CN117777689A - Magnetic PLA/PBAT composite material for FDM type 3D printing and preparation method and application thereof - Google Patents
Magnetic PLA/PBAT composite material for FDM type 3D printing and preparation method and application thereof Download PDFInfo
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- CN117777689A CN117777689A CN202311702922.2A CN202311702922A CN117777689A CN 117777689 A CN117777689 A CN 117777689A CN 202311702922 A CN202311702922 A CN 202311702922A CN 117777689 A CN117777689 A CN 117777689A
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- 229920001896 polybutyrate Polymers 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 27
- 238000010146 3D printing Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- 239000006247 magnetic powder Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 229920006167 biodegradable resin Polymers 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 2
- 125000005498 phthalate group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000004626 polylactic acid Substances 0.000 description 39
- 229920000747 poly(lactic acid) Polymers 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000006698 induction Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920005692 JONCRYL® Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 polybutylene terephthalate-adipate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- WUUBVRZLVWWXDM-UHFFFAOYSA-N dioctoxy phosphono phosphate Chemical compound C(CCCCCCC)OOP(=O)(OOCCCCCCCC)OP(=O)(O)O WUUBVRZLVWWXDM-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a magnetic PLA/PBAT composite material for FDM 3D printing, a preparation method and application thereof, wherein the PLA/PBAT composite material comprises the following components in parts by weight: 150-210 parts of PLA resin, 100-140 parts of PBAT resin, 90-150 parts of magnetic powder, 3.4-5 parts of compatilizer and 1-1.5 parts of coupling agent, wherein the mass ratio of the PLA resin to the PBAT resin is (1.5-2): 1. The PLA/PBAT composite material provided by the invention has better magnetic force performance, and simultaneously can give consideration to the dryness and mechanical performance of the material, is a novel magnetic composite 3D printing material, and expands the technical category of FDM type 3D printing technology.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a magnetic PLA/PBAT composite material for FDM type 3D printing, and a preparation method and application thereof.
Background
The 3D printing technology is a rapid additive manufacturing technology for generating three-dimensional entities by adding stacked materials layer by layer, and compared with the traditional subtractive manufacturing technology, the rapid additive manufacturing technology has the characteristics of low loss, intelligentization, precision and high efficiency in product manufacturing, and the 3D printing technology can show great superiority when the high-end manufacturing field of complex shapes is involved. But the development of 3D printing technology is limited to the development of 3D printing materials to a great extent, so the development of more various and multifunctional 3D printing materials becomes a hot spot and key for research and application. Polylactic acid (PLA) is an aliphatic polyester polymer material which can be completely biodegraded, is usually synthesized from biomass materials such as corn starch or sucrose and the like through multi-step reaction, and has the advantages of good chemical inertness, good biocompatibility, easy processing, capability of being completely decomposed into carbon dioxide and water which are nontoxic and harmless to the environment under natural conditions such as microorganisms, acid and alkali after corresponding products are abandoned, and the like. However, PLA resins have only 10% elongation at break, are brittle, have low impact strength, and poor flexibility, which greatly limit the use of PLA in the field of 3D printed materials.
The technique of fused extrusion deposition modeling (FDM) is a common technique for 3D printing, which uses thermoplastic polymers in a fused state to extrude from a printing nozzle, solidify into a contour thin layer and then superpose one layer by one layer, and is the most widely used and least expensive shaping technique, while the use of FDM-type 3D printed magnetic composite materials is very small in the market, wherein most products are designed Fe 3 O 4 The PLA material is doped for preparation molding, and the product prepared by the method has poor magnetic effect, only has the characteristic of soft magnetic material, and can be attracted by a strong magnetic field under specific conditions so as not to be applied in a large range, thus being incapable of meeting the requirement of a real magnetic material. Therefore, a magnetic FDM type 3D printing material capable of combining magnetic functions and mechanical properties is needed to fill the blank of the industry and expand the application range of the FDM type 3D printing material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a magnetic PLA/PBAT composite material for FDM type 3D printing, and a preparation method and application thereof.
The invention provides a magnetic PLA/PBAT composite material for FDM 3D printing, which comprises the following components in parts by weight:
wherein the mass ratio of the PLA resin to the PBAT resin is (1.5-2) 1;
the PBAT resin (polybutylene terephthalate-adipate) is a biodegradable thermoplastic copolymer, is generally synthesized by raw materials such as butanediol, adipic acid, terephthalic acid and the like, has biodegradability, regenerability, thermoplasticity, elasticity and toughness, and can increase the toughness of the whole extrusion material by compounding the PLA resin with the high-toughness PBAT resin; because the compatibility of the PBAT resin and the PLA resin is poor, the addition of the compatilizer can help the materials to be mixed better; after the magnetic powder is added, a coupling agent is needed to be added to solve the problem of interfacial anisotropy between materials in order to overcome the interfacial energy difference between the magnetic substance and the composite material.
