CN115785571A - 3D printing polypropylene particle for large industrial model and outdoor building and preparation method thereof - Google Patents
3D printing polypropylene particle for large industrial model and outdoor building and preparation method thereof Download PDFInfo
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- 238000001816 cooling Methods 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
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- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides 3D printing polypropylene particles applied to large industrial models and outdoor buildings and a preparation method thereof, and solves the technical problems that the existing 3D printing polypropylene has large shrinkage, is easy to warp and has poor interlayer bonding force. The 3D printing polypropylene particles provided by the invention are prepared by mixing polypropylene, a toughening agent, an adhesive, a compatilizer, an organic nucleating agent, an antioxidant and a plasticizer according to a certain mass component in proportion, and meanwhile, carrying out side feeding on glass fibers and mineral powder on a double-screw extruder, and extruding to obtain the modified polypropylene particles. The invention is especially suitable for 3D printing of large industrial models and outdoor buildings, has high rigidity, good dimensional stability and interlayer bonding force, and has wide application prospect in the 3D printing technology of granular materials.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to 3D printing polypropylene particles for large industrial models and outdoor buildings, and a preparation method and application thereof.
Background
The additive manufacturing technology can directly carry out die-free manufacturing through computer-aided design (CAD), and die-free production, design freedom and manufacturing time are short, so that the process is very suitable for producing parts with high design varieties in small batches. Different additive manufacturing techniques vary widely and have different industrial benefits. Only a few manufacturing processes are particularly suitable for producing large polymer parts (greater than 0.5x0.5x0.5 m). Particle-based additive manufacturing techniques are most suitable for producing large parts because of their scalable build volumes and their economic value to production due to high build rates.
Fused particle fabrication (FGF) is a particle-based additive manufacturing technology that has increased interest in the industry because of its economic advantages (shorter production times and reduced material costs) and availability of multiple materials. Essentially standard granules (injection molded or extruded material) can be used with the extruder. However, different processing conditions often require changes to the standard materials. In particular, polypropylene (PP) is a promising material for industrial applications because of its high impact strength, chemical resistance and low cost.
However, 3D printing processing of PP is also challenging, especially due to poor adhesion of PP material to the printing bed and warping. In many cases, PP plates or tapes are used as printing surfaces, and due to the high adhesion, the warpage of the printed polypropylene parts is significantly reduced. A big challenge with using PP sheet is the risk of welding parts on the printed surface, with a narrow process window between achieving good adhesion to the printed surface and welding parts on the printed surface. However, the parts adhering to the heated bed can in principle be adjusted by the temperature of the bed, but studies have shown that large-area parts can still be detached from the printing surface, since these parts are particularly prone to tilting. Besides low adhesion, the strong shrinkage rate caused by the crystallinity of PP is also a main factor influencing the warping of products.
Meanwhile, the forming mode of 3D printing brings great convenience and has some defects, one of the defects is that the interface bonding property between layers is obviously different from that of a traditional material body, the mechanical performance in certain directions is seriously reduced and is often less than 50% of the raw material, the performance and the application of the device are seriously influenced, and the device is printed only when being displayed as a model.
In order to increase the application of polypropylene materials in FGF industrial-grade large-scale printing, 3D printing polypropylene particles with high rigidity, good dimensional stability and interlayer bonding force need to be developed, so as to solve the technical deficiencies of the existing materials.
Disclosure of Invention
The invention aims to provide 3D printing polypropylene particles for large industrial models and outdoor buildings and a preparation method thereof, and solves the problems of poor interlayer bonding force, severe warping due to crystallization and the like of the existing 3D printing polypropylene material. According to the invention, the inorganic filler and the toughening agent are added to reduce the shrinkage rate of polypropylene, so that the dimensional stability is greatly improved; meanwhile, the added adhesive contains more ester groups, has strong cohesive strength and adhesive force, can effectively bond materials between layers in the printing process, and can enable the printed materials to be in a molten state for a long time in the printing process due to the lower melting point, so that the next layer of printed materials can be better adhered.
