CN111621126B - Polylactic acid composite material with aggregation-induced emission effect, polylactic acid 3D printing material and preparation method thereof - Google Patents

Polylactic acid composite material with aggregation-induced emission effect, polylactic acid 3D printing material and preparation method thereof Download PDF

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CN111621126B
CN111621126B CN202010348533.4A CN202010348533A CN111621126B CN 111621126 B CN111621126 B CN 111621126B CN 202010348533 A CN202010348533 A CN 202010348533A CN 111621126 B CN111621126 B CN 111621126B
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polylactic acid
aggregation
induced emission
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CN111621126A (en
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董先明
杨飞文
郭晓宇
黄咏仪
肖嘉林
周武艺
罗颖
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South China Agricultural University
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    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention belongs to the technical field of organic luminescent materials and fused deposition modeling 3D printing materials, and relates to a polylactic acid composite material with aggregation-induced emission effect, which is prepared from the following raw materials: the weight ratio of the aggregation-induced emission material to the polylactic acid to the organic solvent is (1-10): 1: (10-20), can solve the problems of poor interface compatibility, weak luminous intensity and the like of fluorescent powder and a polylactic acid matrix in the existing fluorescent luminous polylactic acid composite material. The polylactic acid 3D printing material with the aggregation-induced emission effect comprises a polylactic acid composite material with the aggregation-induced emission effect, an antioxidant, a lubricant and polylactic acid master batches, can effectively overcome the problems of poor mechanical property and single function of the polylactic acid 3D printing material, solves the problem of aggregation fluorescence quenching effect of the existing fluorescence emission 3D printing material, and is simple in preparation process, green and environment-friendly, and strong in fluorescence emitted by the material under an ultraviolet lamp.

Description

Polylactic acid composite material with aggregation-induced emission effect, polylactic acid 3D printing material and preparation method thereof
Technical Field
The invention belongs to the technical field of organic luminescent materials and fused deposition modeling 3D printing materials, and particularly relates to a polylactic acid composite material with aggregation-induced emission effect, a polylactic acid 3D printing material and a preparation method thereof.
Background
In recent years, organic fluorescent dyes and phosphors are often doped with high polymers in order to prepare luminescent 3D printing materials. For example, chinese patent CN 109880323 a proposes a 3D printing composite material containing organic fluorescent dye, which is prepared by dissolving organic fluorescent dye in organic solvent, and then smearing the organic fluorescent dye on a printed material to obtain a polylactic acid 3D printing wire dyed by the organic fluorescent dye; finally, the wire is printed by a Fused Deposition Modeling (FDM) 3D printer to obtain a 3D printed object containing the organic fluorescent dye. However, such a fluorescent 3D printed material has an aggregate-fluorescent-quenching (ACQ) effect, i.e. the fluorescence of the fluorescent chromophore is reduced or even not emitted at high concentrations.
The group of tangzhi academy members proposed in 2001 to exploit the Aggregation of organic molecules to achieve aggregate-state fluorescence enhancement, i.e., Aggregation Induced Emission (AIE). Specifically, some groups in the AIE molecules have active relative motion in a dilute solution, and the molecules in an excited state consume light energy in the forms of heat energy and the like through a vibration-rotation mode to generate weak fluorescence emission; when these molecules are aggregated together, the pinning action of each other restricts the movement inside the molecules, and thus the proportion of energy dissipated via the movement form decreases, thereby exhibiting a phenomenon of fluorescence enhancement. The Chinese patent CN 107200832A discloses a polymer with aggregation-induced emission effect and a preparation method thereof, and the graphene composite material which is soluble in organic solvent and has AIE effect is prepared by in-situ reduction of graphene oxide, so that the graphene composite material has wide application prospect in the aspects of chemical sensors, biological probes, solid fluorescent materials and the like.
