CN112759909A - 3D printing raw material based on PLA reclaimed materials, 3D printing material and preparation method thereof - Google Patents
3D printing raw material based on PLA reclaimed materials, 3D printing material and preparation method thereof Download PDFInfo
- Publication number
- CN112759909A CN112759909A CN202110088178.6A CN202110088178A CN112759909A CN 112759909 A CN112759909 A CN 112759909A CN 202110088178 A CN202110088178 A CN 202110088178A CN 112759909 A CN112759909 A CN 112759909A
- Authority
- CN
- China
- Prior art keywords
- pla
- printing
- reclaimed
- parts
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 113
- 238000010146 3D printing Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 title claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 9
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 78
- 239000004626 polylactic acid Substances 0.000 claims description 78
- 238000001125 extrusion Methods 0.000 claims description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 239000012745 toughening agent Substances 0.000 claims description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 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 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- 239000010456 wollastonite Substances 0.000 claims description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims description 5
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 34
- 238000007639 printing Methods 0.000 description 25
- 238000002156 mixing Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000003031 feeding effect Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to the technical field of 3D printing, and particularly relates to a PLA reclaimed material-based 3D printing raw material, a 3D printing material and a preparation method of the 3D printing material. The 3D printing raw material based on the PLA reclaimed material comprises the following components in parts by weight: 60-100 parts of PLA reclaimed materials, 0.2-1 part of plasticizer, 0.2-1 part of cross-linking agent, 1-10 parts of chain extender, 1-5 parts of flexibilizer, 0.2-1 part of lubricant, 0.2-1 part of antioxidant and 5-20 parts of inorganic filler. The invention solves the problem that PLA waste materials with different degradation degrees are difficult to be reused in the field of 3D printing.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a PLA reclaimed material-based 3D printing raw material, a 3D printing material and a preparation method of the 3D printing material.
Background
PLA is a completely biodegradable green polymer material, and due to excellent printing performance, the role played in 3D printing consumables is more and more important, and with the continuous expansion of the 3D printing field, the market share also increases year by year, and according to incomplete statistics, the usage amount of PLA in the 3D field reaches 2W tons by 2020. With the increase of the consumption of the PLA in a well-spraying manner, waste products generated in the application process are multiplied, so that how to recycle the PLA waste products and save social and natural resources to the maximum extent is a prospective subject.
CN107825702A discloses a recycling system for consumables ABS and PLA of 3D printer, which recycles and processes images printed by using ABS and PLA as materials, and corresponding waste products and leftover materials through a recycling device with a special design.
CN206106154U discloses preparation 3D printing consumables device is retrieved to plastics, adopts the mode that liquid nitrogen low temperature embrittlement combined cooling crushing technique and production 3D printing consumables combined together, makes one kind and collects the equipment that cooling technique smashed plastics and production 3D printing consumables in an organic whole, carries out recovery processing to plastics and recycles.
Above-mentioned technique has all adopted device or equipment that has certain special design, carries out recovery processing to 3D printing type abandonment consumptive material or plastics and recycles, all does not consider some 3D printing type abandonment consumptive materials, for example PLA waste product has appeared under the condition of the degradation of different degree, and its physical properties has reduced by a wide margin with performance, can't directly carry out 3D after above-mentioned recovery processing and print the problem that the performance is extremely poor.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a 3D printing raw material based on a PLA reclaimed material, a 3D printing material and a preparation method of the 3D printing material, and aims to solve the problem that PLA waste materials with different degradation degrees are difficult to be reused in the field of 3D printing.
The technical scheme provided by the invention is as follows:
A3D printing raw material based on a PLA reclaimed material comprises the following components in parts by weight: 60-100 parts of PLA reclaimed materials, 0.2-1 part of plasticizer, 0.2-1 part of cross-linking agent, 1-10 parts of chain extender, 1-5 parts of flexibilizer, 0.2-1 part of lubricant, 0.2-1 part of antioxidant and 5-20 parts of inorganic filler.
