CN113372698A - Elastomer PLA/TPU3D printing wire and preparation method thereof - Google Patents
Elastomer PLA/TPU3D printing wire and preparation method thereof Download PDFInfo
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- CN113372698A CN113372698A CN202110824475.2A CN202110824475A CN113372698A CN 113372698 A CN113372698 A CN 113372698A CN 202110824475 A CN202110824475 A CN 202110824475A CN 113372698 A CN113372698 A CN 113372698A
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- 238000007639 printing Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920001971 elastomer Polymers 0.000 title claims abstract description 21
- 239000000806 elastomer Substances 0.000 title claims abstract description 21
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 37
- 238000010094 polymer processing Methods 0.000 claims abstract description 36
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 238000010146 3D printing Methods 0.000 claims abstract description 21
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 24
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000005491 wire drawing Methods 0.000 abstract description 11
- 238000009825 accumulation Methods 0.000 abstract description 10
- 239000002861 polymer material Substances 0.000 abstract description 5
- 239000004626 polylactic acid Substances 0.000 description 93
- 229920000747 poly(lactic acid) Polymers 0.000 description 92
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 72
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 72
- 238000012360 testing method Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/10—Pre-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses an elastomer PLA/TPU3D printing wire and a preparation method thereof, and relates to a printing material. The invention aims to provide a 3D printing high polymer material with better toughness. The technical scheme of the invention is as follows: 1. the formula comprises the following components in percentage by weight: 84-98% of PLA, 1-10% of TPU, 1-5% of compatilizer, 0.01-1% of (fluorine) polymer processing aid PPA and 0.1-0.5% of antioxidant. According to the invention, the elastomer compatilizer is used for improving the interfacial adhesion between PLA and TPU, the (fluorine) polymer processing aid PPA is added for improving and even eliminating the wire drawing phenomenon caused by the accumulation of PLA/TPU3D wires at the nozzle of a 3D printer, and the printing wire of the 3D printing product which is rich in elasticity and easy to print is provided.
Description
Technical Field
The invention relates to the technical field of fused extrusion deposition modeling (FDM)3D printing, in particular to an elastomer PLA/TPU3D printing wire and a preparation method thereof.
Background
The 3D printing technology, i.e. additive manufacturing technology, is an emerging rapid prototyping technology. The method is a technology for constructing an object by using a bondable material such as powder metal or plastic and the like in a layer-by-layer printing mode on the basis of a digital model file, does not need to manufacture a die, and saves the time and the cost for manufacturing the die. The basic principle is laminate manufacturing, a technique of adding material layer by layer to create a three-dimensional entity. As a core technology for promoting the third industrial revolution, 3D printing has the characteristics of networking, digitalization, individualization, and the like, and is gradually applied to the fields of medicine, bioengineering, construction, clothing, aviation, and the like.
The fused extrusion deposition modeling (FDM) technique is generally used for printing on a desktop, and because of its simple operation, the materials used are generally available, which is a commonly used technique in the 3D printing technique. The principle is that a thermoplastic polymer material is extruded from a nozzle in a molten state, is solidified to form a thin layer with a profile shape, and is stacked layer by layer to finally form a product. The used materials are mainly environment-friendly high polymer materials, such as: PLA, ABS, PCL, PHA, PBS, etc. to avoid the odor generated by the melted polymer material or the safety problem caused by the contact of harmful substances generated by decomposition with human, among which polylactic acid (PLA) is the most widely used polymer material in FDM technology because of its abundant and renewable raw material sources, biodegradability and biocompatibility. However, since the glass transition temperature of PLA is high, PLA has a hard and brittle nature at room temperature, and is difficult to be applied to joint printing, thereby severely limiting its application in the field of 3D printing.
Thermoplastic polyurethane elastomers (TPU) are flexible and 3D consumable developers are constantly trying to toughen polylactic acid with TPU. J. et al (Preparation and characterization of biodegradable polylactic/thermoplastic polyurethane elastomer blends [ J.]Journal of applied Polymer Science,2011,120 (6): 3217-3223) the following results were found after toughening modification of PLA with TPU: at a TPU content of 30 wt.%, elongation at break and impact strengths of 602% and 40.7kJ/m are obtained2A PLA/TPU blend of (1). Phase morphology observation shows that the two phases of PLA and TPU are only partially compatible, and the melting point of the elastomer TPU is much higher than that of PLA, so that higher temperature is needed to melt the TPU, and the temperature is easy to degrade the PLA partially; in addition, when the PLA/TPU composite material is used for printing a 3D product by adopting a melt extrusion stacking forming technology, the material is easily accumulated at a nozzle, and the 3D printed product is seriously drawn.