3D printing, also known as additive manufacturing, with Fused Deposition Modeling (FDM) being the most widely used 3D printing technique. The method is a technology for constructing an object by using materials such as high molecular polymers and the like in a layer-by-layer printing mode on the basis of a digital model file. At present, polylactic acid (PLA) is the most common material applied to FDM, and the material is used as a biodegradable high-molecular polymer and has good processing performance and mechanical property. However, since the luminescent 3D printing composite material is prepared by doping fluorescent powder in the market at present, the luminescent performance of the composite material after printing is often weakened, and therefore, research and development of a 3D printing material with high-efficient luminescent performance is urgently needed.
Disclosure of Invention
In order to solve the problems of poor interface compatibility, weak luminous intensity and the like of fluorescent powder and a polylactic acid matrix in the existing fluorescent luminous polylactic acid composite material, the invention provides the polylactic acid composite material with aggregation-induced emission effect by simply processing an AIE material and polylactic acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polylactic acid composite material with aggregation-induced emission effect is prepared from the following raw materials: aggregation-induced emission material, polylactic acid and organic solvent, preferably in the ratio of (1-10): 1: (10-20).
Preferably, the preparation method comprises the following steps:
(1) soaking the polylactic acid particles in a closed container containing an organic solvent, and stirring at normal temperature of 100-300rpm until the polylactic acid particles are completely dissolved;
(2) adding aggregation-induced emission material, and stirring at normal temperature of 150-;
(3) pouring into an open container, drying to obtain the polylactic acid composite material, and crushing to 50-300 meshes for later use.
Preferably, the polylactic acid in the step (1) is injection molding grade, and the molecular weight is 1 multiplied by 105-5×106(ii) a The organic solvent is one or two of dichloromethane, trichloromethane and acetone.
Preferably, the aggregation-induced emission material in step (2) is a powder material, preferably tetraphenylethylene and its derivatives, or polyarylalkene compounds, or polycyclic polymers.
Preferably, the drying temperature in the step (3) is 40-80 ℃.
In order to overcome the problems of poor mechanical property and single function of the polylactic acid 3D printing material and solve the problem of the aggregate fluorescence quenching (ACQ) effect of the existing fluorescence luminescent 3D printing material, the invention also provides the polylactic acid 3D printing material with the aggregate induced luminescence effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polylactic acid 3D printing material with aggregation-induced emission effect comprises the polylactic acid composite material with aggregation-induced emission effect, an antioxidant, a lubricant and polylactic acid master batches.
Preferably, the polylactic acid 3D printing material comprises the following raw materials in percentage by weight: 0.5-10% of polylactic acid composite material with aggregation-induced emission effect, 0.1-3% of antioxidant, 0.1-5% of lubricant and 85-95% of polylactic acid master batch.
Preferably, the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), and bis (octadecyl) pentaerythritol diphosphite (antioxidant 618).
Preferably, the lubricant is one or more of butyl stearate, calcium stearate and stearic acid.
Preferably, the molecular weight of the polylactic acid master batch is 1 × 105-5×106。
The preparation method of the polylactic acid 3D printing material with the aggregation-induced emission effect comprises the following steps:
(1) mixing the polylactic acid composite material with an antioxidant, a lubricant and polylactic acid at a high speed according to a ratio to obtain a blend, and drying the blend at 70-100 ℃ for later use;
(2) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 70-100 ℃ for later use;
wherein the temperatures of the sections 1-6 of the extruder are respectively 140-.
(3) Drawing the obtained granules by a single-screw extruder to form a 3D printing wire, wherein the temperatures of 1-4 sections of the extruder are respectively 150-.
The rolled wire is printed by a desktop FDM type 3D printer, the temperature of a printing nozzle is 180-220 ℃, the diameter of the nozzle is 0.4mm, the printing speed is 30-80mm/min, and the temperature of a printing platform is 40-80 ℃.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention utilizes the aggregation-induced emission material and polylactic acid to prepare the polylactic acid composite material with the aggregation-induced emission effect, the added AIE material has different emission colors and different emission performances, the defects and the defects of poor interface compatibility between powder and a polylactic acid matrix, weak emission intensity and the like in the fluorescent light-emitting polylactic acid composite material are effectively solved, and the application value of the polylactic acid material is improved.
