3D printing composite material based on quantum dot modification and preparation method and application thereof

Abstract

The invention belongs to the technical field of 3D printing materials, and provides a 3D printing composite material based on quantum dot modification and a preparation method and application thereof. The method comprises the following steps: mixing a modified quantum dot solution with sulfydryl-modified silica powder, and reacting to obtain modified silica powder; blending and extruding the modified silica powder and a 3D printing matrix material to obtain the 3D printing composite material based on quantum dot modification. By introducing the quantum dots and the silica powder, the luminous efficiency, the environmental stability and the mechanical property of the material are improved, so that the 3D printing composite material which is multifunctional, low in energy consumption and long in service life is provided; the method can be widely applied to the fields of intelligent building supplies, personalized living supplies, safety sign supplies, traffic facility supplies, intelligent wearable equipment supplies or medical equipment supplies and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing materials, and particularly to a 3D printing composite material modified by quantum dots, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, 3D printing technology has developed rapidly and is widely used in fields such as manufacturing, medical treatment, architecture, and art. However, the existing 3D printing materials are mainly plastics, metals, and ceramics. Although these materials perform well in terms of strength and durability, they have problems such as single function, insufficient luminescent properties, and poor environmental adaptability in applications. Traditional 3D printing materials are mostly single-functional and difficult to meet the requirements of intelligence and multi-function. Most materials do not have the function of self-luminescence or induced luminescence and cannot provide additional visual effects in low-light or lightless environments. In addition, some materials have unstable performance, short service life, and low reliability in harsh environments such as high temperature and high humidity. Therefore, it is of great significance to provide a 3D printing material with multi-function, high luminous efficiency, low energy consumption, and long life. Summary of the Invention

[0003] The purpose of the present invention is to overcome the problems existing in the prior art and provide a 3D printing composite material modified by quantum dots, a preparation method thereof, and an application thereof.

[0004] In order to achieve the above invention purpose, the present invention provides the following technical solutions:

[0005] The present invention provides a preparation method of a 3D printing composite material modified by quantum dots, comprising the following steps:

[0006] (1) Under a protective atmosphere, injecting a selenium source solution into a cadmium source solution to react to obtain CdSe quantum dots;

[0007] (2) Mixing the CdSe quantum dots, a zinc source solution, and a sulfur source solution to react to obtain CdSe / ZnS quantum dots;

[0008] (3) Mixing the CdSe / ZnS quantum dots, an organic solvent, and a multifunctional ligand to react to obtain a modified quantum dot solution;

[0009] (4) Mixing the modified quantum dot solution and mercapto-modified silicon micropowder to react to obtain modified silicon micropowder;

[0010] (5) Co-extruding the modified silicon micropowder and a 3D printing matrix material to obtain the 3D printing composite material modified by quantum dots;

[0011] The preparation method of the mercapto-modified silicon micropowder comprises the following steps: mixing silicon micropowder, ethanol, and a silanizing agent to react to obtain mercapto-modified silicon micropowder.

[0012] Preferably, the selenium source in the selenium source solution in step (1) includes selenium powder, and the solvent of the selenium source solution includes tri-n-octylphosphine oxide or trioctylphosphine; the concentration of the selenium source solution is 0.2 to 0.5 mol / L;

[0013] The cadmium source in the cadmium source solution includes cadmium oxide, cadmium acetate or cadmium nitrate, and the solvent of the cadmium source solution includes one or more of oleic acid, 1-octene, cetylamine and alkenylamine solvents; the alkenylamine solvents include one or more of n-octylamine, n-dodecylamine and n-hexadecylamine; the concentration of the cadmium source solution is 0.1 to 0.3 mol / L;

[0014] The molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution in step (1) is 1:1 to 2.

[0015] Preferably, the temperature of the reaction in step (1) is 260 to 290 °C, and the reaction time is 20 to 40 min.

[0016] Preferably, the zinc source in the zinc source solution in step (2) includes zinc oxide, zinc acetate or zinc nitrate; the concentration of the zinc source solution is 0.4 to 0.6 mol / L;

[0017] The sulfur source in the sulfur source solution includes sodium sulfide, ammonium sulfide or thiourea; the concentration of the sulfur source solution is 0.4 to 0.6 mol / L;

[0018] The molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution and the sulfur source in the sulfur source solution in step (2) is 1:8 to 12:13 to 17;

[0019] The temperature of the reaction in step (2) is 100 to 140 °C, and the reaction time is 0.5 to 1.5 h.

[0020] Preferably, the organic solvent in step (3) includes one or more of n-hexane, n-octane, n-dodecane and toluene; the multifunctional ligand includes one or more of ethyl 2-mercaptoacetate, 3-mercaptopropionic acid and mercaptoacetic acid;

[0021] The mass-volume ratio of the CdSe / ZnS quantum dots, the organic solvent and the multifunctional ligand in step (3) is 1 kg:8 to 15 L:0.2 to 1 L;

[0022] The temperature of the reaction in step (3) is 20 to 30 °C, and the reaction time is 0.5 to 2.5 h.

[0023] Preferably, when preparing the thiol-modified silica powder, the particle size of the silica powder is 50-200 nm; the silanizing agent includes one or more of 3-mercaptopropyltrimethoxysilane solution, 3-mercaptopropyltriethoxysilane solution, and 3-mercaptopropylmethyldimethoxysilane solution; the mass fraction of the silanizing agent is 0.5-1.5%;

[0024] The mass-volume ratio of the silica powder, ethanol, and the silanizing agent is 0.9-1.1 kg: 8-12 L: 0.4-0.6 L;

[0025] The reaction temperature is 20-30 °C, and the reaction time is 1.5-2.5 h.

[0026] Preferably, in the modified quantum dot solution described in step (4), the mass ratio of the modified quantum dots to the thiol-modified silica powder is 1:8-14; the mass fraction of the modified quantum dot solution is 5-10%;

[0027] The reaction temperature in step (4) is 20-30 °C, and the reaction time is 0.5-2.5 h.

[0028] Preferably, the 3D printing matrix material described in step (5) includes polycarbonate, polymethyl methacrylate, transparent nylon, or transparent polyurethane;

[0029] The mass ratio of the modified silica powder to the 3D printing matrix material in step (5) is 5-15:100;

[0030] The temperature of the co-extrusion in step (5) is 190-280 °C.

[0031] The present invention also provides a 3D printing composite material modified with quantum dots prepared by the preparation method of the 3D printing composite material modified with quantum dots described above.

[0032] The present invention also provides the application of the 3D printing composite material modified with quantum dots in intelligent building supplies, personalized daily necessities, safety sign supplies, traffic facility supplies, intelligent wearable device supplies, or medical device supplies.