After the PLA material is used, the physical property and the service performance of waste products are greatly reduced under the condition that the waste products are degraded to different degrees, and the waste products cannot be directly subjected to 3D printing or have extremely poor printing performance after being subjected to less than recycling treatment.
After degradation, the PLA material can form a segment with a functional group or a structure such as carboxyl (-COOH), hydroxyl (-OH) and the like. Based on the chemical properties of the fragments, the technical scheme adopts the chain extender and the cross-linking agent to carry out chain extension or cross-linking on the degraded fragments, thereby recovering the performance of the PLA material and meeting the use requirement of the PLA material as a new printing material.
Specifically, the plasticizer is selected from one or more of poly epsilon-caprolactone (PCL), acetyl tributyl citrate (ATBC), epoxidized soybean oil, a propylene oxide condensate (PPG) and dibutyl phthalate (DBP).
Specifically, the crosslinking agent is selected from any one or more of dibenzoyl peroxide (BPO), dicumyl peroxide (DCP), di-tert-butylperoxyisopropyl benzene (BIPB), tert-butyl Peroxyester (PHV) or tert-butyl peroxyhexane (HXA).
Based on the technical scheme, the degraded PLA and the cross-linking agent can be cross-linked under the conditions of the working temperature and the pressure of the double-screw extruder.
Specifically, the chain extender is any one or a mixture of more of styrene-glycidyl methacrylate copolymer (ADR), diisocyanate (HDI), phosphite ester, dianhydride and diepoxy compound.
Based on the technical scheme, the degraded PLA and the chain extender can be crosslinked under the conditions of the working temperature and the pressure of the double-screw extruder.
Specifically, the toughening agent is any one or a mixture of more of polylactic acid-based thermoplastic polyurethane elastomer (PLA-TPU), methyl acrylate copolymer (FM40), styrene thermoplastic elastomer (SBS), Ethylene Propylene Diene Monomer (EPDM) and ethylene-octene copolymer (POE).
Specifically, the lubricant is any one or a mixture of stearic acid, zinc stearate, polyethylene wax, paraffin and silicone powder.
Specifically, the antioxidant is selected from one or more of antioxidants 168, 1010, AS4500, Revonox 608 and Revonox 608T.
Specifically, the inorganic filler is any one or mixture of more of talcum powder, calcium carbonate, wollastonite, silane coupling agent modified talcum powder, silane coupling agent modified calcium carbonate and silane coupling agent modified wollastonite.
The invention also provides a preparation method of the 3D printing material based on the PLA reclaimed material, which comprises the following steps: and carrying out double-screw extrusion and granulation on the uniformly mixed 3D printing raw material based on the PLA reclaimed material to obtain the 3D printing material based on the PLA reclaimed material, wherein the melting temperature of the double-screw extrusion is 160-190 ℃, and the extrusion pressure of the double-screw extrusion is 2.0-5.0 MPa.
Based on the technical scheme, on the premise of not needing to transform or add new equipment, the 3D printing raw material based on the PLA reclaimed material can be crosslinked and chain-extended in the high-temperature and high-pressure melt extrusion process by adopting double-screw extrusion.
Further, the method also comprises the following steps: and drawing and winding the obtained granular material through a single-screw extruder to obtain the PLA reclaimed material-based 3D printing material, wherein the single-screw extrusion temperature is 200-220 ℃, and the single-screw extrusion pressure is 2.0-5.0 MPa.
Specifically, the preparation method of the 3D printing material based on the PLA reclaimed material comprises the following steps:
1) raw material treatment of 3D printing raw materials based on PLA reclaimed materials;
2) material blending and double-screw extrusion;
3) obtaining a 3D printing material based on a PLA reclaimed material;
4) the 3D printing material based on PLA regrind is drawn into filaments by a single screw extruder.