(2) The polylactic acid 3D printing material with aggregation-induced emission effect prepared by the invention not only has aggregation-induced emission (AIE) effect, but also has excellent mechanical property and biocompatibility. The 3D printing material has potential application prospect in the fields of luminescent materials, polymer performance detection, furniture, artworks and the like.
Drawings
FIG. 1 is a graph showing the change of fluorescence intensity of the poly (lactic acid) 3D printing material with aggregation-inducing effect at different tetraphenylethylene contents in examples 1-3 (examples 1-3 are shown in the figure from bottom to top);
FIG. 2 is a photograph of the polylactic acid 3D printed material with aggregation inducing effect printed with standard sample strips and its UV luminescence in example 1;
fig. 3 is a photograph of the polylactic acid 3D printing material printing wire with aggregation inducing effect and the printed artwork ultraviolet luminescence thereof in example 2;
FIG. 4 is a photograph of the polylactic acid 3D printed material with aggregation induced emission effect printed wire and printed standard sample strip in example 3;
FIG. 5 is a photograph of the UV emission of the 3D printed standard sample strip of the phosphor-enhanced polylactic acid of comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples of the present invention are conventional raw materials or reagents unless otherwise specified, and the experimental methods used are conventional in the art unless otherwise specified. The specific method for testing the mechanical property of the standard sample strip is as follows: the tensile test is executed according to the national standard GB/T1040-; the bending test is carried out according to the national standard GB/T9341-.
Example 1
The polylactic acid 3D printing material with aggregation-induced emission effect of the embodiment is prepared by the following method:
(1) soaking polylactic acid particles in a closed container containing dichloromethane, and stirring at normal temperature of 150rpm until the polylactic acid particles are completely dissolved, wherein the mass-volume ratio of the polylactic acid to the dichloromethane is 1: 10;
(2) adding tetraphenyl ethylene (TPE) powder into the mixed solution in the step (1), and stirring at the normal temperature and 200rpm for 0.5 h; the mass ratio of the Tetraphenylethylene (TPE) powder to the polylactic acid granules is 1: 1;
(3) pouring the mixed solution obtained in the step (2) into an open container, and drying in an oven at 60 ℃ for 20h to obtain the bulk polylactic acid composite material with the AIE effect;
(4) putting the blocky polylactic acid composite material with the AIE effect obtained in the step (3) into a high-speed grinder, and grinding for 4min to obtain polylactic acid composite material powder with the AIE effect;
(5) mixing 1% of the polylactic acid composite material with the AIE effect, 0.1% of a mixture of an antioxidant 1010 and an antioxidant 168 in a ratio of 1:2, 0.1% of lubricant butyl stearate and 98.8% of polylactic acid at a high speed according to a mass ratio (wherein tetraphenylethylene accounts for 0.5% of the 3D printing composite material) to obtain a mixture, and drying at 80 ℃ for 15 hours for later use;
(6) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 80 ℃ for 15 hours for later use; wherein the temperatures of 1-6 sections of the extruder are respectively 150 ℃, 165 ℃, 170 ℃, 180 ℃, 185 ℃ and 180 ℃, and the rotating speeds of the host machine and the feeding machine are respectively 10rpm and 8 rpm;
(7) and drawing the obtained granules into a 3D printing wire rod by a single-screw extruder, wherein the temperatures of 1-4 sections of the extruder are respectively 150 ℃, 170 ℃, 180 ℃ and 178 ℃, and the traction speed is 13 mm/s, so that the polylactic acid 3D printing material is obtained, the diameter of the obtained wire rod is about 1.75mm, and the diameter error is within +/-0.05.
The rolled wire rods are printed with standard splines through a desktop FDM type 3D printer, the temperature of a printing spray head is 200 ℃, the diameter of a spray nozzle is 0.4mm, the printing speed is 50mm/min, and the temperature of a printing platform is 65 ℃.