Further, the mass ratio of PLA resin to PBAT resin is 3:2.
Further, the magnetic powder is NdFeB.
Further, the compatilizer is one or more of biodegradable resin chain extender YMX-06, basf chain extender joncryl ADR-4468, maleic anhydride, dicumyl peroxide and ethylene-methyl acrylate-glycidyl methacrylate, preferably basf chain extender joncryl ADR-4468, and the compatibility between different polycondensate materials can be improved by using the basf chain extender as the compatilizer.
Further, the coupling agent is selected from one or more of a phthalate coupling agent and a silane coupling agent.
Further, the coupling agent is selected from phthalate coupling agents, which can improve interface compatibility between different materials, in particular, improve binding force between reinforcing filler (magnetic powder) and a polymer matrix, and has two different functional groups, one end of the coupling agent can react with the polymer material, the other end of the coupling agent can react with inorganic filler or other substances, and the coupling agent has the function of preventing hydrolysis. An aqueous solution of the amine salt of bis (dioctyl-oxy pyrophosphate) ethylene titanate GR-311W is preferred.
Further, the weight average molecular weight (Mw) of the PLA resin is 180000-220000, if the Mw is too low, the polymer chain is shorter, the PLA strength and toughness are reduced, the PLA is easy to break, the PLA is easier to degrade in the processing process, the heat resistance is reduced, the viscosity of the material is changed in the processing process of the material, and if the viscosity is too high, the nozzle is blocked, so that the screw cannot extrude the composite material; if the viscosity is too low, the composite material is difficult to form, and continuous and uniform 3D printing materials cannot be manufactured; when the Mw of PLA is too high, the viscosity of PLA is affected, resulting in internal stress inside the material and poor formability.
Further, the weight average molecular weight (Mw) of the PBAT resin is 50000-80000.
The invention also provides a preparation method of the PLA/PBAT composite material, which comprises the following steps:
s1, drying PLA resin and PBAT resin;
s2, weighing the components according to the weight parts, stirring and mixing, then drying again, and extruding and shearing by using a dynamic double-screw extruder to prepare the PLA/PBAT composite material;
the drying step is that the mixture is dried for 8-12 hours on a hot plate at 70-90 ℃, and the mixture is put into a moisture absorption bag to be dried in the hot plate at 70-90 ℃ for 8-12 hours when the mixture is dried again, so that the problem that the printing effect is affected due to too low dryness of the mixture can be avoided, wherein the extrusion temperature is 190-200 ℃, and the extrusion speed is 75-85%.
The mechanical properties of the material are easily deteriorated due to various reasons such as agglomeration, segregation and the like in the coupling process of the magnetic powder and the PLA/PBAT, so that the problem of performance degradation of the material caused by the coupling of heterogeneous materials is alleviated by adding and stirring the coupling agent.
The invention also provides application of the PLA/PBAT composite material in preparing a magnetic FDM type 3D printing filament.
In conclusion, compared with the prior art, the invention achieves the following technical effects:
(1) The PLA/PBAT composite material provided by the invention has high magnetic property;
(2) The PLA/PBAT composite material provided by the invention has high mechanical property;
(3) The PLA/PBAT composite material prepared by the method has high dryness.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a specific preparation process of PLA/PBAT composite material in example 1 of the invention;
FIG. 2 is a physical diagram of the PLA/PBAT composite material prepared in example 1 of the invention;
FIG. 3 is a graph showing the diameter measurement of the PLA/PBAT composite material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the magnetic induction intensity measurement of the PLA/PBAT composite material prepared in example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, shall fall within the scope of the invention.
Examples
The present invention will be further described with reference to the following specific examples, which are all preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples, and are not particularly limited to the types of raw materials of the components used in the following specific examples.
1. The raw material sources for the examples and comparative examples are as follows:
PLA resin: number 4032D, mw 1.5X10 5 ，Nature Works；
PBAT resin: the brand is TH801T, mw is 50000-80000, xinjiang river company of China;
magnetic powder: ndFeB,100 mesh powder, elemental weight percent: ne 17.7%, PR 5.7%, B1%, fe 75.4%, hebei beyond the company of metal alloy materials Co., ltd;
and (3) a compatilizer: basf chain extender, brand joncryl ADR-4468, basf;
coupling agent: phthalate coupling agent with the brand of GR-311W, nanjing and wetting coupling agent;
the preparation method of the PLA/PBAT composite material of the embodiment 1 comprises the following steps:
s1, drying PLA resin and PBAT resin;
s2, weighing the components according to the weight parts, wherein the mass ratio of PLA resin to PBAT is 3:2, stirring and mixing the components, drying the components again, and extruding and shearing the components by using a dynamic double-screw extruder to obtain the PLA/PBAT composite material;
wherein the drying step is to dry for 10 hours on a hot plate at 70 ℃, and the mixed material is put into a moisture absorption bag to dry for 10 hours in the hot plate at 70 ℃ when the mixed material is dried again, the extrusion temperature is 190-200 ℃, and the extrusion speed is 75% -85%.
