Two-component dopant, preparation method thereof, room-temperature phosphorescent afterglow material and application of room-temperature phosphorescent afterglow material

Abstract

The invention discloses a two-component dopant and a preparation method thereof, a room-temperature phosphorescent afterglow material and application of the room-temperature phosphorescent afterglow material, preparation raw materials at least comprise a host material and an organic guest material, and the organic guest material is a heteroatom organic molecule with a large conjugate plane structure. The room-temperature phosphorescence afterglow material prepared from the obtained two-component dopant can prolong the room-temperature phosphorescence service life and improve the quantum yield. The multicolor room-temperature phosphorescent afterglow material regulated and controlled by the water content has the characteristic of intelligently regulating the form, is stable in luminescent property, and can be used in air without inert gas protection or a vacuum environment. The afterglow is long in service life, visible to naked eyes, large in wavelength adjusting range, obvious in color change and suitable for various gel remodeling, three-dimensional casting molds, thermal mapping materials and flexible special materials.

Description

Technical Field

[0001] The present invention relates to the field of heterocyclic compounds, and in particular to a two-component dopant and a preparation method thereof, a room temperature phosphorescent afterglow material and an application thereof. Background Art

[0002] Room temperature phosphorescence (RTP) has attracted widespread attention due to its long-lasting luminescence properties and large Stokes shift. It has shown great application potential in fields such as information storage, bioimaging, and gel remodeling. Constructing long-life RTP afterglow materials is an important research direction. Traditional RTP afterglow materials have a relatively simple morphology and limited application scenarios. Using water content to control the morphology of RTP afterglow materials can adapt to applications in a variety of scenarios, but the presence of water will quench triplet excitons and affect the service life of the RTP afterglow material. Therefore, it is crucial to develop a RTP afterglow material whose morphology can be controlled by water content without affecting its service life.

[0003] Chinese invention patent application CN118047753A discloses a pyrrocarbonylcarbazole derivative and its application in phosphorescent materials. The pyrrocarbonylcarbazole derivative is mixed with a host compound in chloroform at a specific ratio, and the solvent is slowly evaporated at room temperature to produce a phosphorescent afterglow material. Compared to earlier phosphorescent materials, this material is less toxic and less expensive, and has great potential in the field of phosphorescent anti-counterfeiting. However, the material's morphology cannot be changed, resulting in a limited range of applications. Chinese invention patent application CN118620610A discloses a long-life organic room-temperature phosphorescent material, its synthesis method, and its application. By incorporating NH3·H2O into a host-guest structure composed of CA and BDA, an NH3·H2O-stimuli-responsive OURTP material, CB-N, is constructed. Its phosphorescence lifetime and quantum yield are significantly improved, but water vapor quenches the phosphorescence, and the material's morphology cannot be adjusted using water content, limiting its application. Summary of the Invention

[0004] In order to develop a room-temperature phosphorescent afterglow material whose morphology is regulated by water content and which does not affect its service life, the first aspect of the present invention provides a two-component dopant, the preparation raw materials of which include at least a host material and an organic guest material, the organic guest material is a heteroatom organic molecule with a large conjugated planar structure, and the host material is boric acid and its derivatives.

[0005] In one embodiment, the organic guest material includes at least one of 1,8-naphthalene dicarboxylic anhydride, 2,3-naphthalene dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, or 4,4',4"-triphenylamine tricarboxylate.

[0006] As an embodiment, when the organic guest material is 1,8-naphthalene dicarboxylic anhydride, the room temperature phosphorescent afterglow material is yellow; when the organic guest material is 2,3-naphthalene dicarboxylic anhydride, the room temperature phosphorescent afterglow material is green; when the organic guest material is 1,4,5,8-naphthalene tetracarboxylic anhydride, the room temperature phosphorescent afterglow material is red; when the organic guest material is 4,4',4"-triphenylamine tricarboxylate, the room temperature phosphorescent afterglow material is blue.