The graph of the change of the fluorescence intensity of the polylactic acid 3D printing material with aggregation-induced emission effect prepared in the example is shown in FIG. 1, and the 3D printing standard sample bar and the photograph of the ultraviolet emission are shown in FIG. 2. And (3) performing mechanical property test on the standard sample strip according to the national standard, wherein the test results of the mechanical property and the 3D printing property are shown in Table 1.
Example 2
The polylactic acid 3D printing material with aggregation-induced emission effect of the embodiment is prepared by the following method:
(1) soaking polylactic acid particles in a closed container containing dichloromethane, and stirring at normal temperature of 150rpm until the polylactic acid particles are completely dissolved, wherein the mass-volume ratio of the polylactic acid to the dichloromethane is 1: 10;
(2) adding tetraphenyl ethylene (TPE) powder into the mixed solution in the step (1), and stirring at the normal temperature and 200rpm for 0.5 h; the mass ratio of the Tetraphenylethylene (TPE) powder to the polylactic acid granules is 3: 1;
(3) pouring the mixed solution obtained in the step (2) into an open container, and drying in an oven at 60 ℃ for 20h to obtain the bulk polylactic acid composite material with the AIE effect;
(4) putting the blocky polylactic acid composite material with the AIE effect obtained in the step (3) into a high-speed grinder, and grinding for 4min to obtain polylactic acid composite material powder with the AIE effect;
(5) mixing 1.33% of the polylactic acid composite material with the AIE effect, 0.1% of a mixture of an antioxidant 1010 and an antioxidant 168 in a ratio of 1:2, 0.1% of a lubricant butyl stearate and 98.47% of polylactic acid at a high speed according to the mass ratio (wherein tetraphenylethylene accounts for 1% of the 3D printing composite material) to obtain a mixture, and drying the mixture for 15 hours at 80 ℃ for later use;
the remaining experimental procedures were the same as those of steps (6) and (7) of example 1. The graph of the change of the fluorescence intensity of the polylactic acid 3D printing material with aggregation-induced emission effect prepared in the example is shown in FIG. 1, and the 3D printing standard sample bar and the photograph of the ultraviolet emission are shown in FIG. 3. And (3) performing mechanical property test on the standard sample strip according to the national standard, wherein the test results of the mechanical property and the 3D printing property are shown in Table 1.
Example 3
The polylactic acid 3D printing material with aggregation-induced emission effect of the embodiment is prepared by the following method:
(1) soaking polylactic acid particles in a closed container containing dichloromethane, and stirring at normal temperature of 150rpm until the polylactic acid particles are completely dissolved, wherein the mass-volume ratio of the polylactic acid to the dichloromethane is 1: 10;
(2) adding tetraphenyl ethylene (TPE) powder into the mixed solution in the step (1), and stirring at the normal temperature and 200rpm for 0.5 h; the mass ratio of the Tetraphenylethylene (TPE) powder to the polylactic acid granules is 5: 1;
(3) pouring the mixed solution obtained in the step (2) into an open container, and drying in an oven at 60 ℃ for 20h to obtain the bulk polylactic acid composite material with the AIE effect;
(4) putting the blocky polylactic acid composite material with the AIE effect obtained in the step (3) into a high-speed grinder, and grinding for 4min to obtain polylactic acid composite material powder with the AIE effect;
(5) mixing 1.8% of the polylactic acid composite material with the AIE effect, 0.1% of a mixture of an antioxidant 1010 and an antioxidant 168 in a ratio of 1:2, 0.1% of lubricant butyl stearate and 98% of polylactic acid at a high speed according to a mass ratio (wherein tetraphenylethylene accounts for 1.5% of the 3D printing composite material) to obtain a mixture, and drying at 80 ℃ for 15 hours for later use;
the remaining experimental procedures were the same as those of steps (6) and (7) of example 1. The graph of the change of the fluorescence intensity of the polylactic acid 3D printing material with aggregation-induced emission effect prepared in the example is shown in FIG. 1, and the 3D printing standard sample bar and the photograph of the ultraviolet emission are shown in FIG. 4. And (3) performing mechanical property test on the standard sample strip according to the national standard, wherein the test results of the mechanical property and the 3D printing property are shown in Table 1.