Comparative example 1 differs from example 1 in that the mass ratio of PLA resin to PBAT is 4:1.
Comparative example 2 differs from example 1 in that the mass ratio of PLA resin to PBAT is 0.5:1
2. Performance test method
Induced magnetic field strength: and (3) measuring the magnetic induction intensity of the magnet by using a measuring Gaussian meter, and obtaining a corresponding magnetic field measured value by enabling a measuring component of the Gaussian meter to be close to the magnetic sample.
Example 1
The composite material prepared in the example 1 is shown in fig. 2, and has good appearance, diameter kept at 1.75mm, tolerance of + -0.03 mm and certain toughness; meanwhile, the magnetism of the composite material meets the basic requirement, the measurement result of the Gaussian meter is shown in fig. 1, the measured value of the intensity of the induction magnetic field of the magnetic composite filament is 118Gs, the magnetic property is good, and the application expansion of the magnetic material which can be used for FDM type 3D printing is realized.
The composite material prepared by the invention has the induction magnetic field intensity of 100-150Gs (10-15 mT), high mechanical property, obvious advantage compared with a comparative example, and can effectively meet the high standard requirements of customers and markets.
Comparative example 1
The mass ratio of PLA to PBAT of comparative example 1 is 4:1, the extrusion viscosity of the composite material is too small, and thus it is difficult to mold.
Comparative example 2
The mass ratio of PLA to PBAT in comparative example 2 was 0.5:1, the extrusion of the composite material was difficult and the twin screw extruder was prone to burn out.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The magnetic PLA/PBAT composite material for FDM type 3D printing is characterized by comprising the following components in parts by weight:
150-210 parts of PLA resin;
100-140 parts of PBAT resin;
90-150 parts of magnetic powder;
3.4-5 parts of compatilizer;
1-1.5 parts of a coupling agent;
wherein the mass ratio of the PLA resin to the PBAT resin is (1.5-2): 1.
2. The PLA/PBAT composite of claim 1, wherein the mass ratio of PLA resin to PBAT resin is 3:2.
3. The PLA/PBAT composite of claim 1, wherein the magnetic powder is NdFeB.
4. The PLA/PBAT composite of claim 1, wherein the compatibilizer is one or more of a biodegradable resin chain extender, a basf chain extender, maleic anhydride, dicumyl peroxide, and ethylene-methyl acrylate-glycidyl methacrylate.
5. The PLA/PBAT composite of claim 1, wherein the coupling agent is selected from one or more of a phthalate coupling agent and a silane coupling agent.
6. The PLA/PBAT composite of claim 4, wherein the coupling agent is selected from phthalate coupling agents.
7. The PLA/PBAT composite of claim 1, wherein the PLA resin has a weight average molecular weight of 180000 to 220000.
8. The PLA/PBAT composite of claim 1, wherein the PBAT resin has a weight average molecular weight of 50000-80000.
9. A method of preparing a PLA/PBAT composite material according to any one of claims 1 to 8, comprising the steps of:
s1, drying PLA resin and PBAT resin;
and S2, weighing the components according to the weight parts, stirring and mixing, then drying again, and extruding and shearing by using a dynamic double-screw extruder to obtain the PLA/PBAT composite material.
10. Use of the PLA/PBAT composite of any of claims 1-8 in the preparation of a magnetic FDM type 3D printed filament.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311702922.2A CN117777689A (en) | 2023-12-11 | 2023-12-11 | Magnetic PLA/PBAT composite material for FDM type 3D printing and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311702922.2A CN117777689A (en) | 2023-12-11 | 2023-12-11 | Magnetic PLA/PBAT composite material for FDM type 3D printing and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117777689A true CN117777689A (en) | 2024-03-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311702922.2A Pending CN117777689A (en) | 2023-12-11 | 2023-12-11 | Magnetic PLA/PBAT composite material for FDM type 3D printing and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117777689A (en) |
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2023
- 2023-12-11 CN CN202311702922.2A patent/CN117777689A/en active Pending
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