[0007] As an embodiment, the chemical structural formula of the 1,8-naphthalene dicarboxylic anhydride is shown in Formula (II-1), the chemical structural formula of the 2,3-naphthalene dicarboxylic anhydride is shown in Formula (II-2), the chemical structural formula of the 1,4,5,8-naphthalene tetracarboxylic anhydride is shown in Formula (II-3), and the chemical structural formula of the 4,4',4"-triphenylamine tricarboxylate is shown in Formula (II-4).

[0008]

[0009] In one embodiment, the organic guest material includes 2,3-naphthalene dicarboxylic anhydride.

[0010] As an embodiment, the weight ratio of the host material to the organic guest material is (95-99.5): (0.5-5).

[0011] As an embodiment, the host material is boric acid.

[0012] As an embodiment, the preparation raw materials further include water and an organic solvent, and the organic solvent includes at least one of dioxane, ethanol, methanol or tetrahydrofuran.

[0013] As an embodiment, the organic solvent includes dioxane.

[0014] During their experiments, the inventors discovered that using 2,3-naphthalic anhydride as an organic guest material and doping it with boric acid as a host material resulted in a dual-component room-temperature phosphorescent (RTP) afterglow material that achieved a long RTP lifetime of 1384.6 ms and a high quantum yield of 28.8%. The use of 2,3-naphthalic anhydride, a heteroatom organic molecule with a large conjugated planar structure, as an organic guest material extended the RTP lifetime and improved the quantum yield.

[0015] A second aspect of the present invention provides a method for preparing a dual-component dopant, comprising the following steps:

[0016] Mixing the host material and water to prepare a first solution;

[0017] mixing an organic guest material and an organic solvent to prepare a second solution;

[0018] The first solution and the second solution are mixed, and heated to volatilize water and organic solvent to obtain a precursor powder;

[0019] The precursor powder is placed in an air atmosphere and heat treated to obtain a dual-component doped body.

[0020] As an embodiment, the heat treatment temperature is 110-150°C, and the heat treatment time is 10-30 min.

[0021] As an embodiment, the heat treatment temperature is 120-140°C, and the heat treatment time is 15-25 min.

[0022] As an embodiment, the heat treatment temperature is 130°C, and the heat treatment time is 20 min.

[0023] As an embodiment, the heating temperature to volatilize water and organic solvent is 70-90°C.

[0024] As an embodiment, the heating temperature to volatilize water and organic solvent is 80°C.

[0025] A third aspect of the present application provides a room-temperature phosphor afterglow material, and the preparation raw materials at least include the above-mentioned dual-component doped body and choline chloride.

[0026] As an embodiment, the weight ratio of the dual-component doped body and choline chloride is 1:(1-3).

[0027] As an embodiment, the weight ratio of the dual-component doped body and choline chloride is 1:1.

[0028] As an embodiment, the room-temperature phosphor afterglow material is morphology-controlled by water content, and the water content is 0-200 μL / g.

[0029] As an embodiment, when the water content is 0 μL / g, the room-temperature phosphor afterglow material is in a powder state, when the water content is 40 μL / g, the room-temperature phosphor afterglow material is in a gel state, and when the water content is 200 μL / g, the room-temperature phosphor afterglow material is in a flow state.

[0030] The inventors mix choline chloride in the dual-component doped body to obtain a water content-controlled multi-morphology room-temperature phosphor afterglow material. The eutectic mixture formed based on different water contents exhibits different physical properties, the material has stable luminescence properties, can be used in air without inert gas protection or vacuum environment, has a long afterglow lifetime and is visible to the naked eye, has a large wavelength range and obvious color change, and is suitable for various gel remodeling, three-dimensional casting and flexible special materials and other application scenarios.

[0031] The fourth aspect of the present application provides an application of the room temperature phosphorescent afterglow material, which is applied in plastic gel materials, thermal mapping materials or flexible special materials.

[0032] As an implementation, the flexible special material includes but is not limited to ink writing materials.

[0033] As an implementation, the plastic gel material includes but is not limited to gel remodeling or three-dimensional casting.

[0034] Compared with the prior art, the present application has the following beneficial effects:

[0035] (1) The two-component doped body for preparing the room temperature phosphorescent afterglow material adopts a heteroatom organic molecule with a large conjugate plane structure as an organic guest material, and the room temperature phosphorescent afterglow material prepared from the obtained two-component doped body can prolong the room temperature phosphorescent lifetime and improve the quantum yield.