[0033] The beneficial effects of the present invention are:

[0034] The present invention provides a 3D printing composite material modified with quantum dots. By introducing quantum dots and silicon micropowder, the luminescence efficiency, environmental stability and mechanical properties of the material are improved, thereby providing a multifunctional, low-energy consumption and long-life 3D printing composite material, which can be widely applied to fields such as intelligent building supplies, personalized daily necessities, safety sign supplies, traffic facility supplies, intelligent wearable device supplies or medical device supplies. Specifically, the 3D printing composite material modified with quantum dots prepared by the present invention has the following advantages: (1) Multifunctional integration: The 3D printing composite material modified with quantum dots integrates functions such as self-luminescence, environmental response and high mechanical strength, meeting the requirements of various application scenarios; (2) High luminescence efficiency: By introducing CdSe / ZnS core-shell structure quantum dots, the luminescence efficiency of the material is significantly improved, enabling it to provide good visual effects even in low-light or no-light environments; (3) Excellent environmental stability: The modified silicon micropowder has high reflectivity and good mechanical properties, ensuring the stability and long life of the composite material in harsh environments such as high temperature and high humidity; (4) Low energy consumption: The high quantum yield and excellent photostability of the quantum dot material reduce the energy consumption of the material, making it suitable for application scenarios with long-term and high-frequency use; (5) Multicolor display ability: By adjusting the size and composition of the quantum dots, the composite material can achieve luminescence displays of multiple colors, increasing its application flexibility in intelligent buildings and personalized daily necessities; (6) Processability: Good processability makes the 3D printing composite material modified with quantum dots easy to use and form during the 3D printing process; (7) Wide application prospects: It is applicable to multiple fields such as intelligent building supplies, personalized daily necessities, safety sign supplies, traffic facility supplies, intelligent wearable device supplies, medical device supplies, etc., and has broad market application prospects. Detailed implementation mode

[0035] The present invention provides a preparation method of a 3D printing composite material modified with quantum dots, comprising the following steps:

[0036] (1) Under a protective atmosphere, inject a selenium source solution into a cadmium source solution and react to obtain CdSe quantum dots;

[0037] (2) Mix the CdSe quantum dots, a zinc source solution and a sulfur source solution and react to obtain CdSe / ZnS quantum dots;

[0038] (3) Mix the CdSe / ZnS quantum dots, an organic solvent and a multifunctional ligand and react to obtain a modified quantum dot solution;

[0039] (4) Mix the modified quantum dot solution and mercapto-modified silicon micropowder and react to obtain modified silicon micropowder;

[0040] (5) Mix the modified silica powder and the 3D printing matrix material by co-extrusion to obtain the 3D printing composite material based on quantum dot modification;

[0041] The preparation method of the thiol-modified silica powder comprises the following steps: mix the silica powder, ethanol and a silylating reagent, and carry out a reaction to obtain the thiol-modified silica powder.

[0042] In the present invention, the protective atmosphere in step (1) is preferably nitrogen.

[0043] In the present invention, the selenium source in the selenium source solution in step (1) preferably includes selenium powder, and the solvent of the selenium source solution preferably includes tri-n-octylphosphine oxide (TOPO) or trioctylphosphine (TOP); the concentration of the selenium source solution is preferably 0.2 - 0.5 mol / L, more preferably 0.25 - 0.45 mol / L, and still more preferably 0.3 - 0.4 mol / L.

[0044] In the present invention, the cadmium source in the cadmium source solution in step (1) preferably includes cadmium oxide, cadmium acetate or cadmium nitrate, and the solvent of the cadmium source solution preferably includes one or more of oleic acid, 1-octene, cetylamine and alkenylamine solvents; the alkenylamine solvents preferably include one or more of n-octylamine, n-dodecylamine and n-hexadecylamine; the concentration of the cadmium source solution is preferably 0.1 - 0.3 mol / L, more preferably 0.15 - 0.25 mol / L, and still more preferably 0.2 mol / L.

[0045] In the present invention, the molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution in step (1) is preferably 1:1 - 2, more preferably 1:1.2 - 1.8, and still more preferably 1:1.5 - 1.6; setting the molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution within the above range can ensure that the reaction between Cd and Se can proceed fully, so as to obtain stable CdSe quantum dots.

[0046] In the present invention, the temperature of the reaction in step (1) is preferably 260 - 290 °C, more preferably 265 - 285 °C, and still more preferably 270 - 280 °C; the reaction time is preferably 20 - 40 min, more preferably 25 - 35 min, and still more preferably 30 min.

[0047] In the present invention, after the reaction in step (1) is completed, the obtained system is naturally cooled and then centrifuged to separate the sample. The sample is washed with ethanol to remove unreacted impurities and by-products, and finally vacuum dried to obtain CdSe quantum dots. The target temperature for natural cooling is preferably 20 - 30 °C, more preferably 22 - 28 °C, and even more preferably 25 - 26 °C. The rotation speed for centrifugation is preferably 6000 - 10000 r / min, more preferably 7000 - 9000 r / min, and even more preferably 8000 r / min. The centrifugation time is preferably 15 - 30 min, more preferably 20 - 25 min, and even more preferably 22 min. The number of times for ethanol washing is preferably 2 - 3 times. The temperature for vacuum drying is preferably 50 - 70 °C, more preferably 55 - 65 °C, and even more preferably 60 °C. The vacuum degree for vacuum drying is preferably 1×10 2 ~1×10 3 Pa, more preferably 2×10 2 ~8×10 2 Pa, and even more preferably 5×10 2 ~6×10 2 Pa. The time for vacuum drying is preferably 4 - 6 h, more preferably 4.5 - 5.5 h, and even more preferably 5 h.

[0048] In the present invention, the zinc source in the zinc source solution in step (2) preferably includes zinc oxide, zinc acetate or zinc nitrate. The solvent of the zinc source solution is preferably water. The concentration of the zinc source solution is preferably 0.4 - 0.6 mol / L, more preferably 0.45 - 0.55 mol / L, and even more preferably 0.5 mol / L.

[0049] In the present invention, the sulfur source in the sulfur source solution preferably includes sodium sulfide, ammonium sulfide or thiourea. The solvent of the sulfur source solution is preferably water. The concentration of the sulfur source solution is preferably 0.4 - 0.6 mol / L, more preferably 0.45 - 0.55 mol / L, and even more preferably 0.5 mol / L.