Example 4
The polylactic acid 3D printing material with aggregation-induced emission effect of the embodiment is prepared by the following method:
(1) soaking polylactic acid particles in a closed container containing dichloromethane, and stirring at normal temperature of 100rpm until the polylactic acid particles are completely dissolved, wherein the mass-volume ratio of the polylactic acid to the dichloromethane is 1: 20;
(2) adding tetraphenyl ethylene (TPE) powder into the mixed solution in the step (1), and stirring at the normal temperature at 300rpm for 0.1 h; the mass ratio of the Tetraphenylethylene (TPE) powder to the polylactic acid granules is 10: 1;
(3) pouring the mixed solution obtained in the step (2) into an open container, and drying in an oven at 40 ℃ for 12h to obtain the bulk polylactic acid composite material with the AIE effect;
(4) putting the blocky polylactic acid composite material with the AIE effect obtained in the step (3) into a high-speed grinder, and grinding for 4min to obtain polylactic acid composite material powder with the AIE effect;
(5) mixing 0.5% of the polylactic acid composite material with the AIE effect, 10103% of antioxidant, 5% of lubricant butyl stearate and 91.5% of polylactic acid at a high speed according to the mass ratio (wherein tetraphenylethylene accounts for 0.45% of the 3D printing composite material) to obtain a mixture, and drying for 15h at 80 ℃ for later use;
(6) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 80 ℃ for 15 hours for later use; wherein the temperatures of 1-6 sections of the extruder are respectively 140 ℃, 155 ℃, 170 ℃, 180 ℃, 185 ℃ and 180 ℃, and the rotating speeds of the host machine and the feeding machine are respectively 10rpm and 8 rpm;
(7) and drawing the obtained granules into a 3D printing wire rod by a single-screw extruder, wherein the temperatures of 1-4 sections of the extruder are respectively 150 ℃, 170 ℃, 180 ℃ and 175 ℃, and the traction speed is 13 mm/s, so that the polylactic acid 3D printing material is obtained, the diameter of the obtained wire rod is about 1.75mm, and the diameter error is within +/-0.05.
Example 5
The polylactic acid 3D printing material with aggregation-induced emission effect of the embodiment is prepared by the following method:
(1) soaking polylactic acid particles in a closed container containing dichloromethane, and stirring at normal temperature and 200rpm until the polylactic acid particles are completely dissolved, wherein the mass-volume ratio of the polylactic acid to the dichloromethane is 1: 15;
(2) adding tetraphenyl ethylene (TPE) powder into the mixed solution in the step (1), and stirring at the normal temperature and 200rpm for 0.5 h; the mass ratio of the Tetraphenylethylene (TPE) powder to the polylactic acid granules is 8: 1;
(3) pouring the mixed solution obtained in the step (2) into an open container, and drying in a 60 ℃ oven for 16h to obtain the bulk polylactic acid composite material with the AIE effect;
(4) putting the blocky polylactic acid composite material with the AIE effect obtained in the step (3) into a high-speed grinder, and grinding for 4min to obtain polylactic acid composite material powder with the AIE effect;
(5) mixing 3% of the polylactic acid composite material with the AIE effect, 1683% of antioxidant, 3% of lubricant butyl stearate and 91% of polylactic acid at a high speed according to the mass ratio (wherein tetraphenylethylene accounts for 2.67% of the 3D printing composite material) to obtain a mixture, and drying for 15h at 80 ℃ for later use;
(6) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 80 ℃ for 15 hours for later use; wherein the temperatures of 1-6 sections of the extruder are respectively 145 ℃, 160 ℃, 172 ℃, 183 ℃, 188 ℃ and 180 ℃, and the rotating speeds of the main machine and the feeding machine are respectively 10rpm and 8 rpm;
(7) and drawing the obtained granules into a 3D printing wire rod by a single-screw extruder, wherein the temperatures of 1-4 sections of the extruder are respectively 160 ℃, 175 ℃, 183 ℃, 186 ℃, and the traction speed is 13 mm/s, so that the polylactic acid 3D printing material is obtained, the diameter of the obtained wire rod is about 1.75mm, and the diameter error is within +/-0.05.