The ACR resin is a thermoplastic graft polymer obtained by emulsion polymerization of methyl methacrylate and acrylate monomers, and is a plastic additive with dual functions of impact resistance modification and processing modification. It can not only improve the impact resistance of the product, but also obviously improve the melt fluidity, the thermal deformation, the weather resistance, the luster of the product surface and the like of the resin, and shows excellent comprehensive performance. Carrying out free radical polymerization on ACR resin, glycidyl methacrylate, Lauroyl Peroxide (LPO), an antioxidant and DMF (dimethyl formamide) at a normal-pressure microwave synthesis reaction workstation, and grafting the glycidyl methacrylate on the ACR resin. On one hand, epoxy functional groups carried on the glycidyl methacrylate react with hydroxyl of PLA and hydroxyl of TPU to form covalent bonds, so that the interfacial adhesion of the PLA/TPU is enhanced; on the other hand, the melting point of ACR is low, and the ACR can toughen PLA, reduce the consumption of TPU and lower the melting temperature; the ACR improves the melt fluidity of the PLA and the luster of the surface of the 3D wire rod, and achieves multiple purposes. At present, an elastomer compatilizer is prepared by carrying out free radical polymerization on ACR resin, glycidyl methacrylate, Lauroyl Peroxide (LPO) and an antioxidant through a MAS type normal pressure microwave synthesis reaction workstation, and is applied to the field of PLA/TPU3D wires and has not been reported.
The (fluoro) polymer processing aid PPA is a polymer processing aid from Shanghai Shangri Plastic Ltd. The polymer processing aid is based on high tech fluorochemical compounds. The processing aid can act at a lower addition amount, reduce or eliminate melt fracture, reduce the torque of an extruder, reduce the pressure of a machine head, and reduce die orifice accumulation during extrusion processing. Aiming at the problem that printing and wire drawing are caused by easy material accumulation at the nozzle of a 3D printer in the printing process of a PLA/TPU3D wire for a melt extrusion deposition modeling technology (FDM), the invention applies a (fluorine) polymer processing aid PPA to the 3D wire in the field, and improves or even eliminates the wire drawing problem caused by the material accumulation at the nozzle of the 3D printer by reducing the material accumulation at the nozzle of the 3D printer.
Disclosure of Invention
Based on the above background and problems, it is an object of the present invention to provide an elastomeric PLA/TPU3D printing wire and a method of making the same. According to the invention, ACR, glycidyl methacrylate, Lauroyl Peroxide (LPO), an antioxidant and DMF are adopted to prepare a compatilizer in a MAS type normal pressure microwave synthesis reaction workstation of Shanghai new instrument microwave chemistry Co., Ltd, so that the interfacial adhesion of PLA/TPU is enhanced; the accumulation phenomenon of the PLA/TPU3D printing wire at the nozzle of the 3D printer is reduced by adding the PPA (fluorine) polymer processing aid, so that the problem of wire drawing caused by the accumulation of the nozzle is improved or eliminated.
The purpose of the invention is realized by the following technical scheme:
the invention relates to an elastomer PLA/TPU3D printing wire and a preparation method thereof, which are characterized in that:
(1) the paint consists of the following components in percentage by weight:
PLA 84～98％
TPU 1～10％
1 to 5 percent of compatilizer
0.01-1% of PPA (fluorine) polymer processing aid
0.1 to 0.5 percent of antioxidant
The compatilizer is prepared by free radical polymerization of ACR, glycidyl methacrylate, Lauroyl Peroxide (LPO), an antioxidant and DMF (dimethyl formamide) through a MAS (Multi-agent System) type normal-pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemical technology Limited company;
(2) the preparation method comprises the following steps:
A. a compatilizer preparation stage: according to the formula of the weight percentage, ACR, glycidyl methacrylate, Lauroyl Peroxide (LPO), an antioxidant and DMF are weighed. Placing the weighed components in a reaction kettle prepared by a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd, and keeping the rotating speed of 300-1000 rpm/min, reacting for 120-180 min, and controlling the reaction temperature at 180-200 ℃; and drying the prepared product in a vacuum drying box, and then cutting and granulating.
