1. The preparation method of the 3D printing material with photoluminescence is characterized by comprising the following steps:

step 1, dissolving polycaprolactone in a toluene solution to obtain a mixed solution; the volume ratio of the mass of the polycaprolactone to the mass of the toluene is 10-50 mg:1 mL;

step 2, dissolving lead halide, methyl ammonium halide, oleic acid and n-octylamine in a solvent to obtain a precursor solution MAPbX of the perovskite quantum dot₃X represents at least one of halogen elements Br, I and Cl;

the mass ratio of the lead halide to the methyl ammonium halide is 4: 4-4: 5;

the volume ratio of the sum of the lead halide and the methyl ammonium halide to the toluene is 0.36mmol: 50-100 ml;

and 3, dropwise adding the precursor solution of the perovskite quantum dots obtained in the step 2 into the mixed solution obtained in the step 1, centrifuging, removing the precipitate to obtain a supernatant, and evaporating toluene in the supernatant to obtain the composite material.

2. The method for preparing the 3D printing material with photoluminescence as claimed in claim 1, wherein the lead halide is lead halidePbBr₂、PbI₂、PbCl₂The methyl ammonium halide is at least one of MABr, MAI and MACl.

3. The preparation method of the photoluminescent 3D printing material according to claim 1, wherein the addition volume ratio of the oleic acid to the n-octylamine is 20: 1-25: 1; the ratio of the total mass of the lead halide and the methyl ammonium halide to the addition volume of the oleic acid is 1mmol: 1-2 mL.

4. The method for preparing a 3D printing material with photoluminescence according to claim 2, wherein the amount of the solvent added in the step 2 is 0.16mmol:0.2mmol:5ml according to the amount of the methyl ammonium halide substance: the amount of the lead halide substance: the volume of the solvent.

5. The method for preparing a 3D printing material with photoluminescence according to claim 1 or 4, wherein the solvent is one or more of mixed solution of dimethylformamide, acetonitrile and dimethyl sulfoxide.

6. The method for preparing the 3D printing material with photoluminescence property according to claim 1, wherein the centrifugal rotation speed is 6000-8000 rpm.

7. The method for preparing the 3D printing material with photoluminescence property according to claim 1, wherein the evaporation temperature is 40-60 ℃.

8. A 3D printing material with photoluminescence prepared by the preparation method of any one of claims 1 to 7; the 3D printing material comprises a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

9. The preparation method of the 3D printing wire with photoluminescence is characterized in that the 3D printing material prepared by the preparation method of any one of claims 1 to 7 or the 3D printing material of claim 8 is used as a raw material to be subjected to melt extrusion molding, so that the 3D printing wire with photoluminescence is obtained.

Background

3D printing has shown its value in small-lot, personalized material manufacturing, such as the foundry industry, the construction industry, the aerospace industry, the solid forming of medical body images, and the like. Fused Deposition Modeling (FDM) is a form of 3D printing that has become one of the most prominent and popular forms of additive manufacturing technology. The FDM generally uses a high molecular material as a wire material for melt extrusion molding, and the wire material is polylactic acid PLA, acrylonitrile-butadiene-styrene copolymer ABS, etc., and these high molecular materials have a problem of single function, which limits the application of the FDM printing technology in the preparation of functional materials and functional devices.

The preparation of the 3D printing material with the light-emitting characteristic can endow wires with the fluorescent characteristic, for example, the wires with the light-emitting characteristic can be used for manufacturing light pipes, other complex fluorescent devices, fluorescent displays and the like by 3D printing, and can also be used for anti-counterfeiting application, so that the problem of single functionality of the materials in the current 3D printing industry is solved, and the application range of 3D printing can be wider.

At present, the 3D printing wire rod is prepared by embedding gradient alloy cadmium sulfide selenide quantum dots (CdSSe quantum dots) into a PLA (polylactic acid) matrix, but the CdSSe quantum dots are harsh in synthesis conditions, need to be synthesized at high temperature under an inert atmosphere, are high in cost and limit further application of the wire rod.