More specifically, the preparation method of the 3D printing material based on the PLA reclaimed material comprises the following steps:
1) screening impurities from the PLA reclaimed materials, crushing the PLA reclaimed materials in a crusher, and then drying the PLA reclaimed materials in a vacuum drying oven; simultaneously drying and placing the cross-linking agent, the chain extender, the flexibilizer, the lubricant, the antioxidant and the inorganic filler;
2) weighing the PLA reclaimed materials, the plasticizer, the cross-linking agent, the chain extender, the toughening agent, the lubricant, the antioxidant and the inorganic filler according to the proportion, putting the weighed materials into a high-speed mixer for mixing, uniformly mixing, then carrying out melt blending extrusion through a double-screw extruder, and carrying out water-cooling granulation;
3) obtaining a 3D printing material based on a PLA reclaimed material, and drying in a vacuum drying oven;
4) and drawing the obtained 3D printing material based on the PLA reclaimed material into filaments with the diameter of 1.75mm by a single-screw extruder, and winding the filaments by using a 3D printing wire coil at the tail end.
More specifically, the preparation method of the 3D printing material based on the PLA reclaimed material comprises the following steps:
1) screening impurities of the recovered PLA material, crushing the recovered PLA material into particles with the diameter of 5mm by a crusher, and drying the particles in a vacuum drying oven at the drying temperature of 65 ℃ for 4 hours; simultaneously drying and placing the cross-linking agent, the chain extender, the flexibilizer, the lubricant, the antioxidant and the inorganic filler;
2) weighing the PLA reclaimed materials, the plasticizer, the cross-linking agent, the chain extender, the toughening agent, the lubricant, the antioxidant and the inorganic filler according to the proportion, putting the weighed materials into a high-speed mixer for mixing for 15min, uniformly mixing, then carrying out melt blending extrusion through a double-screw extruder, carrying out water-cooling granulation, wherein the processing temperature of the double-screw extruder is 160-190 ℃, the rotating speed of a main machine is 150-200 r/min, and the feeding frequency is 5-8 Hz;
3) obtaining a 3D printing material based on a PLA reclaimed material, drying the 3D printing material in a vacuum drying oven at 65 ℃ for 4 hours, and measuring that the moisture content is lower than 0.2%;
4) and (3) drawing the obtained 3D printing material based on the PLA reclaimed material into filaments with the diameter of 1.75mm by a single-screw wire drawing machine, winding the filaments by using a 3D printing wire coil at the tail end, wherein the processing temperature of a single-screw extruder is 200-220 ℃, and the rotating speed of a main machine is 80-120 r/min.
The resulting filament was subjected to 3D printing test using an FDM3D printer, the printing test model used being a classical FDM3D printing test model.
The invention also provides the 3D printing material based on the PLA reclaimed material prepared by the preparation method.
The invention has the beneficial effects that:
according to the secondary utilization technology of the PLA reclaimed material in the field of 3D printing, the PLA waste material is recycled and modified on the premise of not modifying or adding new equipment, so that the PLA reclaimed material has the basic 3D printing performance of the PLA material, can be reused in the field of 3D printing, can be changed into valuable, saves social and natural resources to the maximum extent, protects the environment, and has great economic benefits. The preparation method for modifying the PLA reclaimed material provided by the invention is simple and easy to implement, can be implemented only by using the existing equipment of a production enterprise, does not increase the burden of the enterprise, and is suitable for being pushed in industrial production.
Drawings
FIG. 1 is a comparative graph of the torque rheometer test of example 1.
FIG. 2 is a comparative graph of the torque rheometer test of example 2.
FIG. 3 is a comparative graph of the torque rheometer test of example 3.
