Preparation method and application of cuprous halide-based fluorescent light-emitting material

Abstract

The invention discloses a preparation method and application of a cuprous halide-based fluorescent luminescent material, the fluorescent luminescent material is obtained by mixing cuprous halide, organic phosphine oxide and metal halide, fully grinding in a mortar at room temperature for 5-20 minutes and reacting, and the molar ratio of the cuprous halide to the organic phosphine oxide is 0.5-2.0; the molar ratio of the cuprous halide to the metal halide is 0.5-2.0; the obtained fluorescent light-emitting material has the advantages of high quantum yield, adjustable fluorescent light-emitting wavelength, simple preparation method and low cost. Furthermore, the fluorescent luminescent material and hot melt resin are subjected to solvent-free banburying and mixing in a molten state to prepare the environment-friendly fluorescent hot melt adhesive, and the fluorescent hot melt adhesive can be used for preparing fluorescent colloidal particles, fluorescent wires and fluorescent films.

Description

Technical Field

[0001] The invention relates to the field of fluorescent materials, and in particular to a cuprous halide-based fluorescent luminescent material, a preparation method thereof, and application thereof in the field of solvent-free fluorescent hot melt adhesives. Background Art

[0002] Fluorescent materials have a wide range of uses in information display, luminescence technology, X-ray enhancement, biodiagnostic markers, sensor technology, cell imaging and other fields. Common fluorescent materials include inorganic phosphors doped with inorganic rare earth or transition metal ions, inorganic semiconductor nanocrystals, organic dyes, transition metal complexes and carbon dots. In recent years, lead halide perovskite nanocrystal fluorescent materials have attracted extensive research interest due to their high luminescence efficiency, tunable spectrum, solution preparation and low cost. However, their practical application is greatly limited by the presence of heavy metal lead. Recent studies have found that non-lead halide metal structural materials, such as Cs3Sb2Br9, Cs2InBr5·H2O, Cs4MnBi2Cl 12 , Cs2Ag 0.60 Na 0.40 InCl6 and (C8NH 12 )4Bi 0.57 Sb 0.43 Br7·H2O, etc., also have excellent luminescent properties and are considered to be able to replace lead-containing materials. However, these materials still contain heavy metals such as Sb, In, and Bi, and large-scale application will still cause potential environmental problems.

[0003] Recently, cuprous halide luminescent materials have attracted extensive research interest due to their rich luminescent properties. Cuprous ions have rich coordination chemical properties. Under the induction of organic cations, various cuprous halide cluster structures can be formed. Commonly used organic cations are organic amine cations and organic phosphorus cations. By changing the structure of the cations, the luminescent properties of cuprous halide luminescent materials can be regulated. However, due to the poor stability of organic amine cations and organic phosphorus cations, they are easily decomposed at temperatures above 100 degrees, which limits their promotion and application. Summary of the invention

[0004] In view of the problem of poor stability of existing cuprous halide luminescent materials, the purpose of the present invention is to provide a new cuprous halide luminescent material, which is prepared by the reaction of organic phosphine oxide, metal halide and cuprous halide, wherein the organic phosphine oxide and metal halide coordinate to form positive ions, which are combined with cuprous halide clusters to form cuprous halide fluorescent luminescent materials, and the material has the advantages of high fluorescence quantum yield, adjustable fluorescence wavelength, simple preparation method and low cost. Furthermore, the present invention mixes the above-mentioned fluorescent luminescent material with hot-melt resin in a molten state by solvent-free banburying to prepare an environmentally friendly fluorescent hot melt adhesive, which can be used for the preparation of fluorescent colloid particles, fluorescent wires and fluorescent films.