Disclosure of Invention

Aiming at the technical requirements, the invention provides a 3D printing material with photoluminescence, a 3D printing wire and a preparation method, and solves the problems of poor stability, high preparation condition requirement and the like of the existing 3D printing material with photoluminescence.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a 3D printing material with photoluminescence comprises the following steps:

step 1, dissolving polycaprolactone in a toluene solution to obtain a mixed solution; the volume ratio of the mass of the polycaprolactone to the mass of the toluene is 10-50 mg:1 mL;

step 2, dissolving lead halide, methyl ammonium halide, oleic acid and n-octylamine in a solvent to obtain a precursor solution MAPbX of the perovskite quantum dot₃X represents at least one of halogen elements Br, I and Cl;

the mass ratio of the lead halide to the methyl ammonium halide is 4: 4-4: 5;

the volume ratio of the sum of the lead halide and the methyl ammonium halide to the toluene is 0.36mmol: 50-100 ml;

and 3, dropwise adding the precursor solution of the perovskite quantum dots obtained in the step 2 into the mixed solution obtained in the step 1, centrifuging, removing the precipitate to obtain a supernatant, and evaporating toluene in the supernatant to obtain the composite material.

Preferably, the lead halide is PbBr₂、PbI₂、PbCl₂The methyl ammonium halide is at least one of MABr, MAI and MACl.

Preferably, the volume ratio of the oleic acid to the n-octylamine is 20: 1-25: 1; the ratio of the total mass of the lead halide and the methyl ammonium halide to the addition volume of the oleic acid is 1mmol: 1-2 mL.

Preferably, the amount of the solvent added in the step 2 is 0.16 mmol/0.2 mmol/5 ml of the amount of the methyl ammonium halide substance/lead halide substance/volume of the solvent.

Preferably, the solvent is one or more of dimethylformamide, acetonitrile and dimethyl sulfoxide.

Preferably, the centrifugal rotating speed is 6000-8000 rpm.

Preferably, the evaporation temperature is 40-60 ℃.

The invention also discloses the 3D printing material with photoluminescence prepared by the preparation method, and the 3D printing material comprises a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The invention also discloses a preparation method of the 3D printing wire with photoluminescence, which comprises the following steps: the 3D printing material prepared by the preparation method or the 3D printing material provided by the invention is used as a raw material to be subjected to melt extrusion molding, so that the 3D printing wire with photoluminescence is obtained.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the method, a certain amount of PCL particles are dissolved in a toluene solution, then a precursor solution of perovskite quantum dots is dripped into a PCL-toluene mixed solution, so that the perovskite quantum dots form a PQDs-PCL colloidal solution in the PCL-toluene mixed heterogeneous solution through heterogeneous nucleation, and a material with photoluminescence property can be obtained after redundant toluene is evaporated.

(2) The invention forms the PQDs-PCL composite material in one step, and simplifies the steps of the composite material.

Drawings

FIG. 1 is a transmission electron micrograph of the composite material prepared in example 1.

FIG. 2 is an energy spectrum of the composite material prepared in example 1.

Fig. 3 is an absorption spectrum (dotted line) and a fluorescence spectrum (solid line) of the composite materials prepared in example 1, example 2, and example 3, and the pure quantum dots.

FIG. 4 is the results of the water stability and light stability tests of the composite material prepared in example 1, wherein (a) is light stability; (b) is water stability, and the inset shows the change in color of the sample under the uv lamp.

FIG. 5 is the result of a thermal stability test of the composite material prepared in example 1, wherein (a) is a fluorescence spectrum of the composite material at different temperatures; (b) is a graph of the variation trend of the emission peak intensity along with the temperature, and the insert graph at the upper right corner is the fluorescence spectrum of the pure perovskite quantum dot at different temperatures.