[0036] (2) The two-component doped body for preparing the room temperature phosphorescent afterglow material adopts 2,3-naphthalene dicarboxylic anhydride as an organic guest material and boronic acid as a host material for doping, and the room temperature phosphorescent afterglow material prepared from the obtained two-component doped body can achieve a long room temperature phosphorescent lifetime of 1384.6 ms and a high quantum yield of 28.8%.

[0037] (3) The room temperature phosphorescent afterglow material has the characteristics of intelligent adjustment of morphology by water content regulation, stable material luminescent properties, and can be used in air without inert gas protection or vacuum environment.

[0038] (4) The room temperature phosphorescent afterglow material has a long afterglow lifetime and is visible to the naked eye, has a large wavelength regulation range and obvious color change, and is suitable for various gel remodeling, three-dimensional casting, thermal mapping materials and flexible special materials.

[0039] (5) The room temperature phosphorescent afterglow material is regulated by water content, the material flexibility is enhanced with the increase of water content, and the lifetime is almost unchanged, which expands the application range of the room temperature phosphorescent afterglow material. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 The figure is a schematic diagram of the two-component doped body for preparing the room temperature phosphorescent afterglow material prepared in Embodiment 1-4 of the present application;

[0041] Figure 2 The figure is a room temperature phosphorescent excitation and emission spectrum of the two-component doped body prepared in Embodiment 1-4 of the present application;

[0042] Figure 3 The figure is a room temperature phosphorescent afterglow color coordinate diagram of the two-component doped body prepared in Embodiment 1-4 of the present application;

[0043] Figure 4 This is a room temperature phosphorescence emission decay lifetime diagram of the dual-component dopant prepared in Examples 1-4 of the present application;

[0044] Figure 5 This is an afterglow photograph of the dual-component dopant prepared in Examples 1-4 of the present application;

[0045] Figure 2-5 In Chinese: Example 1 corresponds to II-1; Example 2 corresponds to II-2; Example 3 corresponds to II-3; Example 4 corresponds to II-4.

[0046] Figure 6 A graph showing the relationship between the room temperature phosphorescence intensity and lifetime and the water content of the room temperature phosphorescent afterglow materials prepared in Examples 5-7 of the present application;

[0047] Figure 7 Afterglow images of the room temperature phosphorescent afterglow materials prepared in Examples 5-7 of the present application at different water content states, from left to right are Example 5, Example 6, and Example 7; the top is the UV-on state, and the bottom is the UV-off state;

[0048] Figure 8 Schematic diagram of gel molding and reshaping of the room temperature phosphorescent afterglow material prepared in Example 6 of the present application;

[0049] Figure 9 Schematic diagram of the application of the room temperature phosphorescent afterglow material gel three-dimensional mold prepared in Example 6 of the present application; from top to bottom, UV on state and UV off state;

[0050] Figure 10 This is a schematic diagram of the writing application of the room temperature phosphorescent afterglow material fluid ink prepared in Example 7 of the present application, from top to bottom: natural light, UV on state, and UV off state. DETAILED DESCRIPTION

[0051] The schematic diagram of the prepared dual-component dopant is shown in Figure 1 .

[0052] Example 1

[0053] A two-component dopant is prepared from raw materials including a host material and an organic guest material, water, and an organic solvent. The organic guest material is a heteroatom organic molecule with a large conjugated planar structure, such as 1,8-naphthalene dicarboxylic anhydride. The host material is boric acid.

[0054] The weight ratio of the host material to the organic guest material is 99:1.

[0055] The organic solvent is dioxane.

[0056] A method for preparing a two-component dopant comprises the following steps:

[0057] Mixing the main material and water, wherein the mass concentration of the main material is 1%, to prepare a first solution;

[0058] Mixing an organic guest material and an organic solvent, wherein the mass concentration of the organic guest material is 1%, to prepare a second solution;

[0059] mixing the first solution and the second solution, and heating until water and the organic solvent are volatilized to obtain a precursor powder;

[0060] The precursor powder is placed in an air atmosphere and subjected to heat treatment to obtain a two-component doped body.