[0050] In the present invention, the molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution and the sulfur source in the sulfur source solution in step (2) is preferably 1:8 - 12:13 - 17, more preferably 1:9 - 11:14 - 16, and even more preferably 1:10:15. Limiting the mass - volume ratio of the CdSe quantum dots, the zinc source solution and the sulfur source solution within the above range can ensure that the ZnS shell is uniformly coated on the surface of the CdSe quantum dots, thereby improving the luminescence efficiency and stability of the quantum dots.

[0051] In the present invention, the temperature of the reaction in step (2) is preferably 100 - 140 °C, more preferably 110 - 130 °C, and even more preferably 120 - 125 °C; the reaction time is preferably 0.5 - 1.5 h, more preferably 0.75 - 1.25 h, and even more preferably 1 h.

[0052] In the present invention, after the reaction in step (2) is completed, the resulting system is naturally cooled, then centrifuged to separate the sample, the sample is washed to remove unreacted precursors and by-products, and finally vacuum dried to obtain CdSe / ZnS quantum dots; the target temperature for natural cooling is preferably 20 - 30 °C, more preferably 22 - 28 °C, and even more preferably 25 - 26 °C; the rotation speed for centrifugation is preferably 6000 - 10000 r / min, more preferably 7000 - 9000 r / min, and even more preferably 8000 r / min; the centrifugation time is preferably 15 - 30 min, more preferably 20 - 25 min, and even more preferably 22 min; the washing reagent is preferably ethanol or n-hexane; the number of washing times is preferably 2 - 3 times, the temperature for vacuum drying is preferably 50 - 70 °C, more preferably 55 - 65 °C, and even more preferably 60 °C; the vacuum degree for vacuum drying is preferably 1×10 2 ~1×10 3 Pa, more preferably 2×10 2 ~8×10 2 Pa, and even more preferably 5×10 2 ~6×10 2 Pa; the time for vacuum drying is preferably 4 - 6 h, more preferably 4.5 - 5.5 h, and even more preferably 5 h.

[0053] In the present invention, the CdSe / ZnS quantum dots obtained from the reaction in step (2) have CdSe as the core and ZnS as the shell. The formation of the ZnS shell is beneficial to improving the stability and luminescence efficiency of the quantum dots; among them, when the sizes of the obtained CdSe / ZnS quantum dots are different, luminescence of different wavelengths can be achieved.

[0054] In the present invention, the size of the CdSe / ZnS quantum dots is mainly regulated by the following reaction conditions: (a) reaction temperature: the higher the temperature, the larger the size of the quantum dots; at a higher temperature, the crystal nuclei of CdSe quantum dots grow faster, resulting in an increase in particle size; (b) reaction time: the longer the reaction time, the larger the size of the quantum dots. Prolonging the reaction time will cause the crystal nuclei of the quantum dots to continue growing; (c) precursor concentration: a higher precursor concentration can accelerate the growth of crystal nuclei, thereby increasing the size of the quantum dots. Conversely, a low concentration of precursors is beneficial for the formation of small-sized quantum dots; (d) ligand type: using different ligands can affect the surface passivation effect of the quantum dots, thereby indirectly affecting the growth rate of the crystal nuclei.

[0055] In the present invention, the organic solvent in step (3) preferably includes one or more of n-hexane, n-octane, n-dodecane, and toluene; the multifunctional ligand preferably includes one or more of ethyl 2-mercaptoacetate (MEA), 3-mercaptopropionic acid (MPA), and mercaptoacetic acid (MTA).

[0056] In the present invention, the mass-volume ratio of the CdSe / ZnS quantum dots, the organic solvent, and the multifunctional ligand in step (3) is preferably 1 kg: 8-15 L: 0.2-1 L, more preferably 1 kg: 10-12 L: 0.5-0.8 L, and even more preferably 1 kg: 11 L: 0.6 L; limiting the mass-volume ratio of the CdSe / ZnS quantum dots, the organic solvent, and the multifunctional ligand within the above range can ensure good dispersion of the quantum dots in the organic solvent, and the appropriate amount of the multifunctional ligand enhances the binding force between the quantum dots and the matrix material, thereby improving the stability and mechanical properties of the composite material.

[0057] In the present invention, the temperature of the reaction in step (3) is preferably 20-30 °C, more preferably 22-28 °C, and even more preferably 25 °C; the reaction time is preferably 0.5-2.5 h, more preferably 1-2 h, and even more preferably 1.5 h. After the reaction in step (3) is completed, the surface of the modified quantum dots has mercapto and carboxyl groups, which can improve the binding force and dispersibility with silica powder in the subsequent process.

[0058] In the present invention, when preparing mercapto-modified silica powder, the silica powder is dispersed in ethanol, and after being dispersed evenly, a silanizing agent is added, and the reaction is carried out under stirring conditions.

[0059] In the present invention, the particle size of the silica powder is preferably 50-200 nm, more preferably 100-150 nm, and even more preferably 125 nm; the silanizing agent preferably includes one or more of 3-mercaptopropyltrimethoxysilane solution, 3-mercaptopropyltriethoxysilane solution, and 3-mercaptopropylmethyldimethoxysilane solution; the mass fraction of the silanizing agent is preferably 0.5-1.5%, more preferably 0.7-1.3%, and even more preferably 1%.

[0060] In the present invention, when preparing mercapto-modified silica powder, the mass-volume ratio of the silica powder, ethanol, and the silanizing agent is preferably 0.9-1.1 kg: 8-12 L: 0.4-0.6 L, more preferably 0.95-1.05 kg: 8.5-11 L: 0.45-0.55 L, and even more preferably 1-1.02 kg: 9-10 L: 0.48-0.5 L.

[0061] In the present invention, when preparing the mercapto-modified silicon micropowder, the stirring speed of the reaction is preferably 300 - 500 r / min, more preferably 350 - 450 r / min, and even more preferably 400 r / min; the reaction temperature is preferably 20 - 30 °C, more preferably 22 - 28 °C, and even more preferably 25 - 27 °C; the reaction time is preferably 1.5 - 2.5 h, more preferably 1.7 - 2.3 h, and even more preferably 2 h; the reaction temperature and time are limited within the above ranges to ensure that the silanization reagent reacts fully with the surface of the silicon micropowder.

[0062] In the present invention, when preparing the mercapto-modified silicon micropowder, after the reaction ends, the obtained system is centrifuged to separate the sample, and the sample is washed with ethanol to remove the unreacted silanization reagent, and finally vacuum dried to obtain the mercapto-modified silicon micropowder; the centrifugation speed is preferably 6000 - 10000 r / min, more preferably 7000 - 9000 r / min, and even more preferably 8000 r / min; the centrifugation time is preferably 15 - 30 min, more preferably 20 - 25 min, and even more preferably 22 min; the number of times of ethanol washing is preferably 2 - 3 times, the vacuum drying temperature is preferably 50 - 70 °C, more preferably 55 - 65 °C, and even more preferably 60 °C; the vacuum degree of vacuum drying is preferably 1×10 2 ~1×10 3 Pa, more preferably 2×10 2 ~8×10 2 Pa, and even more preferably 5×10 2 ~6×10 2 Pa; the vacuum drying time is preferably 4 - 6 h, more preferably 4.5 - 5.5 h, and even more preferably 5 h.