PLA/TPU blending stage: the PLA and TPU were vacuum dried separately. Weighing the dried PLA, the dried TPU, the dried compatibilizer, the (fluorine) polymer processing aid PPA and the antioxidant according to the weight percentage formula. Placing the weighed components in a high-speed kneader, keeping the rotating speed at 500-6000 rpm/min, and stirring at high speed for 5-60 min.
And C, extruding and granulating PLA/TPU blended particles: adding the uniformly mixed PLA, TPU, compatilizer, (fluoro) polymer processing aid PPA and antioxidant into a feed inlet of a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48: 1, the parameters of the double-screw extruder are as follows: the temperature of the first zone is 145-155 ℃, the temperature of the second zone is 155-165 ℃, the temperature of the third zone is 165-170 ℃, the temperature of the fourth zone is 170-175 ℃, the temperature of the fifth zone is 175-180 ℃, the temperature of the sixth zone is 180-185 ℃, the temperature of the seventh zone is 185-190 ℃, the temperature of the eighth zone is 185-190 ℃, the temperature of a machine head is 175-190 ℃, the rotating speed is 50-350 rpm/min, and PLA/TPU blended particles are obtained after traction and particle cutting;
PLA/TPU3D prints wire preparation stage: adding PLA/TPU blended particles into a single-screw extruder of a 3D wire production line, wherein the extrusion temperature is 145-150 ℃ in a first area, 150-160 ℃ in a second area, 160-170 ℃ in a third area, 170-190 ℃ in a fourth area, 180-190 ℃ at a head, and the rotating speed is 20-200 rpm/min, and cooling PLA/TPU wires extruded by a die orifice of the single-screw extruder through a first water cooling tank and a second water cooling tank respectively to obtain extruded wires;
E. and (3) rolling the water-cooled extruded wire into a bundle by using a wire winder to obtain the PLA/TPU3D printed wire, wherein the frequency of a tractor in the wire winder is 8-35 HZ.
Further, elastomer PLA/TPU3D printing wire, its characterized in that: the compatilizer comprises the following components in percentage by weight:
ACR 90～95.5％
4-8% of glycidyl methacrylate
0.4 to 1% of Lauroyl Peroxide (LPO)
0.1-1% of antioxidant;
DMF 40～50％.
the (fluorine) polymer processing aid PPA is a polymer processing aid FR8250, a polymer processing aid FR8120 and a polymer processing aid FR8170 of Shanghai Shangri plastic Co., Ltd.
The antioxidant is at least one compound selected from phenolic antioxidants 1076 and 1010 or phosphite antioxidants 168.
The elastomer 3D printing wire is applied to the technical field of fused extrusion deposition modeling (FDM)3D printing.
The preparation method of the elastomer 3D printing wire is applied to the technical field of fused extrusion deposition modeling (FDM)3D printing.
The invention has the beneficial effects that: 1. according to the invention, the compatilizer is prepared, and on one hand, epoxy functional groups carried by the compatilizer react with hydroxyl groups of PLA and TPU to form covalent bonds, so that the interfacial adhesion of PLA/TPU is enhanced; on the other hand, the melting point of ACR is low, and PLA can be toughened, so that the using amount of TPU is reduced, and the melting temperature is reduced; the ACR improves the melt fluidity of the PLA and the luster of the surface of the 3D wire rod, and achieves multiple purposes. 2. The (fluorine) polymer processing aid PPA is added to reduce the material accumulation of the PLA/TPU3D printing wire at the nozzle of the 3D printer, and the wire drawing problem caused by the material accumulation of the nozzle is improved or eliminated.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but it should not be construed that the scope of the present invention is limited to the examples.
Example 1
1. The utility model provides an elastomer PLA/TPU3D prints wire rod which characterized in that:
(1) the formula comprises the following components in percentage by weight:
PLA 97.49％
TPU 1％
1 percent of compatilizer
Polymer processing aid FR 82500.01%
1010/1680.5％
The compatilizer is prepared by free radical polymerization of 95.5 percent of ACR, 4 percent of glycidyl methacrylate, 0.4 percent of Lauroyl Peroxide (LPO), 1010/1680.1 percent and 40 percent of DMF through a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd;
(2) the preparation method comprises the following steps:
A. a compatilizer preparation stage: ACR was dried in vacuo. Weighing the dried ACR, the dried glycidyl methacrylate, the dried Lauroyl Peroxide (LPO), the antioxidant and the DMF according to the weight percentage formula. Placing the weighed components in a reaction kettle prepared by a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd, keeping the rotating speed at 300rpm/min, reacting for 180min, and controlling the reaction temperature at 200 ℃; and drying the prepared product in a vacuum drying box, and then cutting and granulating.
