A phosphorescent gel with three-dimensional shaping function, its preparation method and application

Abstract

The present invention discloses a phosphorescent gel with three-dimensional shaping function, its preparation method and application. The preparation method of the phosphorescent gel with three-dimensional shaping function of the present invention comprises the following steps: mixing phosphoric acid, diethylenetriamine and water in a volume ratio of (10-15):(12-32):(20-45) to form a mixed solution, and then carrying out microwave hydrothermal reaction on the mixed solution for 1.5-13 min under the condition of microwave power of 200-800 W to obtain the phosphorescent gel with three-dimensional shaping function. The phosphorescent gel not only has good fluorescence performance, but also has excellent three-dimensional plasticity, and can be applied to the preparation of luminous glue, decorative materials, smart windows and phosphorescent devices.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and more specifically, to a phosphorescent gel with three-dimensional shaping function, its preparation method and application. Background Art

[0002] In recent years, as one of the afterglow materials, room temperature phosphorescent materials have shown outstanding application advantages in the fields of optical anti-counterfeiting, LED display, biological imaging, etc. after being combined with organic materials due to their unique triplet state, long afterglow lifetime, high electroluminescence efficiency and other characteristics. However, the generation of room temperature phosphorescence mainly stems from the spin-forbidden transition of electrons, and it is extremely easy to be destroyed by water or oxygen in the air at room temperature. Therefore, there are many difficulties in realizing room temperature phosphorescence.

[0003] Currently, room temperature phosphorescence is mainly achieved by preparing carbon quantum dot nanomaterials. For example, a preparation method of a long afterglow material is disclosed in the prior art. Using polyethyleneimine as the amine source, phosphoric acid as the phosphorus source, and mixing with ultrapure water and then heating by microwave to form a crude product; then, dissolving it in ultrapure water, centrifuging and separating, taking the supernatant and filtering, and then putting the filtrate into a dialysis bag with a molecular weight cut-off of 1000Da for dialysis; finally, freeze-drying the dialyzed product in a vacuum freeze dryer to obtain the long afterglow material. This long afterglow material has the advantages of small particle size, high phosphorescence intensity and long duration, but without being compounded with other matrices, the three-dimensional plasticity of the phosphorescent molecules themselves is poor. Summary of the Invention

[0004] The purpose of the present invention is to maintain the high phosphorescence performance of the existing phosphorescent materials while overcoming the defects and deficiencies of their own difficulty in shaping, and provide a preparation method of a phosphorescent gel with three-dimensional shaping function. By carrying out microwave hydrothermal reaction for 1.5 - 13 minutes at a power of 200 - 800W with phosphoric acid, diethylenetriamine and water in a specific volume ratio, a phosphorescent gel with three-dimensional shaping function can be prepared.

[0005] Another purpose of the present invention is to provide a phosphorescent gel with three-dimensional shaping function.

[0006] Another purpose of the present invention is to provide a phosphorescent device.

[0007] Another purpose of the present invention is to provide the application of the phosphorescent gel with three-dimensional shaping function in the preparation of luminous glue, decorative materials, smart windows and phosphorescent devices.

[0008] The above purposes of the present invention are achieved through the following technical solutions:

[0009] A method for preparing a phosphorescent gel with a three-dimensional shaping function comprises the following steps: uniformly mixing a phosphorus source, a polyamine, and water to form a mixed solution, and then subjecting the mixed solution to a microwave hydrothermal reaction, wherein the phosphorescent gel with a three-dimensional shaping function is obtained after the reaction is complete;

[0010] The phosphorus source is phosphoric acid; the polyamine is diethylenetriamine;

[0011] The volume ratio of the phosphorus source: polyamine: water is (10-15): (12-32): (20-45);

[0012] The microwave power of the microwave hydrothermal reaction is 200-800W, and the time of the microwave hydrothermal reaction is 1.5-13 minutes.

[0013] The present invention utilizes a combination of a specific phosphorus source (phosphoric acid) and a polyamine (diethylenetriamine) and, by regulating the microwave power and reaction time of a microwave hydrothermal reaction, is able to produce a phosphorescent gel with excellent three-dimensional shaping capabilities. It was also found that when the amount of phosphoric acid added is too high, the phosphorescent gel becomes darker (brown or tan) and has reduced transparency. However, when the amount of phosphoric acid added is too low, the gel cannot be fully solidified, and its phosphorescence afterglow is dramatically reduced, or even completely invisible.