[0005] The specific technical solution for achieving the purpose of the present invention is:

[0006] A method for preparing a cuprous halide-based fluorescent luminescent material, characterized in that the method comprises:

[0007] Cuprous halide, organic phosphine oxide and metal halide are weighed according to stoichiometric amount, and fully ground in a mortar for 5-20 minutes at room temperature to obtain the cuprous halide-based fluorescent luminescent material; wherein the molar ratio of cuprous halide to organic phosphine oxide is 0.5-2.0; the molar ratio of cuprous halide to metal halide is 0.5-2.0; wherein,

[0008] The cuprous halide is one or two of cuprous iodide, cuprous bromide and cuprous chloride;

[0009] The metal halide is at least two of zinc iodide, zinc bromide, zinc chloride, cadmium iodide, cadmium bromide, cadmium chloride, magnesium iodide, magnesium bromide, magnesium chloride, calcium iodide, calcium bromide, calcium chloride, strontium iodide, strontium bromide, strontium chloride, barium iodide, barium bromide, barium chloride, lithium iodide, lithium bromide, lithium chloride, sodium iodide, sodium bromide, sodium chloride, potassium iodide, potassium bromide, potassium chloride, rubidium iodide, rubidium bromide, rubidium chloride, cesium iodide, cesium bromide and cesium chloride;

[0010] The organic phosphine oxide is an organic compound containing a phosphine oxide group, including tri(ethyl)phosphine oxide, tri(propyl)phosphine oxide, tri(butyl)phosphine oxide, tri(octyl)phosphine oxide, tri(cyclohexyl)phosphine oxide, di(phenyl)phosphine oxide, tri(phenyl)phosphine oxide, tri(3-methyl-phenyl)phosphine oxide, tri(3-chloro-phenyl)phosphine oxide, tri(3-methoxy-phenyl)phosphine oxide, tri(3-fluoro-phenyl)phosphine oxide, tripyrrolidinephosphine oxide, tri(4-morpholinyl)phosphine oxide, bis(ortho)phosphine oxide, One or at least two of the group consisting of (methoxyphenyl)phosphine oxide, methoxymethyl (diphenyl)phosphine oxide, bis(1-naphthyl)phosphine oxide, diphenylethylphosphine oxide, tri(4-methoxyphenyl)phosphine oxide, (methoxymethyl)diphenylphosphine oxide, di(p-tolyl)phosphine oxide, (3-bromophenyl)diphenylphosphine oxide, (diphenyl ether (2,1-phenylene))bis(diphenylphosphine oxide), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl phenyl phosphite and butyl phenyl phosphite.

[0011] A cuprous halide-based fluorescent luminescent material prepared by the above method.

[0012] An application of the cuprous halide-based fluorescent luminescent material in the preparation of a solvent-free fluorescent hot melt adhesive comprises the following specific steps:

[0013] 1) The cuprous halide-based fluorescent material and the hot-melt resin are mixed by solvent-free kneading, the heating temperature is determined according to the melting point of the resin, the hot-melt resin is heated until it reaches a colloid molten state, and the mixture is stirred, and the fluorescent hot-melt adhesive is prepared after the two are evenly mixed; wherein the mass ratio of the hot-melt resin to the fluorescent material is 5 to 100;

[0014] 2) putting the fluorescent hot melt adhesive prepared in step 1) into a particle mold through an extrusion process, and waiting for the hot melt adhesive to cool down to obtain fluorescent hot melt adhesive particles;

[0015] 3) putting the fluorescent hot-melt adhesive pellets prepared in step 2) into a desktop extruder, setting the heating temperature according to the melting point of the hot-melt adhesive pellets, and melting the adhesive pellets by two-stage heating to obtain fluorescent wires;

[0016] 4) Putting the fluorescent hot melt adhesive prepared in step 1) into a hot press, setting the heating temperature according to the melting point of the hot melt adhesive particles, and obtaining a fluorescent film; wherein:

[0017] The hot-melt resin is one or at least two of thermoplastic water-white petroleum resin, terpene resin, rosin resin, ethylene-vinyl acetate copolymer (EVA) and polyolefin elastomer resin (POE).