[0063] In the present invention, in the modified quantum dot solution in step (4), the mass ratio of the modified quantum dots to the mercapto-modified silicon micropowder is preferably 1:8 - 14, more preferably 1:9 - 13, and even more preferably 1:10 - 12; the mass fraction of the modified quantum dot solution is preferably 5 - 10%, more preferably 6 - 9%, and even more preferably 7 - 8%.

[0064] In the present invention, in step (4), the stirring speed of the reaction is preferably 400 - 600 r / min, more preferably 450 - 550 r / min, and even more preferably 500 r / min; the reaction temperature is preferably 20 - 30 °C, more preferably 22 - 28 °C, and even more preferably 25 °C; the reaction time is preferably 0.5 - 2.5 h, more preferably 1 - 2 h, and even more preferably 1.5 h.

[0065] In the present invention, after the reaction in step (4) is completed, the resulting system is centrifuged to separate the modified silicon micropowder. The modified silicon micropowder is washed with ethanol and then dried under vacuum, and then used in step (5); the rotation speed of centrifugation is preferably 6000 - 10000 r / min, more preferably 7000 - 9000 r / min, and even more preferably 8000 r / min; the time of centrifugation is preferably 15 - 30 min, more preferably 20 - 25 min, and even more preferably 22 min; setting the rotation speed of centrifugation within the above range helps to separate smaller quantum dot particles, and setting the time of centrifugation within the above range can ensure the complete sedimentation of quantum dots and silicon micropowder, avoiding impurity residues, so as to obtain high-purity modified silicon micropowder; the number of times of washing with ethanol is preferably 2 - 3 times, the temperature of vacuum drying is preferably 50 - 70 °C, more preferably 55 - 65 °C, and even more preferably 60 °C; the vacuum degree of vacuum drying is preferably 1×10 2 ~1×10 3 Pa, more preferably 2×10 2 ~8×10 2 Pa, and even more preferably 5×10 2 ~6×10 2 Pa; the time of vacuum drying is preferably 4 - 6 h, more preferably 4.5 - 5.5 h, and even more preferably 5 h.

[0066] In the present invention, the 3D printing matrix material in step (5) preferably includes polycarbonate (PC), polymethyl methacrylate (PMMA), transparent nylon (PA12), or transparent polyurethane (TPU).

[0067] In the present invention, the mass ratio of the modified silicon micropowder to the 3D printing matrix material in step (5) is preferably 5 - 15:100, more preferably 7 - 12:100, and even more preferably 8 - 10:100.

[0068] In the present invention, the temperature of the co - extrusion in step (5) is 190 - 280 °C; specifically, when the 3D printing matrix material is polycarbonate, the temperature of the co - extrusion is preferably 250 - 280 °C, more preferably 260 - 270 °C, and even more preferably 265 °C; when the 3D printing matrix material is polymethyl methacrylate, the temperature of the co - extrusion is preferably 220 - 250 °C, more preferably 230 - 240 °C, and even more preferably 245 °C; when the 3D printing matrix material is transparent nylon, the temperature of the co - extrusion is preferably 200 - 230 °C, more preferably 210 - 220 °C, and even more preferably 215 °C; when the 3D printing matrix material is transparent polyurethane, the temperature of the co - extrusion is preferably 190 - 220 °C, more preferably 200 - 210 °C, and even more preferably 205 °C.

[0069] In the present invention, after the blending and extrusion in step (5), the obtained filamentous material is rapidly cooled and formed to obtain the quantum dot-modified 3D printing composite material; the cooling method is conventionally adjusted according to actual needs, preferably water cooling or air cooling; the cooling speed is preferably 3-7 m / min, more preferably 4-6 m / min, and still more preferably 5 m / min; setting the cooling speed within the above range can ensure that the quantum dot-modified 3D printing composite material can be rapidly shaped and maintain good optical and mechanical properties.

[0070] The present invention also provides a quantum dot-modified 3D printing composite material prepared by the preparation method of the quantum dot-modified 3D printing composite material described above.

[0071] The present invention also provides the application of the quantum dot-modified 3D printing composite material in intelligent building supplies, personalized daily necessities, safety sign supplies, transportation facility supplies, intelligent wearable device supplies or medical device supplies.

[0072] The technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they cannot be understood as limiting the protection scope of the present invention.

[0073] Example 1

[0074] Under a nitrogen atmosphere, a selenium source solution with a concentration of 0.2 mol / L (the selenium source is selenium powder and the solvent is trioctylphosphine) is injected into a cadmium source solution with a concentration of 0.2 mol / L (the cadmium source is cadmium oxide and the solvent contains oleic acid and 1-octene, and the volume ratio of oleic acid to 1-octene is 1:5). The molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution is 1:1. The reaction is carried out at 275 °C for 30 min. After the reaction is completed, the obtained system is naturally cooled to 25 °C, then centrifuged at a speed of 7000 r / min for 20 min to separate the sample. The sample is washed with ethanol 3 times, and finally dried at a vacuum degree of 10 2 Pa and a temperature of 60 °C for 5 h to obtain CdSe quantum dots; the CdSe quantum dots, a zinc source solution with a concentration of 0.5 mol / L (the zinc source is zinc oxide and the solvent is water), and a sulfur source solution with a concentration of 0.5 mol / L (the sulfur source is sodium sulfide and the solvent is water) are mixed. The molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution, and the sulfur source in the sulfur source solution is 1:8:13. The reaction is carried out at 120 °C for 1 h. After the reaction is completed, the obtained system is naturally cooled to 25 °C, then centrifuged at a speed of 8000 r / min for 20 min to separate the sample. The sample is washed with ethanol 3 times, and finally dried at a vacuum degree of 10 2It was dried at 60 °C under a pressure of Pa for 5 h to obtain CdSe / ZnS quantum dots; the CdSe / ZnS quantum dots, an organic solvent (n - hexane), and a multifunctional ligand (ethyl 2 - mercaptoacetate) were mixed. The mass - to - volume ratio of the CdSe / ZnS quantum dots, the organic solvent, and the multifunctional ligand was 1 kg:10 L:0.5 L, and they were reacted at 25 °C for 1 h to obtain a modified quantum dot solution;