FIG. 4 is a comparative graph of the torque rheometer test of example 4.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Taking 85 parts of pre-dried PLA reclaimed material, 0.5 part of plasticizer PCL, 0.5 part of cross-linking agent BPO, 5 parts of chain extender ADR, 3 parts of toughening agent PLA-TPU, 0.25 part of lubricant stearic acid 1840 and polyethylene wax 3316, 0.25 part of antioxidant 1010 and 168 respectively, and adding talcum powder SD-4005 parts treated by silane coupling agent into a high-speed mixer for mixing for 15min, melting, blending and extruding by a double-screw extruder after uniform mixing, and performing water cooling granulation, wherein the working temperature is 175 ℃, and the working pressure is 4.2 MPa. Drying the obtained blending modified particles in a 65 ℃ vacuum drying oven for 4h, measuring that the moisture content is lower than 0.2%, taking out, pouring into a hopper of a single-screw extruder, performing melt extrusion to draw the particles into filaments with the diameter of 1.75mm, performing FDM3D printing test on the filaments by using a special 3D printing wire coil, and performing the test by using a classical FDM3D printing test model, wherein the working temperature is 210 ℃ and the working pressure is 3.8 MPa.
Carrying out Harper torque rheometer test on the PLA reclaimed material, wherein the maximum torque is 2.3 Nm; and (3) carrying out Harper torque rheometer test on the obtained 3D printing material, wherein the maximum torque of the printing material is 10.8Nm under the same condition. The maximum torque value is compared to show that after the melt extrusion of the twin-screw extruder, the molecular weight of the PLA reclaimed material is obviously improved, the crosslinking and chain extension of the PLA reclaimed material in a molten state are realized, and fig. 1 is a torque rheometer test comparison curve.
Example 2
90 parts of pre-dried PLA reclaimed material, 1 part of plasticizer ATBC, 0.5 part of cross-linking agent DCP, 2 parts of chain extender HDI, 402.5 parts of flexibilizer FM, 0.25 part of lubricant silicone powder KJ-B118 and 0.25 part of polyethylene wax 3316, 0.25 part of antioxidant 1010 and AS4500, and 64 parts of calcium carbonate HX-8164 treated by silane coupling agent are put into a high-speed mixer to be mixed for 15min, and the mixture is melted, blended and extruded by a double-screw extruder after being uniformly mixed, and is subjected to water cooling granulation at the working temperature of about 180 ℃ and the working pressure of 3.25 MPa. Drying the obtained blending modified particles in a 65 ℃ vacuum drying oven for 4h, measuring that the moisture content is lower than 0.2%, taking out, pouring into a hopper of a single-screw extruder, performing melt extrusion to draw the particles into filaments with the diameter of 1.75mm, performing FDM3D printing test on the filaments by using a special 3D printing wire coil, and performing the test by using a classical FDM3D printing test model, wherein the working temperature is 210 ℃ and the working pressure is 3.0 MPa.
Carrying out Harper torque rheometer test on the PLA reclaimed material, wherein the maximum torque is 2.3 Nm; and (3) carrying out Harper torque rheometer test on the obtained 3D printing material, wherein the maximum torque of the printing material is 5.1Nm under the same condition. The maximum torque value is compared to show that after the melt extrusion of the twin-screw extruder, the molecular weight of the PLA reclaimed material is obviously improved, the crosslinking and chain extension of the PLA reclaimed material in a molten state are realized, and fig. 2 is a torque rheometer test comparison curve.
Example 3
Taking 85 parts of pre-dried PLA reclaimed material, 0.5 part of plasticizer PPG, 0.2 part of cross-linking agent BIPB, 4.5 parts of chain extender phosphite ester, 3 parts of toughening agent POE, 0.5 part of each of lubricant silicone powder KJ-B118 and paraffin 56#, 0.4 part of each of antioxidant 168 and AS4500, and 5 parts of TH106 wollastonite treated by silane coupling agent, putting into a high-speed mixer, mixing for 15min, melting, blending and extruding by a double-screw extruder after uniform mixing, and water-cooling and granulating at the working temperature of 170 ℃ and the working pressure of 2.8 MPa. Drying the obtained blending modified particles in a 65 ℃ vacuum drying oven for 4 hours, measuring that the moisture content is lower than 0.2%, taking out, pouring into a hopper of a single-screw extruder, performing melt extrusion to draw the particles into filaments with the diameter of 1.75mm, performing FDM3D printing test on the filaments by using a special 3D printing wire coil under the working temperature of 220 ℃ and the working pressure of 2.5MP, and performing test by using a classical FDM3D printing test model.