Fig. 6 is a photograph of the 3D printed wire of example 1 under an ultraviolet lamp, (a) is a photograph of the 3D printed wire under an ultraviolet lamp before water is not added, and (b) is a photograph of the 3D printed wire under an ultraviolet lamp after water is added.

FIG. 7 is a graph showing the water stability of the PQDs-PLA composite of comparative example 2, (a) is a photograph of the PQDs-PLA composite under an ultraviolet lamp before water is not added, and (b) is a photograph of the PQDs-PLA composite under an ultraviolet lamp after water is added.

Detailed Description

Perovskite Quantum Dots (PQDs) have the characteristics of high absorption coefficient, long carrier diffusion length, defect tolerance, flexible bandgap adjustment, and the like, making them revolutionary materials for photovoltaic technology. However, perovskite quantum dots present serious stability problems: they are susceptible to degradation and fluorescence quenching upon exposure to light or to certain humidity conditions and oxygen. Surface passivation is critical to slow its degradation and protect it from external damage. According to the invention, PQDs are encapsulated in a thermoplastic polymer Polycaprolactone (PCL), so that on one hand, PQDs are protected and the stability of PQDs is improved, and on the other hand, PQDs are applied to 3D printing to realize the fluorescent characteristic of a 3D printing material.

The emission wavelength of the luminescent wire is controlled by adjusting the type and content of halogen ions (Br, I, Cl and the like) in the perovskite quantum dot precursor, and the concentration of the perovskite quantum dots in the luminescent wire is controlled by adjusting the content of PCL in toluene.

The toluene is used for dissolving polycaprolactone on one hand, and quantum dots are separated out from the toluene on the other hand; the volume ratio of the mass of polycaprolactone to toluene is 10-50 mg:1mL, and the concentration of perovskite quantum dots in the luminescent wire rod is controlled by adjusting the content of PCL in toluene.

Amount of lead halide substance of the present invention: amount of methylammonium halide species: the volume ratio of the toluene is 0.16mmol:0.2mmol: 50-100 ml, so the volume ratio of the sum of the lead halide and the methyl ammonium halide to the toluene is 0.36mmol: 50-100 ml.

The precipitate in step 3 of the invention is quantum dots with large particles, the particle size reaches the micron level, and the stability is not good. Therefore, the removal is carried out by a centrifugal method, and the preferred centrifugal rotating speed is 6000-8000 rpm. The quantum dots in the centrifuged supernatant can reach a nanometer level, and the quantum dots obtained in the embodiment of the invention are 8-15 nm.

When the precursor solution of the perovskite quantum dot is prepared, the used solvent is dimethylformamide, acetonitrile or dimethyl sulfoxide, and the method specifically comprises the following steps: the solvent may contain dimethylformamide when bromide is present, acetonitrile when iodide is present, and dimethylsulfoxide when chloride is present. Preferably, acetonitrile: dimethylformamide: volume ratio of dimethyl sulfoxide ═ lead iodide: lead bromide: the ratio of the amount of substance of lead chloride.

In the step 3 of the invention, the evaporation temperature is 40-60 ℃, the luminescent property of the quantum dots can be affected by overhigh temperature, and the whole evaporation process is slow, preferably 50 ℃.

When the 3D printing wire is prepared, the 3D material prepared by the method is added into a melting extruder for extrusion molding, the temperature of each section in the melting extruder is higher than the melting point of the composite material, and the number of the sections of different types of extruders is different.

In the invention, MABr represents methyl amine bromide, MAI represents methyl amine iodide, MACl represents methyl amine chloride, and DMF represents N, N-dimethylformamide.