[0075] 1 kg of silicon micropowder with a particle size of 200 nm was dispersed in 10 L of ethanol, stirred for 30 min, and then 0.5 L of a 1% 3 - mercaptopropyltrimethoxysilane solution was added. The reaction was carried out at 25 °C for 2 h under a stirring speed of 400 r / min. After the reaction, the obtained system was centrifuged at 6000 r / min for 20 min to separate the sample. The sample was washed with ethanol 3 times, and finally dried at 60 °C under a pressure of 10 2 Pa for 5 h to obtain mercapto - modified silicon micropowder;

[0076] A 5% modified quantum dot solution and mercapto - modified silicon micropowder were mixed. The mass ratio of the modified quantum dots to the mercapto - modified silicon micropowder in the modified quantum dot solution was 1:10. The reaction was carried out at 500 r / min and 25 °C for 1 h. After the reaction, it was centrifuged at 7000 r / min for 15 min to separate the modified silicon micropowder. The modified silicon micropowder was washed with ethanol 3 times and then dried at 60 °C under a pressure of 10 2 Pa for 5 h to obtain modified silicon micropowder;

[0077] The modified silicon micropowder and polycarbonate (PC) were melt - blended and extruded. Among them, the mass ratio of the modified silicon micropowder to PC was 10:100, and the temperature of the melt - blending extrusion was 260 °C. The filamentous material obtained by the melt - blending extrusion was rapidly cooled and formed through a cooling system. The cooling method was water - cooling with a speed of 5 m / min to obtain a 3D printing composite material modified with quantum dots.

[0078] The modified silicon micropowder prepared in this example was irradiated with an ultraviolet lamp (LED, wavelength 365 nm). The material emitted bright green light under ultraviolet excitation, verifying the luminescence performance of the quantum dots and proving that the modified silicon micropowder prepared in this example has good optical properties and luminescence efficiency.

[0079] Using a standard 3D printing device, the 3D printing composite material modified with quantum dots prepared in this example was printed into an intelligent building exterior wall panel. The obtained intelligent building exterior wall panel has the characteristics of self - luminescence and high mechanical strength, can provide a visual effect at night or in a low - light environment, and at the same time has good environmental adaptability and a long service life, and is suitable for the exterior decoration and functional applications of intelligent buildings.

[0080] Example 2

[0081] Under a nitrogen atmosphere, a selenium source solution with a concentration of 0.2 mol / L (the selenium source is selenium powder and the solvent is trioctylphosphine) was injected into a cadmium source solution with a concentration of 0.2 mol / L (the cadmium source is cadmium oxide and the solvent contains oleic acid and 1-octene, and the volume ratio of oleic acid to 1-octene is 1:5). The molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution was 1:1. The reaction was carried out at 260 °C for 20 min. After the reaction ended, the obtained system was naturally cooled to 25 °C, and then centrifuged at a speed of 7000 r / min for 20 min to separate the sample. The sample was washed 3 times with ethanol, and finally dried at a vacuum of 10 2 Pa and a temperature of 60 °C for 5 h to obtain CdSe quantum dots; the CdSe quantum dots, a zinc source solution with a concentration of 0.5 mol / L (the zinc source is zinc oxide and the solvent is water), and a sulfur source solution with a concentration of 0.5 mol / L (the sulfur source is sodium sulfide and the solvent is water) were mixed. The molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution, and the sulfur source in the sulfur source solution was 1:10:15. The reaction was carried out at 110 °C for 0.75 h. After the reaction ended, the obtained system was naturally cooled to 25 °C, and then centrifuged at a speed of 8000 r / min for 20 min to separate the sample. The sample was washed 3 times with ethanol, and finally dried at a vacuum of 10 2 Pa and a temperature of 60 °C for 5 h to obtain CdSe / ZnS quantum dots; the CdSe / ZnS quantum dots, an organic solvent (n-hexane), and a multifunctional ligand (3-mercaptopropionic acid) were mixed. The mass-volume ratio of the CdSe / ZnS quantum dots, the organic solvent, and the multifunctional ligand was 1 kg:12 L:0.6 L. The reaction was carried out at 25 °C for 1 h to obtain a modified quantum dot solution;

[0082] 1 kg of silicon micropowder with a particle size of 150 nm was dispersed in 10 L of ethanol and stirred for 40 min. Then, 0.45 L of a 3-mercaptopropyltrimethoxysilane solution with a mass fraction of 1% was added. Under the condition of a stirring speed of 400 r / min, the reaction was carried out at 25 °C for 1.5 h. After the reaction ended, the obtained system was centrifuged at a speed of 6000 r / min for 20 min to separate the sample. The sample was washed 3 times with ethanol, and finally dried at a vacuum of 10 2 Pa and a temperature of 60 °C for 4 h to obtain mercapto-modified silicon micropowder;

[0083] Mix a modified quantum dot solution with a mass fraction of 6% and mercapto-modified silica powder. The mass ratio of the modified quantum dots to the mercapto-modified silica powder in the modified quantum dot solution is 1:12. React for 1 h under the conditions of a rotation speed of 500 r / min and a temperature of 25 °C. After the reaction, centrifuge at a rotation speed of 7000 r / min for 15 min to separate the modified silica powder. Wash the modified silica powder 3 times with ethanol and then dry it under the conditions of a vacuum degree of 10 2 Pa and a temperature of 60 °C for 5 h to obtain the modified silica powder;

[0084] Co-blend and extrude the modified silica powder and polymethyl methacrylate (PMMA). Among them, the mass ratio of the modified silica powder to PMMA is 10:100. The co-blending and extrusion temperature is 240 °C. Cool and form the filamentous material obtained by co-blending and extrusion quickly through a cooling system. The cooling method is water cooling with a speed of 4 m / min to obtain a 3D printing composite material modified with quantum dots.

[0085] Irradiate the modified silica powder prepared in this example with an ultraviolet lamp (LED, wavelength 365 nm). The material emits bright blue light under ultraviolet excitation, verifying the luminescence performance of the quantum dots and proving that the modified silica powder prepared in this example has good optical properties and luminescence efficiency.

[0086] Use a standard 3D printing device to print the 3D printing composite material modified with quantum dots prepared in this example into personalized daily necessities. The obtained personalized daily necessities have the characteristics of self-luminescence and high mechanical strength, can be used at night or in an environment with insufficient light, and have good decorative properties and environmental adaptability.