[0018] The significance of the present invention is to provide a preparation technology of a cuprous halide-based fluorescent material and its application in a solvent-free fluorescent hot melt adhesive, wherein the fluorescent material has the advantages of high quantum yield, adjustable fluorescent wavelength, simple preparation method and low cost. Furthermore, the present invention mixes the fluorescent material with a hot melt resin in a molten state by solvent-free banburying to prepare an environmentally friendly fluorescent hot melt adhesive, which can be used for the preparation of fluorescent colloid particles, fluorescent wires and fluorescent films. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a PL spectrum of the fluorescent material obtained in Example 1 of the present invention;

[0020] Figure 2 This is a PL spectrum of the fluorescent material obtained in Example 2 of the present invention;

[0021] Figure 3 This is a PL spectrum of the fluorescent material obtained in Example 3 of the present invention;

[0022] Figure 4 This is a schematic diagram of the fluorescent hot melt adhesive obtained in Example 16 of the present invention under sunlight and 365nm excitation light;

[0023] Figure 5 This is a schematic diagram of the fluorescent colloid particles obtained in Example 17 of the present invention;

[0024] Figure 6 This is a schematic diagram of the fluorescent wire obtained in Example 19 of the present invention;

[0025] Figure 7 This is a schematic diagram of the fluorescent film obtained in Example 21 of the present invention under 365nm excitation light. DETAILED DESCRIPTION

[0026] The present invention is further described in detail in conjunction with the following specific embodiments and drawings, and the protection content of the present invention is not limited to the following embodiments. Without departing from the spirit and scope of the inventive concept, changes that can be thought of by those skilled in the art are included in the present invention and are protected by the attached claims.

[0027] Example 1

[0028] 159.6 mg zinc iodide, 74.95 mg sodium iodide, 190.45 mg cuprous iodide and 278.28 mg triphenylphosphine oxide were fully ground at room temperature for 5 minutes to prepare a fluorescent luminescent material, the PL spectrum of which is shown in the figure below: Figure 1 As shown in the figure, it can be seen that its excitation wavelength is green light at 529 nm.

[0029] Example 2

[0030] 139.06 mg of magnesium iodide, 159.6 mg of zinc iodide, 190.45 mg of cuprous iodide, and 305.31 mg of tri(4-morpholinyl)phosphine oxide were fully ground at room temperature for 5 minutes to prepare a fluorescent luminescent material, the PL spectrum of which is shown in the following figure: Figure 2 As shown in the figure, it can be seen that its excitation wavelength is orange light at 650 nm.

[0031] Example 3

[0032] 146.95 mg of calcium iodide, 183.11 mg of cadmium iodide, 190.45 mg of cuprous iodide, and 305.31 mg of tri(4-morpholinyl)phosphine oxide were fully ground at room temperature for 8 minutes to prepare a fluorescent luminescent material, the PL spectrum of which is shown in the following figure: Figure 3 As shown in the figure, it can be seen that its excitation wavelength is blue light at 455 nm.

[0033] Example 4

[0034] 212.37 mg of rubidium iodide, 190.45 mg of cuprous iodide, and 305.31 mg of tri(4-morpholinyl)phosphine oxide were fully ground at room temperature for 10 minutes to prepare a fluorescent luminescent material.

[0035] Example 5

[0036] 133.85 mg of lithium iodide, 190.45 mg of cuprous iodide, and 296.43 mg of tricyclohexylphosphine oxide were fully ground at room temperature for 5 minutes to prepare a fluorescent light-emitting material.

[0037] Example 6

[0038] 199.9 mg of calcium bromide, 143.45 mg of cuprous bromide, and 386.63 mg of trioctylphosphine oxide were fully ground at room temperature for 5 minutes to prepare a fluorescent luminescent material.

[0039] Example 7

[0040] 246.48 mg of cesium chloride, 98.99 mg of cuprous chloride, and 280.43 mg of tricyclohexylphosphine oxide were fully ground at room temperature for 5 minutes to prepare a fluorescent light-emitting material.

[0041] Example 8

[0042] 110.98 mg of calcium chloride, 98.99 mg of cuprous chloride, and 278.28 mg of triphenylphosphine oxide were fully ground at room temperature for 5 minutes to prepare a fluorescent light-emitting material.

[0043] Example 9

[0044] 246.48 mg of barium chloride, 98.99 mg of cuprous chloride, and 280.43 mg of tricyclohexylphosphine oxide were fully ground at room temperature for 8 minutes to prepare a fluorescent luminescent material.