PbBr used in the following examples of the present invention₂、PbI₂、PbCl₂Dimethylformamide, acetonitrile, dimethyl sulfoxide, oleic acid, n-octylamine and PCL particles are all sold on the market, the toluene is analyzed and purified by the commercially available toluene, and the methyl amine bromide, the methyl amine iodide and the methyl ammonium chloride are respectively prepared by the literature Brightly luminescence and Color Tunable Colloidal CH reported by zhang et al₃NH₃PbX₃(X ═ Br, I, Cl) Quantum Dots: volumetric Alternatives for Display Technology, the melt extruder in the following examples was a twin-screw extruder, model Wuhan Rewling mini twin-screw extruder SJZS-10A, provided with four temperature zones.

The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.

Example 1

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 20mg:1mL, the mixed solution is placed in a glass bottle, and stirring is carried out for 6h, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0734g of PbBr was added₂0.5mL of oleic acid, 20. mu.L of n-octylamine, and 0.0176g of MABr were dissolved in 5mL of DMF in proportion to prepare MAPbBr₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and evaporating the excessive toluene in the solution of the composite material at 50 ℃ to obtain the composite material.

Fig. 1 shows a TEM image of the composite material, and fig. 2 shows an XRD pattern of the composite material by the upper line, and a characteristic peak of the perovskite quantum dots existing near 14 ° can be observed in the XRD pattern, which indicates that the composite material of this embodiment is a PQDs-PCL composite material, and is composed of a polycaprolactone matrix and the perovskite quantum dots distributed in the polycaprolactone matrix.

The absorption spectrum and the fluorescence spectrum of the composite material of the present example are shown in fig. 3, and it can be seen that the composite material of the present example emits light with a wavelength of 526nm, which indicates that the composite material has fluorescence characteristics.

As can be seen from fig. 4(a), the emission peak intensity of the composite material of the present example is not significantly reduced after being irradiated under an ultraviolet lamp for 180 hours; in addition, as can be seen from fig. 4(b), the strength of the composite material is reduced to only 70% of the initial strength after soaking in water for 150 hours, which proves that the composite material of the present example has excellent water stability and light stability.

From fig. 5(a), the emission peak intensity of the composite material of the present example at 100 ℃ is still 30% of that at 40 ℃, and from the top left-hand graph of (b), it can be seen that the pure perovskite quantum dot is already close to quenching at 100 ℃, which indicates that embedding PQDs into PCL improves the thermal stability of the perovskite quantum dot.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 52 ℃, the temperature of a third zone to be 70 ℃ and the temperature of a fourth zone to be 70 ℃, and performing melt extrusion on the 3D printing wire. As shown in fig. 6(a), which is a photograph of the 3D printing wire under the ultraviolet lamp, it can be seen that a significant luminescence is seen under the ultraviolet lamp, and fig. 6(b) it can be seen that the fluorescence of the 3D printing wire does not disappear after the water is added.

Example 2

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 30mg:1mL, the mixed solution is placed in a glass bottle and stirred for 8 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0734g of PbBr was added₂0.5mL of oleic acid, 20. mu.L of n-octylamine, and 0.0176g of MABr were dissolved in 5mL of DMF in proportion to prepare MAPbBr₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix. The absorption spectrum and fluorescence spectrum of the composite material of this example are shown in FIG. 3, and it can be seen that the composite material of this example emits light with a wavelength of 527nm, which is very close to the wavelength of the pure quantum dot (525nm), indicating that the composite material has fluorescence characteristics.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 50 ℃, the temperature of a third zone to be 70 ℃ and the temperature of a fourth zone to be 70 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 3

The method comprises the following steps: the PCL polymer and the toluene solution are mixed according to the proportion of 40mg:1mL, the mixed solution is placed in a glass bottle and stirred for 10 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0734g of PbBr was added₂0.5mL of oleic acid, 20. mu.L of n-octylamine, and 0.0176g of MABr were dissolved in 5mL of DMF in proportion to prepare MAPbBr₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the PQDs-PCL composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix. The absorption spectrum and the fluorescence spectrum of the composite material of the present example are shown in fig. 3, and it can be seen that the composite material of the present example emits light with a wavelength of 528nm, which indicates that the composite material has fluorescence characteristics.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 50 ℃, the temperature of a third zone to be 75 ℃ and the temperature of a fourth zone to be 75 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 4

Step 1: mixing a PCL polymer with a toluene solution according to the proportion of 10mg:1 mL; the mixture was placed in a glass bottle and stirred for 5h to dissolve the PCL completely in the toluene solution.