[0087] Example 3

[0088] Under a nitrogen atmosphere, inject a selenium source solution with a concentration of 0.2 mol / L (the selenium source is selenium powder and the solvent is trioctylphosphine) into a cadmium source solution with a concentration of 0.2 mol / L (the cadmium source is cadmium oxide and the solvent contains oleic acid and 1-octene, and the volume ratio of oleic acid to 1-octene is 1:5). The molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution is 1:1. React at 290 °C for 25 min. After the reaction, naturally cool the obtained system to 25 °C, then centrifuge at a rotation speed of 7000 r / min for 20 min to separate the sample. Wash the sample 3 times with ethanol, and finally under a vacuum degree of 10 2Dry for 5 h under the conditions of Pa and a temperature of 60 °C to obtain CdSe quantum dots; mix the CdSe quantum dots, a zinc source solution with a concentration of 0.5 mol / L (the zinc source is zinc oxide and the solvent is water), and a sulfur source solution with a concentration of 0.5 mol / L (the sulfur source is sodium sulfide and the solvent is water). The molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution, and the sulfur source in the sulfur source solution is 1:12:17. React at 130 °C for 1 h. After the reaction is completed, naturally cool the obtained system to 25 °C, then centrifuge at a rotation speed of 8000 r / min for 20 min to separate the sample. Wash the sample with ethanol 3 times, and finally under a vacuum of 10 2 Dry for 5 h under the conditions of Pa and a temperature of 60 °C to obtain CdSe / ZnS quantum dots; mix the CdSe / ZnS quantum dots, an organic solvent (n - hexane), and a multifunctional ligand (3 - mercaptopropionic acid). The mass - to - volume ratio of the CdSe / ZnS quantum dots, the organic solvent, and the multifunctional ligand is 1 kg:15 L:0.8 L. React at 25 °C for 1 h to obtain a modified quantum dot solution;

[0089] Disperse 1 kg of silicon micro - powder with a particle size of 180 nm in 10 L of ethanol, stir for 35 min, then add 0.55 L of a 3 - mercaptopropylmethyldimethoxysilane solution with a mass fraction of 1%. React at 25 °C for 2 h under the condition of a stirring speed of 350 r / min. After the reaction is completed, centrifuge the obtained system at a rotation speed of 6000 r / min for 20 min to separate the sample. Wash the sample with ethanol 3 times, and finally under a vacuum of 10 2 Dry for 5 h under the conditions of Pa and a temperature of 55 °C to obtain mercapto - modified silicon micro - powder;

[0090] Mix a modified quantum dot solution with a mass fraction of 7% and the mercapto - modified silicon micro - powder. The mass ratio of the modified quantum dots in the modified quantum dot solution to the mercapto - modified silicon micro - powder is 1:14. React at a rotation speed of 500 r / min and a temperature of 25 °C for 1 h. After the reaction is completed, centrifuge at a rotation speed of 7000 r / min for 15 min to separate the modified silicon micro - powder. Wash the modified silicon micro - powder with ethanol 3 times and then dry under a vacuum of 10 2 Dry for 5 h under the conditions of Pa and a temperature of 60 °C to obtain modified silicon micro - powder;

[0091] Co - extrude the modified silicon micro - powder and polyamide (PA12). Among them, the mass ratio of the modified silicon micro - powder to PA12 is 10:100. The co - extrusion temperature is 220 °C. Cool and form the filamentous material obtained by co - extrusion through a cooling system quickly. The cooling method is air cooling and the speed is 3 m / min to obtain a 3D printing composite material modified with quantum dots.

[0092] The modified silica powder prepared in this example was irradiated with an ultraviolet lamp (LED, wavelength 365 nm). The material emitted bright red light under ultraviolet excitation, verifying the luminescence performance of the quantum dots and proving that the modified silica powder prepared in this example has good optical properties and luminescence efficiency.

[0093] Using a standard 3D printing device, the 3D printing composite material based on quantum dot modification prepared in this example was printed into traffic facility signs. The obtained signs have self-luminescence and high mechanical strength, are suitable for use at night or in emergency situations, and have good environmental adaptability and long lifespan.

[0094] Example 4

[0095] Under a nitrogen atmosphere, a selenium source solution with a concentration of 0.2 mol / L (the selenium source is selenium powder and the solvent is trioctylphosphine) was injected into a cadmium source solution with a concentration of 0.2 mol / L (the cadmium source is cadmium oxide and the solvent contains oleic acid and 1-octene, and the volume ratio of oleic acid to 1-octene is 1:5). The molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution is 1:1. The reaction was carried out at 285 °C for 30 min. After the reaction ended, the obtained system was naturally cooled to 25 °C, and then centrifuged at a rotation speed of 7000 r / min for 20 min to separate the sample. The sample was washed with ethanol three times, and finally dried under a vacuum of 10 2 Pa and a temperature of 60 °C for 5 h to obtain CdSe quantum dots; the CdSe quantum dots, a zinc source solution with a concentration of 0.5 mol / L (the zinc source is zinc oxide and the solvent is water), and a sulfur source solution with a concentration of 0.5 mol / L (the sulfur source is sodium sulfide and the solvent is water) were mixed. The molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution, and the sulfur source in the sulfur source solution is 1:10:15. The reaction was carried out at 125 °C for 0.75 h. After the reaction ended, the obtained system was naturally cooled to 25 °C, and then centrifuged at a rotation speed of 8000 r / min for 20 min to separate the sample. The sample was washed with ethanol three times, and finally dried under a vacuum of 10 2 Pa and a temperature of 60 °C for 5 h to obtain CdSe / ZnS quantum dots; the CdSe / ZnS quantum dots, an organic solvent (n-hexane), and a multifunctional ligand (3-mercaptopropionic acid) were mixed. The mass-volume ratio of the CdSe / ZnS quantum dots, the organic solvent, and the multifunctional ligand is 1 kg:12 L:0.5 L. The reaction was carried out at 25 °C for 1 h to obtain a modified quantum dot solution;

[0096] Disperse 1 kg of silicon micro powder with a particle size of 170 nm in 10 L of ethanol, stir for 30 min, then add 0.48 L of a 3-mercaptopropyltriethoxysilane solution with a mass fraction of 1%, and react at 25 °C for 2 h under the condition of a stirring speed of 400 r / min. After the reaction, centrifuge the obtained system at a speed of 6000 r / min for 20 min to separate the sample. Wash the sample 3 times with ethanol, and finally dry it at a vacuum of 10 3 Pa and a temperature of 60 °C for 5 h to obtain thiol-modified silicon micro powder;

[0097] Mix a modified quantum dot solution with a mass fraction of 5% and the thiol-modified silicon micro powder. The mass ratio of the modified quantum dots to the thiol-modified silicon micro powder in the modified quantum dot solution is 1:12. React at a speed of 500 r / min and a temperature of 25 °C for 1 h. After the reaction, centrifuge at a speed of 7000 r / min for 15 min to separate the modified silicon micro powder. Wash the modified silicon micro powder 3 times with ethanol and then dry it at a vacuum of 10 2 Pa and a temperature of 60 °C for 5 h to obtain the modified silicon micro powder;

[0098] Co-extrude the modified silicon micro powder and polyurethane (TPU). Among them, the mass ratio of the modified silicon micro powder to TPU is 10:100, and the co-extrusion temperature is 210 °C. Cool the filamentous material obtained by co-extrusion rapidly through a cooling system. The cooling method is water cooling with a speed of 5 m / min to obtain a 3D printing composite material modified by quantum dots.