Carrying out Harper torque rheometer test on the PLA reclaimed material, wherein the maximum torque is 2.3 Nm; and (3) carrying out Harper torque rheometer test on the obtained 3D printing material, wherein the maximum torque of the printing material is 4.3Nm under the same condition. The maximum torque value is compared to show that after the melt extrusion of the twin-screw extruder, the molecular weight of the PLA reclaimed material is obviously improved, the crosslinking and chain extension of the PLA reclaimed material in a molten state are realized, and fig. 3 is a torque rheometer test comparison curve.
Example 4
82 parts of pre-dried PLA reclaimed material, 0.4 part of plasticizer PCL, 0.6 part of cross-linking agent DCP, 3 parts of chain extender ADR, 5 parts of toughening agent EPDM, 0.25 part of lubricant silicone powder KJ-B118 and 0.25 part of polyethylene wax 3316 respectively, 0.25 part of antioxidant 1010 and Revonox 608 respectively, and 4 parts of talcum powder SD-400 and calcium carbonate HX-816 respectively treated by silane coupling agent are put into a high-speed mixer to be mixed for 15min, and are melted, blended and extruded by a double-screw extruder after being uniformly mixed, and are granulated by water cooling, the working temperature is 190 ℃, and the working pressure is 4.3 MPa. Drying the obtained blending modified particles in a 65 ℃ vacuum drying oven for 4h, measuring that the moisture content is lower than 0.2%, taking out, pouring into a hopper of a single-screw extruder, performing melt extrusion to draw the particles into filaments with the diameter of 1.75mm, performing FDM3D printing test on the filaments by using a special 3D printing wire coil, and performing test by using a classical FDM3D printing test model, wherein the working temperature is 210 ℃ and the working pressure is 3.6 MPa.
Carrying out Harper torque rheometer test on the PLA reclaimed material, wherein the maximum torque is 2.3 Nm; the obtained 3D printing material is subjected to Harper torque rheometer test, and the maximum torque of the material is 10.6Nm under the same condition. The maximum torque value is compared to show that after the melt extrusion of the twin-screw extruder, the molecular weight of the PLA reclaimed material is obviously improved, the crosslinking and chain extension of the PLA reclaimed material in a molten state are realized, and fig. 4 is a torque rheometer test comparison curve.
The basic physical properties of the blend modified particles prepared in examples 1 to 4 were measured, and the results are shown in table 1 below:
TABLE 1
The blending modified wire prepared in the embodiments 1-4 is subjected to printing test, a classic FDM3D printing test model is adopted for evaluation, and the feeding effect and the printing effect are evaluated as follows:
the feeding effect is as follows: the feeding is smooth, the end is not broken, the plug is not blocked, and the smoke is not generated.
Printing effect: the wire rod 3D when printing bonding effect is good, and the model surface of printing is smooth, and there is not deckle edge, and the corner shaping is good, and the goods base does not have the warpage, and whole mellow and smooth not layering, and the material does not have obvious ageing discoloration.
The evaluation effect of the printing test model meets the requirement of 5.4 wire printing and forming in the national standard GB/T37643-.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The 3D printing raw material based on the PLA reclaimed material is characterized by comprising the following components in parts by weight: 60-100 parts of PLA reclaimed materials, 0.2-1 part of plasticizer, 0.2-1 part of cross-linking agent, 1-10 parts of chain extender, 1-5 parts of flexibilizer, 0.2-1 part of lubricant, 0.2-1 part of antioxidant and 5-20 parts of inorganic filler.