Example 6
The polylactic acid 3D printing material with aggregation-induced emission effect of the embodiment is prepared by the following method:
(1) soaking polylactic acid particles in a closed container containing dichloromethane, and stirring at normal temperature of 300rpm until the polylactic acid particles are completely dissolved, wherein the mass-volume ratio of the polylactic acid to the dichloromethane is 1: 12;
(2) adding tetraphenyl ethylene (TPE) powder into the mixed solution in the step (1), and stirring at the normal temperature at 150rpm for 1 h; the mass ratio of the Tetraphenylethylene (TPE) powder to the polylactic acid granules is 6: 1;
(3) pouring the mixed solution obtained in the step (2) into an open container, and drying in an oven at 80 ℃ for 20h to obtain the bulk polylactic acid composite material with the AIE effect;
(4) putting the blocky polylactic acid composite material with the AIE effect obtained in the step (3) into a high-speed grinder, and grinding for 4min to obtain polylactic acid composite material powder with the AIE effect;
(5) mixing 8% of the polylactic acid composite material with the AIE effect, 10100.5% of antioxidant, 2% of lubricant butyl stearate and 89.5% of polylactic acid at a high speed according to the mass ratio (wherein tetraphenylethylene accounts for 6.86% of the 3D printing composite material) to obtain a mixture, and drying at 80 ℃ for 15h for later use;
(6) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 80 ℃ for 15 hours for later use; wherein the temperatures of 1-6 sections of the extruder are respectively 150 ℃, 165 ℃, 175 ℃, 185 ℃, 190 ℃ and 185 ℃, and the rotating speeds of the main machine and the feeding machine are respectively 10rpm and 8 rpm;
(7) and drawing the obtained granules into a 3D printing wire rod by a single-screw extruder, wherein the temperatures of 1-4 sections of the extruder are 165 ℃, 180 ℃, 185 ℃ and 180 ℃, and the traction speed is 13 mm/s, so that the polylactic acid 3D printing material is obtained, the diameter of the obtained wire rod is about 1.75mm, and the diameter error is within +/-0.05.
Comparative example 1
A dry blending method for preparing a polylactic acid 3D printing material with an aggregation-induced emission effect comprises the following steps:
(1) directly mixing 0.5% of tetraphenylethylene powder with 0.1% of a mixture of an antioxidant 1010 and an antioxidant 168 in a ratio of 1:2, 0.1% of a lubricant butyl stearate and 99.3% of polylactic acid at a high speed according to a certain ratio to obtain a mixture, and drying the mixture for 15 hours at 80 ℃ for later use;
(2) and melting and extruding the obtained mixture by a double-screw extruder, granulating to obtain granules, and fully drying at 80 ℃ for 15 hours for later use. Wherein the temperatures of 1-6 sections of the extruder are respectively 150 ℃, 165 ℃, 175 ℃, 185 ℃, 190 ℃ and 185 ℃, and the rotating speeds of the main machine and the feeding machine are respectively 15rpm and 10 rpm.
(3) Drawing the obtained granules by a single-screw extruder to form a 3D printing wire rod, wherein the temperatures of 1-4 sections of the extruder are 155 ℃, 175 ℃, 185 ℃ and 180 ℃, and the traction speed is 15mm/s, so that the wire rod is obtained, the diameter of the obtained wire rod is about 1.75mm, and the diameter error is within +/-0.05;
(4) the rolled wire rods are printed through a desktop FDM type 3D printer, the temperature of a printing spray head is 210 ℃, the diameter of a nozzle is 0.4mm, the printing speed is 50mm/min, and the temperature of a printing platform is 60 ℃.
The polylactic acid 3D printing standard sample strip with aggregation-induced emission effect prepared by dry blending according to the comparative example is subjected to mechanical property test according to the national standard, and the test results of the mechanical property and the 3D printing property are shown in Table 1.