[0099] Irradiate the modified silicon micro powder prepared in this example with an ultraviolet lamp (LED, wavelength 365 nm). The material emits bright red light under ultraviolet excitation, verifying the luminescence performance of the quantum dots and proving that the modified silicon micro powder prepared in this example has good optical properties and luminescence efficiency.

[0100] Use a standard 3D printing device to print the 3D printing composite material modified by quantum dots prepared in this example into safety signs and fire-fighting signs. The obtained safety signs and fire-fighting signs have self-luminous properties, can provide clear instructions for personnel in a dark environment or in an emergency, and at the same time, the material has excellent durability and impact resistance.

[0101] Example 5

[0102] Under a nitrogen atmosphere, a selenium source solution with a concentration of 0.2 mol / L (the selenium source is selenium powder and the solvent is trioctylphosphine) was injected into a cadmium source solution with a concentration of 0.2 mol / L (the cadmium source is cadmium oxide and the solvent contains oleic acid and 1-octene, and the volume ratio of oleic acid to 1-octene is 1:5). The molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution is 1:1. The reaction was carried out at 280 °C for 25 min. After the reaction ended, the obtained system was naturally cooled to 25 °C, and then centrifuged at a speed of 7000 r / min for 20 min to separate the sample. The sample was washed 3 times with ethanol, and finally dried under a vacuum of 10 2 Pa and at a temperature of 60 °C for 5 h to obtain CdSe quantum dots; the CdSe quantum dots, a zinc source solution with a concentration of 0.5 mol / L (the zinc source is zinc oxide and the solvent is water), and a sulfur source solution with a concentration of 0.5 mol / L (the sulfur source is sodium sulfide and the solvent is water) were mixed. The molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution to the sulfur source in the sulfur source solution is 1:11:16. The reaction was carried out at 120 °C for 0.75 h. After the reaction ended, the obtained system was naturally cooled to 25 °C, and then centrifuged at a speed of 8000 r / min for 20 min to separate the sample. The sample was washed 3 times with ethanol, and finally dried under a vacuum of 10 2 Pa and at a temperature of 60 °C for 5 h to obtain CdSe / ZnS quantum dots; the CdSe / ZnS quantum dots, an organic solvent (n-hexane), and a multifunctional ligand (mercaptoacetic acid) were mixed. The mass-volume ratio of the CdSe / ZnS quantum dots, the organic solvent to the multifunctional ligand is 1 kg:10 L:0.6 L. The reaction was carried out at 25 °C for 1 h to obtain a modified quantum dot solution;

[0103] 1 kg of silicon micropowder with a particle size of 160 nm was dispersed in 10 L of ethanol and stirred for 40 min. Then, 0.5 L of a 3-mercaptopropyltrimethoxysilane solution with a mass fraction of 1% was added. Under the condition of a stirring speed of 450 r / min, the reaction was carried out at 25 °C for 2 h. After the reaction ended, the obtained system was centrifuged at a speed of 6000 r / min for 20 min to separate the sample. The sample was washed 3 times with ethanol, and finally dried under a vacuum of 10 3 Pa and at a temperature of 65 °C for 5 h to obtain mercapto-modified silicon micropowder;

[0104] A modified quantum dot solution with a mass fraction of 6% and the mercapto-modified silicon micropowder were mixed. The mass ratio of the modified quantum dots in the modified quantum dot solution to the mercapto-modified silicon micropowder is 1:10. The reaction was carried out at a speed of 500 r / min and a temperature of 25 °C for 1 h. After the reaction ended, the mixture was centrifuged at a speed of 7000 r / min for 15 min to separate the modified silicon micropowder. The modified silicon micropowder was washed 3 times with ethanol and then dried under a vacuum of 10 2Dry it at 65 °C for 5 h to obtain modified silica powder;

[0105] Blend and extrude the modified silica powder and polycarbonate (PC). Among them, the mass ratio of the modified silica powder to PC is 10:100, and the extrusion temperature is 260 °C. Cool the filamentous material obtained by blending and extrusion rapidly through a cooling system. The cooling method is water cooling, and the speed is 5 m / min to obtain a 3D printing composite material modified with quantum dots.

[0106] Irradiate the modified silica powder prepared in this example with an ultraviolet lamp (LED, wavelength 365 nm). The material emits bright red light under ultraviolet excitation, verifying the luminescence performance of the quantum dots and proving that the modified silica powder prepared in this example has good optical properties and luminescence efficiency.

[0107] Use a standard 3D printing device to print the 3D printing composite material modified with quantum dots prepared in this example into a medical device shell. The obtained shell not only has the self-luminescence property, facilitating equipment positioning and operation in the medical environment, but also has excellent antibacterial properties and durability.

[0108] Perform performance tests on the 3D printing composite materials modified with quantum dots prepared in Examples 1 to 5 and traditional 3D printing materials (the manufacturer of PLA / ABS is NatureWorks, model is Ingeo 4032D; the manufacturer of titanium alloy is ATIMetals, model is Titanium; the manufacturer of alumina ceramic is CoorsTek, model is AD-96Alumina) respectively to obtain the performance test results of traditional 3D printing materials as shown in Table 1; the performance test results of the 3D printing composite materials modified with quantum dots in Examples 1 to 5 are shown in Table 2.

[0109] Among them, the test standard for luminescence performance is based on GB / T 2410-2008 (Determination of Transmittance and Haze of Transparent Plastics), and the photon emission efficiency of the material is measured by UV excitation; the test standard for environmental stability is based on GB / T 16422.2-1999 (Test Methods for Exposure of Plastics to Laboratory Light Sources), simulating high-temperature and high-humidity environments to test the aging and weather resistance of the material; the test standard for mechanical strength is based on GB / T 1040.2-2006 (Determination of Tensile Properties of Plastics) to test the tensile strength of the composite material. Exceptionally, the test standard for traditional metals is based on GB / T 228.1-2010, and the test standard for traditional ceramics is based on GB / T 6569-2006; the test standard for luminous efficiency is based on GB / T 2410-2008, using an ultraviolet light source for excitation to measure the luminous efficiency of the quantum dot composite material; the test standard for multi-color display ability is based on GB / T 2410-2008 to measure the optical properties and evaluate the multi-color display ability; the test standard for light reflection performance is GB / T 2680-1994 (Determination of Reflectance and Transmittance of Building Materials); the test standard for the applicable temperature range is GB / T 1634.2-2004 (Determination of Heat Deflection Temperature of Thermoplastics) to test the heat deflection behavior of the material at different temperatures; the test standard for durability is GB / T 16422.2-1999.