PLA/TPU blending stage: the PLA, TPU and compatibilizer are vacuum dried separately. Weighing dry PLA, TPU, compatilizer and polymer processing aids FR8250 and 1010/168 according to the weight percentage formula. Placing the weighed components in a high-speed kneader, keeping the rotating speed at 100rpm/min, and stirring at high speed for 30 min.
And C, extruding and granulating PLA/TPU blended particles: adding uniformly mixed PLA, TPU, compatilizer and (fluoro) polymer processing aids FR8250 and 1010/168 into a feed inlet of a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48: 1, the parameters of the double-screw extruder are as follows: the temperature of the first zone is 145 ℃, the temperature of the second zone is 155 ℃, the temperature of the third zone is 170 ℃, the temperature of the fourth zone is 175 ℃, the temperature of the fifth zone is 180 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 190 ℃, the temperature of the eighth zone is 185 ℃, the temperature of a machine head is 185 ℃, the rotating speed is 180rpm/min, and PLA/TPU blended particles are obtained after traction and grain cutting;
PLA/TPU3D prints wire preparation stage: adding the PLA/TPU blended particles into a single-screw extruder of a 3D wire production line, wherein the extrusion temperature is 145 ℃ in a first area, 160 ℃ in a second area, 170 ℃ in a third area, 190 ℃ in a fourth area, 185 ℃ in a machine head, and the rotating speed is 80rpm/min, and cooling the PLA/TPU wire extruded by a die orifice of the single-screw extruder through a first water cooling tank and a second water cooling tank respectively to obtain an extruded wire;
E. and (3) rolling the water-cooled extruded wire into a bundle by using a wire winder to obtain the PLA/TPU3D printing wire, wherein the frequency of a tractor in the wire winder is 15 HZ.
F. And D, performing 3D printing test on the 1.75 +/-0.05 mm extruded wire obtained in the step D, wherein the printing temperature is 190 ℃, observing the smoothness degree of the printing process, judging whether materials are accumulated at the nozzle of the 3D printer or not, judging whether a wire drawing phenomenon exists or not, and printing the appearance of a product (the surface is smooth and uniform, the appearance is attractive or not, and the dimensional stability) and observing results are shown in Table 1.
G. And D, performing injection molding on the PLA/TPU blended particles obtained in the step C, and performing a tensile property test (GB/T1040.2-2006), a bending strength test (GB/T1446-2006) and an impact property test (GB/T1943-2008) on injection molding splines respectively, wherein the test results are shown in Table 1.
Example 2
1. The utility model provides an elastomer PLA/TPU3D prints wire rod which characterized in that:
(1) the formula comprises the following components in percentage by weight:
PLA 91.49％
TPU 5％
compatilizer 3%
Polymer processing aid FR 82500.01%
1010/1680.5％
The compatilizer is prepared by free radical polymerization of 94.5 percent of ACR, 5 percent of glycidyl methacrylate, 0.4 percent of Lauroyl Peroxide (LPO), 1010/1680.1 percent of DMF40 percent of methyl methacrylate (ACR), and MAS type normal pressure microwave synthesis reaction workstation of Shanghai new instrument microwave chemistry Co., Ltd;
(2) the preparation method comprises the following steps:
A. a compatilizer preparation stage: ACR was dried in vacuo. Weighing the dried ACR, the dried glycidyl methacrylate, the dried Lauroyl Peroxide (LPO), the antioxidant and the DMF according to the weight percentage formula. Placing the weighed components in a reaction kettle prepared by a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd, keeping the rotating speed at 300rpm/min, reacting for 180min, and controlling the reaction temperature at 200 ℃; and drying the prepared product in a vacuum drying box, and then cutting and granulating.
PLA/TPU blending stage: the PLA, TPU and compatibilizer are vacuum dried separately. Weighing dry PLA, TPU, compatilizer and polymer processing aids FR8250 and 1010/168 according to the weight percentage formula. Placing the weighed components in a high-speed kneader, keeping the rotating speed at 100rpm/min, and stirring at high speed for 30 min.