Step 2: 0.0734g of PbBr was added₂0.5mL of oleic acid, 20. mu.L of N-octylamine, and 0.0176g of MABr were dissolved in 5mL of DMF (N, N-dimethylformamide) in proportion to prepare MAPbBr₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and evaporating the excessive toluene from the solution of the composite material at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and putting the composite material into an SJZS-10A double-screw extruder, wherein the temperature of a first zone is set to be 45 ℃, the temperature of a second zone is set to be 52 ℃, the temperature of a third zone is set to be 68 ℃, and the temperature of a fourth zone is set to be 68 ℃, and melting and extruding the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 5

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 10mg:1mL, the mixed solution is placed in a glass bottle, and stirring is carried out for 6h, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0922g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, and 0.0254g of MAI were dissolved in 5mL of acetonitrile in proportion to prepare MAPbI₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 52 ℃, the temperature of a third zone to be 68 ℃ and the temperature of a fourth zone to be 68 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 6

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 20mg:1mL, the mixed solution is placed in a glass bottle, and stirring is carried out for 5 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0922g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, and 0.0254g of MAI were dissolved in 5mL of acetonitrile in proportion to prepare MAPbI₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 52 ℃, the temperature of a third zone to be 70 ℃ and the temperature of a fourth zone to be 65 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 7

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 30mg:1mL, the mixed solution is placed in a glass bottle and stirred for 8 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0922g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, and 0.0254g of MAI were dissolved in 5mL of acetonitrile in proportion to prepare MAPbI₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 50 ℃, the temperature of a third zone to be 70 ℃ and the temperature of a fourth zone to be 70 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 8

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 40mg:1mL, the mixed solution is placed in a glass bottle and stirred for 10 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0922g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, and 0.0254g of MAI were dissolved in 5mL of acetonitrile in proportion to prepare MAPbI₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 50 ℃, the temperature of a third zone to be 75 ℃ and the temperature of a fourth zone to be 75 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 9

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 10mg:1mL, the mixed solution is placed in a glass bottle, and stirring is carried out for 5 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0235g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, 0.0010g of MABr, 0.0033g of PbBr₂Proportionally dissolving in 5mL acetonitrile to prepare MAPbBr_0.5I_2.5And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 52 ℃, the temperature of a third zone to be 68 ℃ and the temperature of a fourth zone to be 68 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 10

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 20mg:1mL, the mixed solution is placed in a glass bottle and stirred for 6h, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0235g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, 0.0010g of MABr, 0.0033g of PbBr₂Proportionally dissolving in 5mL acetonitrile to prepare MAPbBr_0.5I_2.5And (3) precursor solution.

And step 3: and (3) dripping 0.5m L precursor into the solution prepared in the second step, stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 52 ℃, the temperature of a third zone to be 70 ℃ and the temperature of a fourth zone to be 70 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 11

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 30mg:1mL, the mixed solution is placed in a glass bottle and stirred for 8 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0235g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, 0.0010g of MABr, 0.0033g of PbBr₂Proportionally dissolving in 5mL acetonitrile to prepare MAPbBr_0.5I_2.5And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the PQDs-PCL composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 50 ℃, the temperature of a third zone to be 70 ℃ and the temperature of a fourth zone to be 70 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 12