[0110] Table 1 Performance Test Results of Traditional 3D Printing Materials

[0111]

[0112]

[0113] Table 2 Performance Test Results of 3D Printing Composite Materials Modified with Quantum Dots in Examples 1-5

[0114]

[0115]

[0116] As can be seen from the above examples, the present invention provides a 3D printing composite material modified with quantum dots. By introducing quantum dots and silicon micropowder, the luminous efficiency, environmental stability and mechanical properties of the material are improved, thereby providing a multifunctional, low-energy consumption and long-life 3D printing composite material, which can be widely used in fields such as intelligent building supplies, personalized daily necessities, safety sign supplies, transportation facility supplies, intelligent wearable device supplies or medical device supplies.

[0117] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can still be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a 3D printing composite material based on quantum dot modification, characterized in that, It includes the following steps: (1) Under a protective atmosphere, inject a selenium source solution into a cadmium source solution and react to obtain CdSe quantum dots; (2) Mix the CdSe quantum dots, a zinc source solution, and a sulfur source solution and react to obtain CdSe / ZnS quantum dots; (3) Mix the CdSe / ZnS quantum dots, an organic solvent, and a multifunctional ligand and react to obtain a modified quantum dot solution; (4) Mix the modified quantum dot solution and mercapto-modified silica powder and react to obtain modified silica powder; (5) Co-extrude the modified silica powder and a 3D printing matrix material to obtain the described 3D printing composite material modified by quantum dots; The preparation method of the mercapto-modified silica powder includes the following steps: Mix silica powder, ethanol, and a silanization reagent and react to obtain mercapto-modified silica powder.

2. The preparation method of the 3D printing composite material modified based on quantum dots according to claim 1, characterized in that, In step (1), the selenium source in the selenium source solution includes selenium powder, and the solvent of the selenium source solution includes tri-n-octylphosphine oxide or trioctylphosphine; the concentration of the selenium source solution is 0.2 - 0.5 mol / L; The cadmium source in the cadmium source solution includes cadmium oxide, cadmium acetate, or cadmium nitrate, and the solvent of the cadmium source solution includes one or more of oleic acid, 1-octene, hexadecylamine, and alkenylamine solvents; the alkenylamine solvents include one or more of n-octylamine, n-dodecylamine, and n-hexadecylamine; the concentration of the cadmium source solution is 0.1 - 0.3 mol / L; In step (1), the molar ratio of the cadmium source in the cadmium source solution to the selenium source in the selenium source solution is 1:1 - 2.

3. The preparation method of the 3D printing composite material modified by quantum dots according to claim 1 or 2, characterized in that, In step (1), the temperature of the reaction is 260 - 290 °C, and the reaction time is 20 - 40 min.

4. The preparation method of the 3D printing composite material based on quantum dot modification according to claim 3, characterized in that, In step (2), the zinc source in the zinc source solution includes zinc oxide, zinc acetate, or zinc nitrate; the concentration of the zinc source solution is 0.4 - 0.6 mol / L; The sulfur source in the sulfur source solution includes sodium sulfide, ammonium sulfide, or thiourea; the concentration of the sulfur source solution is 0.4 - 0.6 mol / L; In step (2), the molar ratio of the CdSe quantum dots, the zinc source in the zinc source solution, and the sulfur source in the sulfur source solution is 1:8 - 12:13 - 17; In step (2), the temperature of the reaction is 100 - 140 °C, and the reaction time is 0.5 - 1.5 h.

5. The preparation method of the 3D printing composite material based on quantum dot modification according to claim 4, characterized in that, In step (3), the organic solvent includes one or more of n-hexane, n-octane, n-dodecane, and toluene; the multifunctional ligand includes one or more of ethyl 2-mercaptoacetate, 3-mercaptopropionic acid, and mercaptoacetic acid; In step (3), the mass-volume ratio of the CdSe / ZnS quantum dots, the organic solvent, and the multifunctional ligand is 1 kg:8 - 15 L:0.2 - 1 L; In step (3), the temperature of the reaction is 20 - 30 °C, and the reaction time is 0.5 - 2.5 h.

6. The preparation method of the 3D printing composite material based on quantum dot modification according to claim 5, characterized in that, When preparing the mercapto-modified silica powder, the particle size of the silica powder is 50 - 200 nm; the silanization reagent includes one or more of 3-mercaptopropyltrimethoxysilane solution, 3-mercaptopropyltriethoxysilane solution, and 3-mercaptopropylmethyldimethoxysilane solution; the mass fraction of the silanization reagent is 0.5 - 1.5%; The mass-volume ratio of the silica powder, ethanol, and the silanization reagent is 0.9 - 1.1 kg:8 - 12 L:0.4 - 0.6 L; The temperature of the reaction is 20 to 30 °C, and the reaction time is 1.5 to 2.5 h.

7. The preparation method of the 3D printing composite material based on quantum dot modification according to claim 5 or 6, characterized in that, In the modified quantum dot solution described in step (4), the mass ratio of the modified quantum dots to the mercapto-modified silicon micropowder is 1:8 to 14; the mass fraction of the modified quantum dot solution is 5 to 10%. The temperature of the reaction described in step (4) is 20 to 30 °C, and the reaction time is 0.5 to 2.5 h.

8. The preparation method of the 3D printing composite material based on quantum dot modification according to claim 7, wherein, The 3D printing matrix material described in step (5) includes polycarbonate, polymethyl methacrylate, transparent nylon or transparent polyurethane; In step (5), the mass ratio of the modified silicon micropowder to the 3D printing matrix material is 5 to 15:100; The temperature of the co-extrusion in step (5) is 190 to 280 °C.

9. A 3D printing composite material modified with quantum dots prepared by the method for preparing a 3D printing composite material modified with quantum dots according to any one of claims 1 to 8.

10. The application of the 3D printing composite material modified with quantum dots according to claim 9 in intelligent building supplies, personalized daily necessities, safety sign supplies, transportation facility supplies, intelligent wearable device supplies or medical device supplies.

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