[0045] Example 10

[0046] 212.81 mg of rubidium bromide, 143.45 mg of cuprous bromide, and 268.33 mg of cyclohexyldiphenylphosphine oxide were fully ground at room temperature for 5 minutes to prepare a fluorescent light-emitting material.

[0047] Embodiment 11

[0048] 72.65 mg of rubidium bromide, 190.40 mg of manganese iodide, 143.45 mg of cuprous bromide, 268.33 mg of cyclohexyldiphenylphosphine oxide, and 85.07 mg of ethyl phenylphosphite were fully ground at room temperature for 10 minutes to prepare a fluorescent light-emitting material.

[0049] Example 12

[0050] 72.65 mg of rubidium bromide, 159.6 mg of zinc iodide, 98.99 mg of cuprous chloride, 139.14 mg of triphenylphosphine oxide, and 85.07 mg of ethyl phenylphosphite were fully ground at room temperature for 15 minutes to prepare a fluorescent light-emitting material.

[0051] Example 13

[0052] 199.90 mg of calcium bromide, 149.89 mg of sodium iodide, 143.45 mg of cuprous bromide, 190.45 mg of cuprous iodide, 238.31 mg of dibutylphenylphosphine oxide, and 257.32 mg of tripyrrolidinephosphine oxide were fully ground at room temperature for 20 minutes to prepare a fluorescent luminescent material.

[0053] Embodiment 14

[0054] 212.81 mg of strontium bromide, 278.11 mg of magnesium iodide, 98.99 mg of cuprous chloride, 143.45 mg of cuprous bromide, 176.18 mg of tris(3-methoxy-phenyl)phosphine oxide, 158.13 mg of tris(3-fluoro-phenyl)phosphine oxide, and 257.32 mg of tripyrrolidinephosphine oxide were fully ground at room temperature for 20 minutes to prepare a fluorescent luminescent material.

[0055] Embodiment 15

[0056] 66.92 mg of lithium iodide, 146.95 mg of calcium iodide, 143.45 mg of cuprous bromide, 95.23 mg of cuprous iodide, 339.39 mg of bis(1-naphthyl)phosphine oxide, and 115.12 mg of diphenylethylphosphine oxide were fully ground at room temperature for 20 minutes to prepare a fluorescent luminescent material.

[0057] Example 16

[0058] 250 mg of the fluorescent luminescent material prepared in Example 1 was mixed with 2.0 g of water-white petroleum resin and 15.0 g of ethylene-vinyl acetate copolymer in a molten state to obtain an environmentally friendly fluorescent hot melt adhesive, the schematic diagram of which under sunlight and under 365 nm excitation light is shown in FIG. Figure 4 As shown, its excitation wavelength is green light at 529 nm.

[0059] Embodiment 17

[0060] The fluorescent hot melt adhesive prepared in Example 16 was extruded to prepare fluorescent colloid particles, which are shown in the schematic diagram under sunlight. Figure 5 As shown, its color under 365nm excitation light is the same as that of fluorescent hot melt adhesive, and the excitation wavelength is green light at 529nm.

[0061] Embodiment 18

[0062] The fluorescent colloid particles prepared in Example 17 are heated in two stages by a desktop extruder and cooled to obtain fluorescent wires, which are shown in the schematic diagram under sunlight. Figure 6 As shown, its color under 365nm excitation light is the same as that of the fluorescent colloid particles, and the excitation wavelength is green light at 529nm.

[0063] Embodiment 19

[0064] 500 mg of the fluorescent luminescent material prepared in Example 2 was kneaded with 6.0 g of terpene resin and 39.0 g of polyolefin elastomer resin in a molten state to obtain a fluorescent hot melt adhesive.

[0065] Embodiment 20

[0066] 280 mg of the fluorescent luminescent material prepared in Example 3, 4.0 g of rosin resin, and 10.0 g of ethylene-vinyl acetate copolymer were kneaded in a molten state to obtain a fluorescent hot melt adhesive.

[0067] Embodiment 21

[0068] The fluorescent hot melt adhesive prepared in Example 20 was extruded to prepare a fluorescent film, and the schematic diagram thereof under 365 nm excitation light is as shown in FIG. Figure 7 As shown, its excitation wavelength is blue light at 455 nm.