[0014] When too little polyamine is added, it is difficult to form a phosphorescent gel; when too much polyamine is added, a large number of bubbles will appear in the phosphorescent gel, reducing its tensile strength and flexural strength, making it difficult to meet the actual application requirements of the phosphorescent gel, and also resulting in an extremely short phosphorescence afterglow time. When water is used as a solvent, if it is added in too much, the microwave hydrothermal reaction time needs to be extended, resulting in excessive condensation reaction between phosphoric acid and diethylenetriamine, making the molecular weight of the phosphorescent gel larger, the viscosity increased, and the fluidity worse. When preparing complex three-dimensional devices, it is difficult to fully fill the entire mold, resulting in an incomplete shape of the prepared three-dimensional device and a shortened phosphorescence afterglow time. When too little water is added, the initial reaction before the microwave hydrothermal reaction of phosphoric acid and diethylenetriamine is uneven, which can easily lead to local heat accumulation and carbonization of the phosphorescent gel during the microwave heating stage, and a decrease in its shaping ability.

[0015] If the microwave power of the microwave hydrothermal reaction is too high or the reaction time is too long, it will cause local carbonization of the phosphorescent gel, and the molecular weight of the product will be larger and the afterglow time of the phosphorescence will be shorter; if the microwave power is too low or the reaction time is too short, it will make it difficult to remove the water used as the solvent, making the condensation reaction impossible, and further destroying the hydrogen bonds in the product, making it impossible to form a phosphorescent gel.

[0016] Preferably, the volume ratio of the phosphorus source to the polyamine is less than 1.

[0017] When the volume ratio of the phosphorus source to the polyamine is < 1, it is beneficial to increase the amount of chain-like condensates during the condensation reaction, thereby reducing the molecular flexibility, increasing the stiffness of the phosphorescent gel, improving the tensile strength and flexural strength of the phosphorescent gel, and further ensuring that the prepared three-dimensional phosphorescent device can maintain its shape unchanged for a long time.

[0018] Preferably, the volume ratio of the phosphorus source: polyamine: deionized water is (12 - 14):(16 - 22):(32 - 40).

[0019] Preferably, the power of the microwave hydrothermal reaction is 700 - 800 W; the time of the microwave hydrothermal reaction is 1.5 - 2.5 min.

[0020] The present invention also protects a phosphorescent gel with three-dimensional shaping function prepared by the preparation method of the above phosphorescent gel with three-dimensional shaping function.

[0021] In the specific embodiment, the molecular weight of the phosphorescent gel with three-dimensional shaping function of the present invention is ≤ 1000.

[0022] The molecular weight of the phosphorescent gel is analyzed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The specific steps and conditions are as follows: First, the phosphorescent gel is fully dissolved in deionized water to prepare multiple 1 mg / mL test solutions to be measured. Then, DHB (dihydroxybenzoic acid) matrix is added to the test solutions to be measured, and the measurement is carried out in the range of 700 - 3500 da. Finally, the molecular weights of the phosphorescent gels measured are all less than 1000. When the overall molecular weight of the phosphorescent gel is ≤ 1000, it contains a large number of different types of chain-like or cyclic condensation products. These small molecular chains or rings are more likely to interact with each other to form clustered emission centers, which is beneficial to the improvement of phosphorescent properties.

[0023] In the specific embodiment, when the phosphorescent gel with three-dimensional shaping function of the present invention is excited by ultraviolet light at room temperature, it can produce a fluorescence emission peak with a wavelength of 450 - 470 nm and a phosphorescent emission peak with a wavelength of 550 - 570 nm.

[0024] In the specific embodiment, the afterglow time of the phosphorescent gel with three-dimensional shaping function of the present invention is 13 - 20 s.

[0025] In the specific embodiment, the photoluminescence quantum yield of the phosphorescent gel with three-dimensional shaping function of the present invention is 16%, and the lifetime is 1.21 s.

[0026] In the specific embodiment, the Young's modulus of the phosphorescent gel with three-dimensional shaping function of the present invention after curing at room temperature is 1.0 - 1.5 GPa.

[0027] The present invention also protects a phosphorescent device prepared from raw materials including the above-mentioned phosphorescent gel with three-dimensional shaping function.

[0028] The application of the above-mentioned phosphorescent gel with three-dimensional shaping function in the preparation of luminous glue, decorative materials, smart windows and phosphorescent devices is also within the protection scope of the present invention.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] The present invention provides a preparation method of a phosphorescent gel with three-dimensional shaping function. The preparation method uses phosphoric acid and diethylenetriamine as reaction raw materials, and through microwave hydrothermal reaction condensation under specific microwave power conditions to form a phosphorescent gel. The prepared phosphorescent gel not only has good fluorescence performance, and the afterglow time reaches 13-20 s, but also has excellent three-dimensional plasticity performance, with a tensile strength of 3.55-20.08 MPa and a bending strength of 50.25-178.13 MPa. Description of the Drawings

[0031] Figure 1 It is a physical diagram of the phosphorescent gel with three-dimensional shaping function in Example 3.