Comparative example 2
A preparation method of a common fluorescent powder reinforced polylactic acid 3D printing material comprises the following steps:
(1) directly mixing 5% of commercially available strontium calcium aluminate doped europium dysprosium fluorescent powder with 0.1% of a mixture of an antioxidant 1010 and an antioxidant 168 in a ratio of 1:2, 0.1% of a lubricant butyl stearate and 94.8% of polylactic acid at a high speed according to a certain ratio to obtain a mixture, and drying the mixture for 15 hours at 80 ℃ for later use;
the remaining experimental procedure was the same as in example 1. The 3D printing standard sample strip of the common fluorescent powder reinforced polylactic acid prepared by the comparative example is shown in figure 5, and the mechanical property and the 3D printing material performance test result are shown in table 1.
Table 1 appearance and properties of each polylactic acid 3D printing material in the embodiments
Figure DEST_PATH_IMAGE001
The detection result shows that the polylactic acid 3D printing material with aggregation-induced emission effect prepared by the invention has excellent mechanical property, is green and environment-friendly, emits strong fluorescence under an ultraviolet lamp, meets the mechanical strength and appearance requirements of the polylactic acid 3D printing material required in the market, and has excellent FDM type 3D printing property.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Other variations will be anticipated by those skilled in the art in view of the description of the invention, and such variations are intended to be included within the scope of the invention.

Claims (7)

1. A polylactic acid 3D printing material with aggregation-induced emission effect is characterized in that: comprises the following raw materials in percentage by weight: 0.5-10% of polylactic acid composite material with aggregation-induced emission effect, 0.1-3% of antioxidant, 0.1-5% of lubricant and 85-95% of polylactic acid;
the polylactic acid composite material with the aggregation-induced emission effect is prepared from the following raw materials: aggregation-inducing luminescent material, polylactic acid and organic solvent;
the preparation comprises the following steps:
(1) soaking the polylactic acid particles in a closed container containing the organic solvent, and stirring at normal temperature of 100-300rpm until the polylactic acid particles are completely dissolved;
(2) adding the aggregation-induced emission material, and stirring at the normal temperature of 150-;
(3) pouring into an open container for drying to obtain a polylactic acid composite material, and crushing to 50-300 meshes;
the weight ratio of the aggregation-induced emission material to the polylactic acid to the organic solvent is (1-10): 1: (10-20).
2. Polylactic acid 3D printed material according to claim 1, characterized in that: the polylactic acid of the step (1) has a molecular weight of 1X 105-5×106(ii) a The organic solvent is dichloromethane or trichloroOne or both of methane and acetone; the aggregation-induced emission material in the step (2) is a polyaryl ethylene compound or a polyphenyl ring polymer.
3. Polylactic acid 3D printed material according to claim 1, characterized in that: the polylactic acid of the step (1) has a molecular weight of 1X 105-5×106(ii) a The organic solvent is one or two of dichloromethane, trichloromethane and acetone; the aggregation-induced emission material in the step (2) is tetraphenylethylene and derivatives thereof.
4. Polylactic acid 3D printed material according to claim 1, characterized in that: the drying temperature in the step (3) is 40-80 ℃.
5. Polylactic acid 3D printing material according to claim 1, wherein the antioxidant is at least one of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite, bis (octadecyl) pentaerythritol diphosphite; the lubricant is one or more of butyl stearate, calcium stearate and stearic acid.
6. The preparation method of the polylactic acid 3D printing material with aggregation-induced emission effect as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) mixing the polylactic acid composite material with an antioxidant, a lubricant and polylactic acid at a high speed according to a ratio to obtain a blend, and drying the blend at 70-100 ℃ for later use;
(2) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 70-100 ℃ for later use;
(3) and drawing the obtained granules by a single-screw extruder to form a 3D printing wire rod, thus obtaining the wire rod.
7. The method of claim 6, wherein: the temperatures of the sections 1-6 of the double-screw extruder are respectively 140-; the temperatures of the sections 1-4 of the single-screw extruder are respectively 150-.
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