2. The PLA reclaimed material-based 3D printing stock as recited in claim 1, wherein: the plasticizer is selected from one or more of poly epsilon-caprolactone, acetyl tributyl citrate, epoxidized soybean oil, propylene oxide condensate or dibutyl phthalate.
3. The PLA reclaimed material-based 3D printing stock as recited in claim 1, wherein: the cross-linking agent is selected from any one or more of dibenzoyl peroxide, dicumyl peroxide, di-tert-butylperoxyisopropyl benzene, tert-butyl peroxyester or tert-butyl peroxyhexane.
4. The PLA reclaimed material-based 3D printing stock as recited in claim 1, wherein: the chain extender is any one or mixture of more of styrene-glycidyl methacrylate copolymer, diisocyanate, phosphite ester, dianhydride and diepoxy compound.
5. The PLA reclaimed material-based 3D printing stock as recited in claim 1, wherein: the toughening agent is any one or a mixture of more of polylactic acid-based thermoplastic polyurethane elastomer, methyl acrylate copolymer, styrene thermoplastic elastomer, ethylene propylene diene monomer and ethylene-octene high polymer.
6. The PLA reclaimed material-based 3D printing stock as recited in claim 1, wherein: the lubricant is any one or mixture of stearic acid, zinc stearate, polyethylene wax, paraffin and silicone powder.
7. The PLA reclaimed material-based 3D printing raw material as claimed in any one of claims 1 to 6, wherein:
the antioxidant is selected from one or more of antioxidant 168, antioxidant 1010, antioxidant AS4500, antioxidant Revonox 608 and antioxidant Revonox 608T;
the inorganic filler is any one or mixture of more of talcum powder, calcium carbonate, wollastonite, silane coupling agent modified talcum powder, silane coupling agent modified calcium carbonate and silane coupling agent modified wollastonite.
8. A preparation method of a 3D printing material based on a PLA reclaimed material is characterized by comprising the following steps: carrying out twin-screw extrusion and granulation on the uniformly mixed PLA reclaimed material-based 3D printing raw material according to any one of claims 1 to 7 to obtain a PLA reclaimed material-based 3D printing material, wherein the melting temperature of the twin-screw extrusion is 160-190 ℃, and the extrusion pressure of the twin-screw extrusion is 2.0-5.0 MPa.
9. The preparation method of the PLA reclaimed material-based 3D printing material as claimed in claim 8, which further comprises the following steps after granulation: and drawing and winding the obtained granular material through a single-screw extruder to obtain the PLA reclaimed material-based 3D printing material, wherein the single-screw extrusion temperature is 200-220 ℃, and the single-screw extrusion pressure is 2.0-5.0 MPa.
10. A PLA recyclate-based 3D printed material prepared by the method for preparing a PLA recyclate-based 3D printed material according to claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110088178.6A CN112759909A (en) | 2021-01-22 | 2021-01-22 | 3D printing raw material based on PLA reclaimed materials, 3D printing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110088178.6A CN112759909A (en) | 2021-01-22 | 2021-01-22 | 3D printing raw material based on PLA reclaimed materials, 3D printing material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112759909A true CN112759909A (en) | 2021-05-07 |
Family
ID=75705639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110088178.6A Pending CN112759909A (en) | 2021-01-22 | 2021-01-22 | 3D printing raw material based on PLA reclaimed materials, 3D printing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112759909A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539750A (en) * | 2022-03-11 | 2022-05-27 | 深圳光华伟业股份有限公司 | Copolymerization toughening modification material for 3D printing PLA and preparation method thereof |
| CN114621570A (en) * | 2022-03-29 | 2022-06-14 | 湖北中烟工业有限责任公司 | Regeneration method and application of residual materials in cooling section of flue gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410147A (en) * | 2018-03-26 | 2018-08-17 | 华南协同创新研究院 | A kind of 3D printing wire rod and preparation method using the preparation of polylactic acid reclaimed materials |