[0032] Figure 2 It is a transmission electron microscope image of the phosphorescent gel with three-dimensional shaping function in Example 3.

[0033] Figure 3 It is a Fourier transform infrared spectrum diagram of the phosphorescent gel with three-dimensional shaping function in Example 3.

[0034] Figure 4 It is a three-dimensional stereoscopic shaping effect diagram of the phosphorescent gel with three-dimensional shaping function in Example 3.

[0035] Figure 5 It is a steady-state and delayed emission spectrum diagram of the phosphorescent gel with three-dimensional shaping function in Example 3.

[0036] Figure 6 It is a time-resolved photoluminescence spectrum decay curve of the phosphorescent gel with three-dimensional shaping function in Example 3.

[0037] Figure 7 It is a digital photo of the phosphorescent gel with three-dimensional shaping function in Example 5 under ultraviolet irradiation and after turning off.

[0038] Figure 8 It is a) tensile stress-strain curve, b) bending stress-strain curve and c) compression stress-strain curve of the phosphorescent gel with three-dimensional shaping function in Examples 1-3.

[0039] Figure 9Digital photograph of the phosphorescent gel with three-dimensional shaping function in Comparative Example 2. Detailed implementation manners

[0040] The present invention will be further described below in conjunction with the detailed implementation manners, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw material reagents used in the embodiments of the present invention are raw material reagents purchased conventionally.

[0041] Example 1

[0042] A preparation method of a phosphorescent gel with three-dimensional shaping function includes the following steps: magnetically stirring a phosphorus source, a polyamine, and deionized water at room temperature for 10 min, then performing ultrasonic treatment for 5 min to form a mixed solution, and then subjecting the mixed solution to microwave hydrothermal reaction. After the reaction is complete, a phosphorescent gel with three-dimensional shaping function can be obtained (as shown in Figure 1 );

[0043] The phosphorus source is phosphoric acid; the polyamine is diethylenetriamine;

[0044] The volume ratio of the phosphorus source: polyamine: deionized water is 10:12:20;

[0045] The power of the microwave hydrothermal reaction is 700 W, and the time of the microwave hydrothermal reaction is 2.5 min.

[0046] Example 2

[0047] A preparation method of a phosphorescent gel with three-dimensional shaping function includes steps substantially the same as those in Example 1, the difference being that the volume ratio of the phosphorus source: polyamine: deionized water is 15:32:45; the power of the microwave hydrothermal reaction is 700 W, and the time of the microwave hydrothermal reaction is 2.5 min.

[0048] Example 3

[0049] A preparation method of a phosphorescent gel with three-dimensional shaping function includes steps substantially the same as those in Example 1, the difference being that the volume ratio of the phosphorus source: polyamine: deionized water is 12:16:32; the power of the microwave hydrothermal reaction is 700 W, and the time of the microwave hydrothermal reaction is 2.5 min.

[0050] Example 4

[0051] A preparation method of a phosphorescent gel with three-dimensional shaping function includes steps substantially the same as those in Example 1, the difference being that the volume ratio of the phosphorus source: polyamine: deionized water is 14:22:40; the power of the microwave hydrothermal reaction is 700 W, and the time of the microwave hydrothermal reaction is 2.5 min.

[0052] Example 5

[0053] A preparation method of a phosphorescent gel with three-dimensional shaping function, including steps basically the same as those in Example 1, except that the volume ratio of the phosphorus source: polyamine: deionized water is 15:12:20.

[0054] Example 6

[0055] A preparation method of a phosphorescent gel with three-dimensional shaping function, including steps basically the same as those in Example 1, except that the power of the microwave hydrothermal reaction is 200W and the time of the microwave hydrothermal reaction is 13min.

[0056] Example 7

[0057] A preparation method of a phosphorescent gel with three-dimensional shaping function, including steps basically the same as those in Example 1, except that the power of the microwave hydrothermal reaction is 800W and the time of the microwave hydrothermal reaction is 1.5min.

[0058] Comparative Example 1

[0059] A preparation method of a phosphorescent gel with three-dimensional shaping function, including steps basically the same as those in Example 1, except that the volume ratio of the phosphorus source: polyamine: deionized water is 3:12:20;; the power of the microwave hydrothermal reaction is 700W and the time of the microwave hydrothermal reaction is 2.5min.