[0061] The heat treatment temperature is 130° C. and the heat treatment time is 20 min.

[0062] The heating temperature until water and the organic solvent volatilize is 80°C.

[0063] Example 2

[0064] A two-component dopant and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the organic guest material is 2,3-naphthalene dicarboxylic anhydride.

[0065] Example 3

[0066] A two-component dopant and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the organic guest material is 1,4,5,8-naphthalenetetracarboxylic anhydride.

[0067] Example 4

[0068] A two-component dopant and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the organic guest material is 4,4',4"-triphenylamine tricarboxylate.

[0069] Example 5

[0070] A room temperature phosphorescent afterglow material is prepared by using raw materials including the two-component dopant prepared in Example 2 and choline chloride.

[0071] The weight ratio of the two-component dopant to choline chloride is 1:1.

[0072] The preparation method of the room temperature phosphorescent afterglow material is as follows:

[0073] The dual-component dopant prepared in Example 2 was evenly mixed with choline chloride to obtain a room temperature phosphorescent afterglow material.

[0074] Example 6

[0075] A room temperature phosphorescence material, the raw materials for preparation comprising a two-component dopant prepared in Example 2, choline chloride and water.

[0076] The weight ratio of the two-component dopant and choline chloride is 1:1.

[0077] The water content is 40 μL / g.

[0078] The preparation method of the room temperature phosphorescence material is as follows:

[0079] The two-component dopant prepared in Example 2 is mixed with choline chloride uniformly, and then water is added to obtain the room temperature phosphorescence material.

[0080] Example 7

[0081] A room temperature phosphorescence material, the raw materials for preparation comprising a two-component dopant prepared in Example 2, choline chloride and water.

[0082] The weight ratio of the two-component dopant and choline chloride is 1:1.

[0083] The water content is 200 μL / g.

[0084] The preparation method of the room temperature phosphorescence material is as follows:

[0085] The two-component dopant prepared in Example 2 is mixed with choline chloride uniformly, and then water is added to obtain the room temperature phosphorescence material.

[0086] Performance test

[0087] The room temperature phosphorescence excitation and emission spectra of the two-component dopants prepared in Examples 1-4 are shown in Figure 2 , and the phosphorescence color coordinate diagrams of the two-component dopants prepared in Examples 1-4 are shown in Figure 3 The two-component dopant prepared in Example 1 shows room temperature phosphorescence emission at 556 nm, and a yellow long afterglow is visible to the naked eye; the two-component dopant prepared in Example 2 shows room temperature phosphorescence emission at 500 nm, and a green long afterglow is visible to the naked eye; the two-component dopant prepared in Example 3 shows room temperature phosphorescence emission at 602 nm and 655 nm, and a red long afterglow is visible to the naked eye; and the two-component dopant prepared in Example 4 shows room temperature phosphorescence emission at 490 nm, and a blue long afterglow is visible to the naked eye.

[0088] The room temperature phosphorescence emission decay lifetime diagrams of the two-component dopants prepared in Examples 1-4 are shown in Figure 4 , Figure 4After fitting, it was calculated that the room temperature phosphorescence of the two-component doped body in Example 1 was 838.5 ms, the room temperature phosphorescence of the two-component doped body in Example 2 was 1384.6 ms, the room temperature phosphorescence of the two-component doped body in Example 3 was 64.1 ms, and the room temperature phosphorescence of the two-component doped body in Example 4 was 202.6 ms.

[0089] The afterglow photos of the dual-component doped bodies prepared in Examples 1-4 are shown in Figure 5 The two-component doped body prepared in Example 1 can exhibit a long afterglow of 4 seconds at room temperature, the two-component doped body prepared in Example 1 can exhibit a long afterglow of 10 seconds at room temperature, the two-component doped body prepared in Example 3 can exhibit a long afterglow of 1 second at room temperature, and the two-component doped body prepared in Example 4 can exhibit a long afterglow of 3 seconds at room temperature.