| CN110396286A (en) * | 2019-07-23 | 2019-11-01 | 南宁师范大学 | Excellent 3D printing consumptive material and preparation method thereof at a low price |
| CN111875940A (en) * | 2020-08-06 | 2020-11-03 | 苏州环诺新材料科技有限公司 | Toughened heat-resistant polylactic acid 3D printing wire and preparation method thereof |
-
2021
- 2021-01-22 CN CN202110088178.6A patent/CN112759909A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410147A (en) * | 2018-03-26 | 2018-08-17 | 华南协同创新研究院 | A kind of 3D printing wire rod and preparation method using the preparation of polylactic acid reclaimed materials |
| CN110396286A (en) * | 2019-07-23 | 2019-11-01 | 南宁师范大学 | Excellent 3D printing consumptive material and preparation method thereof at a low price |
| CN111875940A (en) * | 2020-08-06 | 2020-11-03 | 苏州环诺新材料科技有限公司 | Toughened heat-resistant polylactic acid 3D printing wire and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539750A (en) * | 2022-03-11 | 2022-05-27 | 深圳光华伟业股份有限公司 | Copolymerization toughening modification material for 3D printing PLA and preparation method thereof |
| CN114621570A (en) * | 2022-03-29 | 2022-06-14 | 湖北中烟工业有限责任公司 | Regeneration method and application of residual materials in cooling section of flue gas |
| CN114621570B (en) * | 2022-03-29 | 2023-09-19 | 湖北中烟工业有限责任公司 | Regeneration method and application of residual materials in flue gas cooling section |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102060564B (en) | Light-weight environmental-friendly stone paper and preparation method thereof | |
| CN101735579A (en) | High-performance recovered PET/ABS alloy | |
| CN112759909A (en) | 3D printing raw material based on PLA reclaimed materials, 3D printing material and preparation method thereof | |
| CN114044968B (en) | High-melt-strength polypropylene material resistant to cyclic processing and preparation method and application thereof | |
| CN101870823A (en) | Completely biodegradable material filling master batch and preparation method thereof | |
| CN101456973A (en) | UPVC/grading complex formulation inorganic powder composite material and preparation method thereof | |
| WO2022041591A1 (en) | Polyoxymethylene composition, preparation method therefor and use thereof | |
| KR20050057644A (en) | Process for the production of resin compositions | |
| CN115011083A (en) | Fully biodegradable composite material capable of being repeatedly processed and preparation method thereof | |
| CN111019211A (en) | Modified high-density polyethylene composite material and preparation method thereof | |
| CN110669277A (en) | Environment-friendly degradable plastic turnover box made of straw or rice hull raw materials | |
| JP2022117416A (en) | Polyester film and method for producing the same | |
| CN113201154A (en) | Antistatic master batch and preparation method thereof | |
| CN113637248A (en) | Preparation of low-shrinkage HDPE sheath material | |
| TW202244117A (en) | Polyester resin composition for injection molding, manufacturing method and injection molded product thereof | |
| CN116751462A (en) | High-elasticity TPV degradable material containing coffee grounds and preparation method and application thereof | |
| CN112574539A (en) | High-dispersion high-carbon-black-content black master batch for completely biodegradable garbage bag | |
| CN105440621B (en) | PLA noctilucence master batch and preparation method thereof | |
| CN114921069B (en) | Full-biodegradable film with high heat seal strength and preparation method and application thereof | |
| CN110922725A (en) | Fully biodegradable film composition, fully biodegradable film and preparation method and application thereof | |
| CN114163721B (en) | Polypropylene calcium carbonate master batch and preparation method and application thereof | |
| CN111792876B (en) | SPC stone plastic floor material and floor thereof | |
| CN114045010A (en) | Biodegradable polyester film and preparation method thereof | |
| CN114350129A (en) | Full-bio-based high-degradation composite material and preparation method thereof | |
| CN114702741A (en) | Low-density polyethylene material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210507 |