[0060] Comparative Example 2

[0061] A preparation method of a phosphorescent gel with three-dimensional shaping function, including steps basically the same as those in Example 1, except that the volume ratio of the phosphorus source: polyamine: deionized water is 20:12:20; the power of the microwave hydrothermal reaction is 700W and the time of the microwave hydrothermal reaction is 2.5min.

[0062] Comparative Example 3

[0063] A preparation method of a phosphorescent gel with three-dimensional shaping function, including steps basically the same as those in Example 1, except that the volume ratio of the phosphorus source: polyamine: deionized water is 10:5:20; the power of the microwave hydrothermal reaction is 700W and the time of the microwave hydrothermal reaction is 2.5min.

[0064] Comparative Example 4

[0065] A preparation method of a phosphorescent gel with three-dimensional shaping function, including steps basically the same as those in Example 1, except that the volume ratio of the phosphorus source: polyamine: deionized water is 10:40:20; the power of the microwave hydrothermal reaction is 700W and the time of the microwave hydrothermal reaction is 2.5min.

[0066] Comparative Example 5

[0067] A preparation method of a phosphorescent gel, comprising steps substantially the same as those in Example 1, except that the phosphorus source is aminotrimethylenephosphonic acid.

[0068] Comparative Example 6

[0069] A preparation method of a phosphorescent gel, comprising steps substantially the same as those in Example 1, except that the polyamine is tetramethylenediamine.

[0070] Comparative Example 7

[0071] A preparation method of a phosphorescent gel with three-dimensional shaping function, comprising steps substantially the same as those in Example 1, except that the polyamine is tetraethylenepentamine.

[0072] Performance Test

[0073] Perform performance tests on the phosphorescent gels prepared in the above examples and comparative examples:

[0074] (1) Transmission electron microscopy, Fourier transform infrared spectroscopy, steady-state and delayed emission spectroscopy, and time-resolved photoluminescence spectroscopy decay curves were all tested by conventional methods. The specific test results are as follows:

[0075] Figure 2 The TEM images of the phosphorescent gel in Example 3 at different magnifications are shown. It can be seen from the figure that the phosphorescent gel has molecules with partial ring structures and chain structures, which are significantly different from the larger aggregated dot images of carbon dots. The test results of other examples are basically the same as those of Example 3.

[0076] Figure 3 The Fourier transform infrared spectrum of the phosphorescent gel in Example 3 is shown. It can be seen from the figure that the absorption peaks at 3415 cm -1 and 3228 cm -1 correspond to the stretching vibrations of -OH and -NH2, the peak at 3023 cm -1 represents -CH2-, the two peaks at 1627 cm -1 and 1458 cm -1 are the bending vibrations of N-H and C-H respectively; the three peaks at 1178 cm -1 , 1070 cm -1 and 972 cm -1 represent the stretching vibrations of C-N / P=O, P-O, and P-N; the two weaker peaks at 898 cm -1 and 717 cm -1 are the P-O-P bonds, indicating the successful preparation of the phosphorescent gel.

[0077] Figure 5 andFigure 6 The steady-state and delayed emission spectra of the phosphorescent gel in Example 3 (the delayed emission spectrum recorded at a delay time Δt = 8 ms) and the time-resolved photoluminescence spectral decay curve, respectively. It can be seen from Figure 5 that the fluorescence wavelength and phosphorescence wavelength emitted by the phosphorescent gel are 450 - 470 nm and 550 - 570 nm, respectively; it can be seen from Figure 6 that the lifetime of the phosphorescent gel at 560 nm is 1.21 s, indicating its excellent phosphorescent properties. At the same time, through the fluorescence spectrum, the photoluminescence quantum yield of the three-dimensional shaping functional phosphorescent gel in Example 3 can be obtained as 16%.

[0078] (2) About 5 g of the phosphorescent gel in Example 3 was respectively placed in silicone molds with regular hexahedron, conical and regular tetrahedron cavities, and then cooled and solidified at room temperature. As Figure 4 shown, the digital photos on the left, in the middle and on the right in the figure correspond to the phosphorescent gel under natural light, ultraviolet light and no light conditions, respectively, indicating that the phosphorescent gel of the present invention has good three-dimensional plasticity. Figure 7 is the delayed capture image of the afterglow obtained after the phosphorescent gel in Example 5 was solidified and then irradiated with ultraviolet light for 5 s and the light was turned off at room temperature, indicating that it can maintain obvious green phosphorescent emission visible to the naked eye for about 20 s at room temperature.