Claims

1. A method for preparing a cuprous halide-based fluorescent material, characterized in that: The method includes: Cuprous halide, organic phosphine oxide and metal halide are weighed according to stoichiometric amount, and fully ground in a mortar for 5-20 minutes at room temperature to obtain the cuprous halide-based fluorescent luminescent material; wherein the molar ratio of cuprous halide to organic phosphine oxide is 0.5-2.0; the molar ratio of cuprous halide to metal halide is 0.5-2.0; wherein, The cuprous halide is one or two of cuprous iodide, cuprous bromide and cuprous chloride; The metal halide is at least two of zinc iodide, zinc bromide, zinc chloride, cadmium iodide, cadmium bromide, cadmium chloride, magnesium iodide, magnesium bromide, magnesium chloride, calcium iodide, calcium bromide, calcium chloride, strontium iodide, strontium bromide, strontium chloride, barium iodide, barium bromide, barium chloride, lithium iodide, lithium bromide, lithium chloride, sodium iodide, sodium bromide, sodium chloride, potassium iodide, potassium bromide, potassium chloride, rubidium iodide, rubidium bromide, rubidium chloride, cesium iodide, cesium bromide and cesium chloride; The organic phosphine oxide is an organic compound containing a phosphine oxide group, including tri(ethyl)phosphine oxide, tri(propyl)phosphine oxide, tri(butyl)phosphine oxide, tri(octyl)phosphine oxide, tri(cyclohexyl)phosphine oxide, di(phenyl)phosphine oxide, tri(phenyl)phosphine oxide, tri(3-methyl-phenyl)phosphine oxide, tri(3-chloro-phenyl)phosphine oxide, tri(3-methoxy-phenyl)phosphine oxide, tri(3-fluoro-phenyl)phosphine oxide, tripyrrolidinephosphine oxide, tri(4-morpholinyl)phosphine oxide, bis(ortho)phosphine oxide, One or at least two of the group consisting of (methoxyphenyl)phosphine oxide, methoxymethyl (diphenyl)phosphine oxide, bis(1-naphthyl)phosphine oxide, diphenylethylphosphine oxide, tri(4-methoxyphenyl)phosphine oxide, (methoxymethyl)diphenylphosphine oxide, di(p-tolyl)phosphine oxide, (3-bromophenyl)diphenylphosphine oxide, (diphenyl ether (2,1-phenylene))bis(diphenylphosphine oxide), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl phenyl phosphite and butyl phenyl phosphite.

2. A cuprous halide-based fluorescent material prepared by the method of claim 1.

3. Use of the cuprous halide-based fluorescent luminescent material according to claim 2 in the preparation of solvent-free fluorescent hot melt adhesive, characterized in that: The specific steps include: 1) The cuprous halide-based fluorescent material and the hot-melt resin are mixed by solvent-free kneading, the heating temperature is determined according to the melting point of the resin, the hot-melt resin is heated until it reaches a colloid molten state, and the mixture is stirred, and the fluorescent hot-melt adhesive is prepared after the two are evenly mixed; wherein the mass ratio of the hot-melt resin to the fluorescent material is 5 to 100; 2) putting the fluorescent hot melt adhesive prepared in step 1) into a particle mold through an extrusion process, and waiting for the hot melt adhesive to cool down to obtain fluorescent hot melt adhesive particles; 3) putting the fluorescent hot-melt adhesive pellets prepared in step 2) into a desktop extruder, setting the heating temperature according to the melting point of the hot-melt adhesive pellets, and melting the adhesive pellets by two-stage heating to obtain fluorescent wires; 4) Putting the fluorescent hot melt adhesive prepared in step 1) into a hot press, setting the heating temperature according to the melting point of the hot melt adhesive particles, and obtaining a fluorescent film; wherein: The hot-melt resin is one or at least two of thermoplastic water-white petroleum resin, terpene resin, rosin resin, ethylene-vinyl acetate copolymer (EVA) and polyolefin elastomer resin (POE).

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