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 40mg:1mL, the mixed solution is placed in a glass bottle and stirred for 10 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.0235g of PbI₂0.2mL of oleic acid, 20. mu.L of n-octylamine, 0.0010g of MABr, 0.0033g of PbBr₂Proportionally dissolving in 5mL acetonitrile to prepare MAPbBr_0.5I_2.5And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 50 ℃, the temperature of a third zone to be 75 ℃ and the temperature of a fourth zone to be 75 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 13

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 10mg:1mL, the mixed solution is placed in a glass bottle, and stirring is carried out for 5 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.2mL of oleic acid, 20. mu.L of n-octylamine, 0.0108g of MACl, 0.0556g of PbCl₂Proportionally dissolving in 5mL of dimethyl sulfoxide to prepare MAPbCl₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 52 ℃, the temperature of a third zone to be 68 ℃ and the temperature of a fourth zone to be 68 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Example 14

Step 1: the PCL polymer and the toluene solution are mixed according to the proportion of 30mg:1mL, the mixed solution is placed in a glass bottle and stirred for 8 hours, so that the PCL is completely dissolved in the toluene solution.

Step 2: 0.2mL of oleic acid, 20. mu.L of n-octylamine, 0.0108g of MACl, 0.0556g of PbCl₂Proportionally dissolving in 5mL of dimethyl sulfoxide to prepare MAPbCl₃And (3) precursor solution.

And step 3: and (3) dripping 0.5mL of precursor solution into the solution prepared in the step (1), stirring for 2-3 min, centrifuging at 7000rpm, and removing large particles to obtain supernatant, namely the solution of the composite material.

And 4, step 4: and (4) evaporating the solution obtained in the step (3) at 50 ℃ to obtain the composite material.

The morphology of the composite material of the embodiment is the same as that of the embodiment 1, and the composite material is composed of a polycaprolactone matrix and perovskite quantum dots distributed in the polycaprolactone matrix.

The composite material prepared by the embodiment is used for preparing a 3D printing wire, and specifically comprises the following components: and (3) putting the composite material into an SJZS-10A double-screw extruder, setting the temperature of a first zone to be 45 ℃, the temperature of a second zone to be 50 ℃, the temperature of a third zone to be 70 ℃ and the temperature of a fourth zone to be 70 ℃, and performing melt extrusion on the 3D printing wire. The obtained 3D printing wire rod has obvious luminescence under an ultraviolet lamp before and after water is added.

Comparative example 1

The use of the bright luminescence and Color Tunable Colloidal CH references reported by zhang et al₃NH₃PbX₃The method for preparing the pure perovskite Quantum dot by the (X ═ Br, I, Cl) Quantum Dots, which is described in the patent Alternatives for Display Technology, specifically comprises the following steps:

mixing a certain proportion of PbX₂、CH₃NH₃X (X ═ Cl, Br, I), octylamine or octylammonium bromide, and oleic acid were dissolved in 5mL of a polar organic solvent. Fully dissolving to obtain clear and transparent precursor solution, adding a certain volume of the precursor solution into 10mL of nonpolar solvent toluene stirred by high-speed magnetic force, fully stirring, centrifuging at 7000rpm at high speed to obtain the upper layerObtaining the corresponding perovskite quantum dot colloidal solution from the clear liquid. Perovskite quantum dots for testing thermal stability were powders obtained after heating at 40 ℃ to evaporate excess toluene.

Comparative example 2

The comparative example combines polylactic acid (PLA) and perovskite quantum dots which are commonly used for 3D printing, and the synthesis method comprises the following steps: because polylactic acid is not soluble with toluene, the polylactic acid material is put into the pure perovskite quantum dot solution prepared in the comparative example 1, and after stirring for 2 hours, the polylactic acid particles are taken out, and obvious luminescence can be seen under an ultraviolet lamp. The water stability of the PQDs-PLA composite was tested by placing the perovskite quantum dot doped particles and lines into water.

As can be seen from FIG. 7, the fluorescence of the PLA-PQDs composite disappeared after the addition of water, indicating quenching of the perovskite quantum dots.