[0079] (3) The stress-strain curve was measured by an electronic universal testing machine (Model: Inspekt Table Blue 5KN, Germany). Tensile test: The sample length was about 60 mm, the width was about 4 mm, and the height was about 3 mm, and the test speed was 20 mm / min; compression and bending tests: The sample length was about 60 mm, and both the width and height were 10 mm, and the test speed was 1 mm / min. The Young's modulus is the slope of the curve near the starting position of the tensile stress-strain curve and is obtained by calculation. Samples 1, 2, and 3 correspond to Examples 3, 2, and 1 respectively. It can be seen from Figure 8 that the phosphorescent gel of the present invention has good tensile strength, bending strength and compression strength. The Young's modulus of the phosphorescent gel in Example 1 was 1.0 GPa, the Young's modulus of the phosphorescent gel in Example 2 was 1.1 GPa, and the Young's modulus of the phosphorescent gel in Example 3 was 1.5 GPa obtained from the tensile stress-strain curve.

[0080] Test Results

[0081] Table 1 Performance Test

[0082]

[0083]

[0084] As can be seen from Examples 1 to 7, the phosphorescent gel of the present invention has excellent mechanical strength while maintaining a relatively long afterglow time, with a tensile strength of 3.55 to 20.08 MPa and a flexural strength of 50.25 to 178.13 MPa.

[0085] As can be seen from Comparative Examples 1 to 4, when the addition amount of phosphoric acid or diethylenetriamine is too much or too little, it is not conducive to the phosphorescent gel having good afterglow time, tensile strength and flexural strength at the same time. Especially when the addition amount of diethylenetriamine is too little, the phosphorescent gel cannot even be formed. When phosphoric acid is added in excess (Comparative Example 2), the prepared phosphorescent gel is as Figure 9 shown, and its transparency is significantly lower than that of Example 3 (as Figure 4 shown).

[0086] As can be seen from Comparative Examples 5 to 7, except for the case where the phosphorus source is phosphoric acid and the polyamine is diethylenetriamine, other combinations of phosphorus sources and polyamines are difficult to form a phosphorescent gel (Comparative Examples 5 and 6), or the tensile strength, flexural strength and afterglow time of the formed phosphorescent gel are significantly inferior to those of the present invention (Comparative Example 7).

[0087] The above examples of the present invention are merely illustrations for clearly explaining the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A preparation method of a phosphorescent gel with three-dimensional shaping function, characterized in that, It includes the following steps: uniformly mix a phosphorus source, a polyamine and water to form a mixed solution, and then carry out microwave hydrothermal reaction on the mixed solution. After the reaction is complete, a phosphorescent gel with three-dimensional shaping function can be obtained; The phosphorus source is phosphoric acid, and the polyamine is diethylenetriamine; The volume ratio of the phosphorus source: polyamine: water is (10 - 15):(12 - 32):(20 - 45); The microwave power of the microwave hydrothermal reaction is 200 - 800 W, and the time of the microwave hydrothermal reaction is 1.5 - 13 min.

2. The preparation method of the phosphorescent gel with three-dimensional shaping function according to claim 1, characterized in that, The volume ratio of the phosphorus source to the polyamine < 1.

3. The preparation method of the phosphorescent gel with three-dimensional shaping function according to claim 2, wherein, The volume ratio of the phosphorus source: polyamine: deionized water is (12 - 14):(16 - 22):(32 - 40).

4. The preparation method of the phosphorescent gel with three-dimensional shaping function according to claim 1, characterized in that, The power of the microwave hydrothermal reaction is 700 - 800 W, and the time of the microwave hydrothermal reaction is 1.5 - 2.5 min.

5. A phosphorescent gel with three-dimensional shaping function prepared by the preparation method of the phosphorescent gel with three-dimensional shaping function according to any one of claims 1 - 4.

6. The phosphorescent gel with three-dimensional shaping function according to claim 5, wherein The afterglow time of the phosphorescent gel with three-dimensional shaping function is 13 - 20 s.

7. The phosphorescent gel with three-dimensional shaping function according to claim 5, wherein When the phosphorescent gel with three-dimensional shaping function is excited by ultraviolet light at room temperature, it can produce a fluorescence emission peak with a wavelength of 450 - 470 nm and a phosphorescence emission peak with a wavelength of 550 - 570 nm.

8. The phosphorescent gel with three-dimensional shaping function according to claim 5, characterized in that, The Young's modulus of the phosphorescent gel with three-dimensional shaping function after curing at room temperature is 1.0 - 1.5 GPa.

9. A phosphorescent device, characterized in that, It is prepared from the raw materials including the phosphorescent gel with three-dimensional shaping function according to claim 5.

10. An application of the phosphorescent gel with three-dimensional shaping function according to claim 5 in the preparation of luminous glue, decorative materials and phosphorescent devices.

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