In order to achieve the purpose, the invention adopts the following technical scheme:
3D printing polypropylene particles for large industrial models and outdoor buildings contain polypropylene resin, a toughening agent, an adhesive, glass fibers, mineral powder, a compatilizer, an organic nucleating agent, an antioxidant and a plasticizer;
wherein the polypropylene resin comprises a homo polypropylene resin and an impact co-polypropylene resin;
based on the total weight of the final 3D printing polypropylene particles, the content of the homopolymerized polypropylene resin is 5-20wt%, the content of the impact-resistant copolymerized polypropylene resin is 20-50wt%, the content of the toughening agent is 5-15wt%, the content of the adhesive is 5-15wt%, the content of the glass fiber is 10-50wt%, the content of the mineral powder is 10-30wt%, the content of the compatilizer is 0.5-5wt%, and the content of the organic nucleating agent, the antioxidant and the plasticizer are all 0.1-1wt%.
Preferably, the homopolypropylene resin has a melt flow index of 10 to 200g/10min at 230 ℃ under a load of 2.16 kg.
Preferably, the impact copolymer polypropylene resin is a polymer obtained by copolymerizing propylene and ethylene, the ethylene content is 3-30 wt%, and the melt flow index under the action of 2.16kg load at 230 ℃ is 1-40g/10min.
Preferably, the toughening agent is one or more of ethylene-butene copolymer and ethylene-octene copolymer, and the melt flow index is 0.5-30 g/10min at 230 ℃ and 2.16kg weight.
Preferably, the adhesive is low-melting polyester polyol, and the melting point measured at the temperature rise rate of 10 ℃/min is 50-80 ℃; the melt flow index at 160 ℃ under a weight of 2.16kg is from 3 to 10g/10min.
Preferably, the glass fiber has a length of 2 to 10mm.
Preferably, the mineral powder is one or more of calcium carbonate, talcum powder, mica, silicon carbide and montmorillonite, and the particle size is 1000-7000 meshes.
Preferably, the compatilizer is obtained by grafting modified polypropylene with maleic anhydride, and the content of the maleic anhydride functional group is 0.5-2wt%.
Preferably, the organic nucleating agent is one or more of sorbitol nucleating agents, phosphate nucleating agents and rosin nucleating agents.
Preferably, the antioxidant is one or more of hindered phenol macromolecule antioxidant, phosphorous acid antioxidant and alkyl ester antioxidant.
Preferably, the plasticizer is one or more of phthalic acid esters, fatty acid esters, phosphoric acid esters and epoxy esters.
The invention also provides a preparation method of the 3D printing polypropylene particles for large industrial models and outdoor buildings, which comprises the following steps:
(1) Uniformly mixing polypropylene resin, a toughening agent, an adhesive, a compatilizer, an organic nucleating agent, an antioxidant and a plasticizer in a high-speed mixer to obtain a mixture;
(2) Feeding the mixture through a main feeding port of a double-screw extruder, adding glass fiber and mineral powder from a side feeding port, extruding, cooling, and granulating by a granulator to obtain a granular modified polypropylene material;
preferably, the extrusion granulation conditions in step (2) include: the extrusion temperature is 180-250 ℃.
The invention also provides application of the 3D printing polypropylene particles as a 3D printing material for large-scale industrial models and outdoor buildings.
Compared with the prior art, the invention has the following technical advantages:
1) The mixture of the copolymerized polypropylene and the homopolymerized polypropylene reduces the crystallinity; by adding a large amount of inorganic filler and toughening agent, the shrinkage rate of the modified polypropylene is remarkably reduced, the dimensional stability is greatly improved, the warping phenomenon basically disappears, and the polypropylene particles have good 3D printing effect and precision.
2) The added adhesive contains more ester groups, has strong cohesive strength and adhesive force, can effectively bond materials between layers in the printing process, and can enable the printed materials to be in a molten state for a long time in the printing process due to the lower melting point of the adhesive, so that the next layer of printed materials can be better adhered.