[0090] The relationship between the room temperature phosphorescence intensity and life span of the room temperature phosphorescence afterglow materials prepared in Examples 5-7 and the water content is shown in FIG. Figure 6 , the room temperature phosphorescence intensity shows a downward trend with the increase of water content, and the life span remains basically unchanged.

[0091] The afterglow pictures of the room temperature phosphorescent afterglow materials prepared in Examples 5-7 under different water contents are shown in Figure 7 The room temperature phosphorescent afterglow materials prepared in Examples 5, 6, and 7 are in three forms: powder, gel, and fluid. All three exhibit bright green ultra-long room temperature phosphorescent afterglow. The gel material exhibits good plasticity, while the fluid material has excellent fluidity.

[0092] The schematic diagram of the gel forming and reshaping of the room temperature phosphorescent afterglow material prepared in Example 6 is shown in FIG. Figure 8 , Figure 8 From left to right, the steps of compression and reshaping are shown, showing that during the forming and reshaping process, the gel provided in Example 6 of the present application exhibits excellent plasticity without loss of phosphorescence performance.

[0093] The schematic diagram of the application of the three-dimensional casting mold of the room temperature phosphorescent afterglow material gel prepared in Example 6 is shown in FIG. Figure 9 By customizing molds containing different texts / patterns, precise preparation of three-dimensional structures can be achieved, demonstrating the application prospects of this material in customized light-emitting devices.

[0094] The schematic diagram of the room temperature phosphorescent afterglow material fluid ink writing application prepared in Example 7 is shown in FIG. Figure 10 ,like Figure 10As shown, the fluid material with high water content has excellent fluidity, which is suitable for fluid painting and ink writing. The fluid and ink prepared based on different water content show green room-temperature phosphorescence after the 365 nm UV light source is turned off. Among them, the "ECUST" fluid coating can firmly adhere to the surface of the paper, and the "Dajiji" ink trace is completely invisible under ambient light, but clearly developed after UV excitation, which demonstrates the information storage function of the material in a covert manner.

Claims

1. A two-component dopant, characterized in that: The preparation raw materials at least include a main material and an organic guest material. The organic guest material is a heteroatom organic molecule with a large conjugated plane structure. The main material is boric acid and its derivatives.

2. The dual-component dopant according to claim 1, characterized in that: The organic guest material includes at least one of 1,8-naphthalene dicarboxylic anhydride, 2,3-naphthalene dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride or 4,4',4"-triphenylamine tricarboxylate.

3. The dual-component dopant according to claim 1, characterized in that: The weight ratio of the host material to the organic guest material is (95-99.5): (0.5-5).

4. The dual-component dopant according to claim 2, characterized in that: The preparation raw materials also include water and an organic solvent, and the organic solvent includes at least one of dioxane, ethanol, methanol or tetrahydrofuran.

5. A method for preparing a dual-component dopant according to any one of claims 1 to 4, characterized in that: The following steps are involved: Mixing the host material and water to prepare a first solution; mixing an organic guest material and an organic solvent to prepare a second solution; mixing the first solution and the second solution, and heating until water and the organic solvent are volatilized to obtain a precursor powder; The precursor powder is placed in an air atmosphere and subjected to heat treatment to obtain a two-component doped body.

6. The method for preparing a dual-component dopant according to claim 5, characterized in that: The heat treatment temperature is 110-150° C., and the heat treatment time is 10-30 minutes.

7. A room temperature phosphorescent afterglow material, characterized in that: The preparation raw materials at least include the two-component dopant according to any one of claims 1 to 4 and choline chloride.

8. The room temperature phosphorescent afterglow material according to claim 7, characterized in that: The weight ratio of the two-component dopant to choline chloride is 1:(1-3).

9. The room temperature phosphorescent afterglow material according to claim 7, characterized in that: The morphology of the room temperature phosphorescent afterglow material is regulated by water content, and the water content is 0-200 μL / g.

10. Use of the room temperature phosphorescent afterglow material according to any one of claims 7 to 9, characterized in that: Used in plastic gel materials, thermal mapping materials or flexible specialty materials.

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