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0121] (1) Weighing an appropriate amount of sample according to the mass ratio of coronene to main polyvinyl pyrrolidone of 1:100, dissolving the weighed coronene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0122] (2) The precursor solution is dropped onto a quartz plate. After the dichloromethane evaporates, another quartz plate is pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), a yellow-green organic room temperature phosphorescent material encapsulated between the quartz plates is obtained.

[0123] Fig.10 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the coronene / PVP material prepared in this example, the excitation light wavelength is 380nm; Fig.11 The phosphorescence effect diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG. Fig.12 The phosphorescence lifetime diagram of the organic room temperature phosphorescent material prepared in this embodiment is shown in FIG.

[0124] Fig.12 The photophysical data of the organic room temperature phosphorescent materials prepared in Examples 1-10 are shown in Table 1, wherein: the wavelength of the fluorescence excitation light is 375 nm, the wavelength of the phosphorescence excitation light is 365 nm, and the delay time is 1 ms.

[0125] Table 1: Photophysical data of organic room temperature phosphorescent materials prepared in Examples 1-10

[0126]

[0127] Embodiment 11

[0128] A preparation method of a room temperature phosphorescent anti-counterfeiting coating having multiple colors comprises the following steps:

[0129] (1) The precursor solutions prepared in step (1) of Examples 1-10 are respectively used as phosphorescent anti-counterfeiting coating inks, denoted as inks 1-10;

[0130] (2) Use ink 1-10 for writing, drawing or coating on a quartz sheet or white paper, and after the solvent evaporates completely, an organic room temperature phosphorescent anti-counterfeiting coating is obtained.

[0131] Fig.13This is an example diagram of the application of the organic room temperature phosphorescent anti-counterfeiting coating prepared in this embodiment in a quartz sheet. Fig.14 This is an example diagram of the application of the organic room temperature phosphorescent anti-counterfeiting coating prepared in this embodiment in white paper.

[0132] Example 12

[0133] A preparation method of an organic room temperature phosphorescent 3D anti-counterfeiting product comprises the following steps:

[0134] (1) Weighing an appropriate amount of sample according to a mass ratio of guest material (structural formula such as any one of Formulas 1-10) to polyvinyl pyrrolidone of 1:100, heating the weighed guest material and polyvinyl pyrrolidone to melt at 200° C., and mixing them uniformly to obtain a precursor melt;

[0135] (2) The precursor melt is poured into molds of different shapes, and after being completely cooled, organic room temperature phosphorescent 3D anti-counterfeiting products of various shapes are obtained through shaping and modification.

[0136] Fig.15 This is a physical picture of the organic room temperature phosphorescent 3D anti-counterfeiting product prepared in this embodiment.

[0137] Example 13

[0138] A preparation method of a programmable label having room temperature phosphorescence property comprises the following steps:

[0139] (1) The precursor solutions prepared in step (1) of Examples 1-10 are respectively evenly applied to a quartz plate, and after the solvent is completely evaporated, a room temperature phosphorescent film is obtained;

[0140] (2) The room temperature phosphorescent film is irradiated with an ultraviolet mask, and a programmable label with room temperature phosphorescent properties is obtained after writing; after writing, it is excited with ultraviolet light, and the written information can be read after the ultraviolet light is removed. After heating and annealing, it can be rewritten and recycled.

[0141] Fig.16 This is an application example diagram of the programmable label with room temperature phosphorescence properties prepared in this embodiment.

[0142] Comparative Example 1

[0143] A preparation method of anthracene / PVP material comprises the following steps:

[0144] Wherein: the guest material is anthracene, and its structural formula is shown in the following formula 11:

[0145] Polyvinyl pyrrolidone (PVP) is the main polymer material.

[0146] (1) Weigh an appropriate amount of sample at a mass ratio of anthracene to main polyvinyl pyrrolidone of 1:100, dissolve the weighed anthracene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polyvinyl pyrrolidone in the obtained precursor solution is 100 mg / mL;

[0147] (2) The precursor solution was dropped onto a quartz plate. After the dichloromethane evaporated, another quartz plate was pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), no phosphorescence was observed.

[0148] Fig.17 The fluorescence emission spectrum of the anthracene / PVP material prepared in this comparative example has an excitation light wavelength of 365 nm.

[0149] Comparative Example 2

[0150] A preparation method of pyrene / PMMA material comprises the following steps:

[0151] Wherein: the guest material is pyrene, and its structural formula is shown in the following formula 12:

[0152] Polymethyl methacrylate (PMMA) is the main polymer material.

[0153] (1) Weigh an appropriate amount of sample according to the mass ratio of pyrene to polymethyl methacrylate of 1:100, dissolve the weighed pyrene and polyvinyl pyrrolidone in dichloromethane, and the concentration of polymethyl methacrylate in the obtained precursor solution is 100 mg / mL;

[0154] (2) The precursor solution was dropped onto a quartz plate. After the dichloromethane evaporated, another quartz plate was pressed onto the surface of the material at 100°C. After irradiation with ultraviolet light for 30 seconds (to consume the residual oxygen in the material), no phosphorescence was observed.

[0155] Fig.18 The fluorescence emission spectrum of the pyrene / PMMA material prepared in this comparative example has an excitation light wavelength of 365 nm.

[0156] For ordinary technicians in the technical field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, without having to go through creative labor. Therefore, simple improvements made to the present invention by those skilled in the art based on the disclosure of the present invention should be within the protection scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all processes similar to the present invention and equivalent changes made should belong to the protection scope of the present invention.

Claims

1. An organic room temperature phosphorescent material, characterized in that: The invention comprises a main material and a guest material, wherein the main material is a rigid polymer, and the guest material is a polycyclic aromatic compound or a derivative thereof without heavy atoms and heteroatoms; the rigid polymer is polyvinyl pyrrolidone, and the structural formula of the polycyclic aromatic compound or a derivative thereof is selected from any one of the following:

2. The organic room temperature phosphorescent material according to claim 1, characterized in that: The guest material is added in an amount of 0.01-20 wt % of the host material.

3. The organic room temperature phosphorescent material according to claim 1, characterized in that: The longest phosphorescence lifetime of the organic room temperature phosphorescent material is >3500ms, and the afterglow visible to the naked eye is >65s.

4. A method for preparing an organic room temperature phosphorescent material according to any one of claims 1 to 3, characterized in that: The preparation method includes a solvent volatilization method or a melt cooling method; the solvent volatilization method includes the following steps: The host material and the guest material are dissolved in an organic solvent to obtain a precursor solution; and the organic solvent is removed to obtain the organic room temperature phosphorescent material.

5. The method for preparing an organic room temperature phosphorescent material according to claim 4, characterized in that: The melt cooling method comprises the following steps: The host material and the guest material are mixed, heated and melted to obtain a precursor melt; and cooled to obtain the organic room temperature phosphorescent material.

6. Application of the organic room temperature phosphorescent material according to any one of claims 1 to 3 in information storage, anti-counterfeiting coatings, 3D anti-counterfeiting products, data encryption and anti-counterfeiting, printing technology, programmable labels or bio-imaging.

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