3) The 3D printing modified polypropylene obtained by the invention is particularly suitable for printing large industrial models and outdoor building particles, has the advantages of simple preparation method, high production efficiency, high rigidity, difficult warping and good interlayer bonding force, and has wide market prospect and benefit.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The preparation method of the polypropylene particles for 3D printing comprises the following steps:
(1) Mixing the reagent with the raw materials: firstly, the homo-polypropylene resin, the co-polypropylene resin and the toughening agent are put into a stirrer, then the adhesive is added, after uniform stirring, the antioxidant, the organic nucleating agent, the compatilizer and the plasticizer are added for subsequent mixing, and the mixing is continued for 2 minutes, so that the mixed raw material is obtained finally.
(2) And (3) extruding and granulating: adding the mixed raw materials obtained in the step (1) into a main feeding bin of a double-screw extruder, adding glass fibers and mineral powder into the side feeding bin of the extruder, adding the mixture into the extruder according to the component proportion, melting and mixing uniformly, keeping the feeding speed uniform and smooth, and controlling the temperature of a melting section to be 180-200 ℃, the temperature of a mixing section to be 210-250 ℃ and the temperature of an extrusion section to be 180-200 ℃ in the double-screw extrusion process. And after cooling, granulating by a granulator to obtain the polypropylene granular material.
Polypropylene melting point and crystallinity test methods: polypropylene melting point and crystallinity measurements were performed using a PeakinElmer type differential scanning calorimeter.
The polypropylene shrinkage test method comprises the following steps: the prepared polypropylene particles are injected into a flat plate with the thickness of 150 multiplied by 300 multiplied by 2mm by adopting a kraussnafei 200-750 CX injection molding machine, the injection molding temperature is 230 ℃, and other parameters adopt default parameters of a system for molding. And standing the injection molding sample plate for 24 hours at room temperature, measuring the side length of the flat plate, and dividing the absolute value of the difference between the side length and the design value by the design value to obtain the shrinkage rate.
The method for testing the interlayer binding force of the polypropylene printing comprises the following steps: A3D printing sample plate with the size of 200mm multiplied by 100mm is vertically printed on the prepared polypropylene particles by adopting a creative three-emperor G5 particle printer, an A-type dumbbell type tensile sample strip required in ISO527 is cut by a sample cutting machine, and the tensile property in the printing Z-axis direction is tested.
In each of the examples and comparative examples, the main raw material sources are as shown in table 1:
TABLE 1 Main raw materials trade marks and sources
Other raw materials and reagents were obtained from commercial sources unless otherwise specified.
Polypropylene particles were prepared according to the above preparation method according to the composition of the components of comparative examples 1 to 4 and examples 1 to 2 in table 2:
table 2 examples 1-4 and comparative examples 1-2 formulations (% by weight)
The polypropylene particles obtained were subjected to the performance test, and the results are shown in Table 3:
TABLE 3 Properties of examples 1-4 and comparative examples 1-2
From the data of the sample differential scanning calorimeter in table 3, it can be seen that the melting point of each sample has no significant change, and the addition of the polypropylene copolymer slightly reduces the melting point to less than 1 ℃; the crystallinity is not obviously changed, but in comparative example 2, the crystallinity is slightly reduced after the polypropylene copolymer is added, so that the shrinkage of the modified polypropylene is reduced sharply by adding the thermoplastic elastomer and the inorganic filler and adding a large amount of glass fiber after the polypropylene copolymer and the polypropylene copolymer are combined, and the printing test result is consistent with the shrinkage test result.
From the printing test result, the fracture in the comparative example is brittle fracture, after the adhesive is added, the fracture is converted into ductile fracture, and the interlayer bonding force in the Z-axis direction is obviously increased; particularly, in comparative examples 1, 2 and 3, 4, when the binder is decreased, although the tensile modulus is increased (as a result of the increase in the content of glass fiber), the elongation at break is decreased, indicating that the binder plays a role of effective adhesion during printing, and can effectively improve the interlayer bonding force of printing.
From the comprehensive test results, the polypropylene particles prepared in the examples 1 to 4 have the advantages of processability, molding precision and small molding shrinkage deformation and warping, are suitable for being used as a material for 3D printing, particularly have high rigidity and good interlayer bonding force, and are extremely suitable for 3D printing of large industrial models and outdoor buildings.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Such modifications and variations are intended to be included within the scope of the present invention.
Claims (10)
1. The 3D printing polypropylene particles for large industrial models and outdoor buildings are characterized by containing polypropylene resin, a toughening agent, an adhesive, glass fibers and mineral powder;
wherein the polypropylene resin comprises a homo-polypropylene resin and an impact co-polypropylene resin;
preferably, based on the 3D printing polypropylene particles, the content of the homo-polypropylene resin is 5-20wt%, the content of the impact co-polypropylene resin is 20-50wt%, the content of the toughening agent is 5-15wt%, the content of the binder is 5-15wt%, the content of the glass fiber is 10-50wt%, and the content of the mineral powder is 10-30wt%.
2. The 3D printing polypropylene particles for large industrial models and outdoor buildings are characterized by comprising polypropylene resin, a toughening agent, an adhesive, glass fibers, mineral powder, a compatilizer, an organic nucleating agent, an antioxidant and a plasticizer;
wherein the polypropylene resin comprises a homo polypropylene resin and an impact co-polypropylene resin;
preferably, based on 3D printing polypropylene particles, the content of the homo-polypropylene resin is 5-20wt%, the content of the impact copolymer polypropylene resin is 20-50wt%, the content of the toughening agent is 5-15wt%, the content of the binder is 5-15wt%, the content of the glass fiber is 10-50wt%, the content of the mineral powder is 10-30wt%, the content of the compatilizer is 0.5-5wt%, and the content of the organic nucleating agent, the antioxidant and the plasticizer is 0.1-1wt%.
3. 3D-printed polypropylene particles according to claim 1 or 2, wherein the homopolypropylene resin has a melt flow index of 10-200g/10min at 230 ℃ under a 2.16kg load; and/or
The impact copolymer polypropylene resin is a polymer obtained by copolymerizing propylene and ethylene, and has a melt flow index of 1-40g/10min at 230 ℃ under the action of a 2.16kg load.
4. 3D printed polypropylene particles according to claim 1 or 2, wherein the toughening agent is one or more of ethylene-butene copolymer and ethylene-octene copolymer having a melt flow index of 0.5 to 30g/10min at 230 ℃ under 2.16kg weight.
5. 3D printed polypropylene particles according to claim 1 or 2, wherein the binder is a low melting polyester polyol, having a melting point of 50 to 80 ℃ measured at a temperature rise rate of 10 ℃/min and a melt flow index of 3 to 10g/10min at 160 ℃ under a weight of 2.16 kg.
6. 3D printed polypropylene particles according to claim 1 or 2, wherein the glass fibers have a length of 2-10mm; and/or
The mineral powder is one or more of calcium carbonate, talcum powder, mica, silicon carbide and montmorillonite, and preferably, the particle size is 1000-7000 meshes.
7. The 3D printed polypropylene particle according to claim 2, wherein the compatibilizer is maleic anhydride graft modified polypropylene, and the content of maleic anhydride functional groups is 0.5 to 2wt%; and/or
The organic nucleating agent is one or more of sorbitol, phosphate and rosin nucleating agents; and/or
The antioxidant is one or more of hindered phenol macromolecule antioxidant, phosphorous acid antioxidant and alkyl ester antioxidant; and/or
The plasticizer is one or more of phthalic acid esters, fatty acid esters, phosphoric acid esters and epoxy esters.
8. The method for the preparation of 3D printed polypropylene particles according to any one of claims 1 to 7, comprising the steps of:
s1, uniformly mixing polypropylene resin, a toughening agent, an adhesive, a compatilizer, an organic nucleating agent, an antioxidant and a plasticizer to obtain a mixture;
and S2, feeding the mixture through a main feeding port of a double-screw extruder, adding glass fiber and mineral powder from a side feeding port, extruding, cooling and granulating by using a granulator.
9. The method of claim 8, wherein the extrusion temperature is 180-250 ℃.
10. Use of the 3D printed polypropylene particles according to any one of claims 1 to 9 as 3D printed material for large industrial models and outdoor construction.
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