And C, extruding and granulating PLA/TPU blended particles: adding uniformly mixed PLA, TPU, compatilizer and (fluoro) polymer processing aids FR8250 and 1010/168 into a feed inlet of a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48: 1, the parameters of the double-screw extruder are as follows: the temperature of the first zone is 145 ℃, the temperature of the second zone is 155 ℃, the temperature of the third zone is 170 ℃, the temperature of the fourth zone is 175 ℃, the temperature of the fifth zone is 180 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 190 ℃, the temperature of the eighth zone is 185 ℃, the temperature of a machine head is 185 ℃, the rotating speed is 180rpm/min, and PLA/TPU blended particles are obtained after traction and grain cutting;
PLA/TPU3D prints wire preparation stage: adding the PLA/TPU blended particles into a single-screw extruder of a 3D wire production line, wherein the extrusion temperature is 145 ℃ in a first area, 160 ℃ in a second area, 170 ℃ in a third area, 190 ℃ in a fourth area, 185 ℃ in a machine head, and the rotating speed is 80rpm/min, and cooling the PLA/TPU wire extruded by a die orifice of the single-screw extruder through a first water cooling tank and a second water cooling tank respectively to obtain an extruded wire;
E. and (3) rolling the water-cooled extruded wire into a bundle by using a wire winder to obtain the PLA/TPU3D printing wire, wherein the frequency of a tractor in the wire winder is 15 HZ.
F. And D, performing 3D printing test on the 1.75 +/-0.05 mm extruded wire obtained in the step D, wherein the printing temperature is 190 ℃, observing the smoothness degree of the printing process, judging whether materials are accumulated at the nozzle of the 3D printer or not, judging whether a wire drawing phenomenon exists or not, and printing the appearance of a product (the surface is smooth and uniform, the appearance is attractive or not, and the dimensional stability) and observing results are shown in Table 1.
G. And D, performing injection molding on the PLA/TPU blended particles obtained in the step C, and performing a tensile property test (GB/T1040.2-2006), a bending strength test (GB/T1446-2006) and an impact property test (GB/T1943-2008) on injection molding splines respectively, wherein the test results are shown in Table 1.
Example 3
1. The utility model provides an elastomer PLA/TPU3D prints wire rod which characterized in that:
(1) the formula comprises the following components in percentage by weight:
PLA 84.4％
TPU 10％
5 percent of compatilizer
Polymer processing aid FR 82500.1%
1010/1680.5％
The compatilizer is prepared by free radical polymerization of 91.3 percent of ACR, 8 percent of glycidyl methacrylate, 0.6 percent of Lauroyl Peroxide (LPO), 1010/1680.1 percent and 40 percent of DMF through a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd;
(2) the preparation method comprises the following steps:
A. preparation of the compatilizer: ACR was dried in vacuo. Weighing the dried ACR, the dried glycidyl methacrylate, the dried Lauroyl Peroxide (LPO), the antioxidant and the DMF according to the weight percentage formula. Placing the weighed components in a reaction kettle prepared by a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd, keeping the rotating speed at 1000rpm/min, reacting for 180min, and controlling the reaction temperature at 200 ℃; and drying the prepared product in a vacuum drying box, and then cutting and granulating.
PLA/TPU blending stage: the PLA, TPU and compatibilizer are vacuum dried separately. Weighing dry PLA, TPU, compatilizer and polymer processing aids FR8250 and 1010/168 according to the weight percentage formula. Placing the weighed components in a high-speed kneader, keeping the rotating speed at 100rpm/min, and stirring at high speed for 30 min.
And C, extruding and granulating PLA/TPU blended particles: adding uniformly mixed PLA, TPU, compatilizer and (fluoro) polymer processing aids FR8250 and 1010/168 into a feed inlet of a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48: 1, the parameters of the double-screw extruder are as follows: the temperature of the first zone is 145 ℃, the temperature of the second zone is 155 ℃, the temperature of the third zone is 170 ℃, the temperature of the fourth zone is 175 ℃, the temperature of the fifth zone is 180 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 190 ℃, the temperature of the eighth zone is 185 ℃, the temperature of a machine head is 185 ℃, the rotating speed is 180rpm/min, and PLA/TPU blended particles are obtained after traction and grain cutting;
PLA/TPU3D prints wire preparation stage: adding the PLA/TPU blended particles into a single-screw extruder of a 3D wire production line, wherein the extrusion temperature is 145 ℃ in a first area, 160 ℃ in a second area, 170 ℃ in a third area, 190 ℃ in a fourth area, 185 ℃ in a machine head, and the rotating speed is 80rpm/min, and cooling the PLA/TPU wire extruded by a die orifice of the single-screw extruder through a first water cooling tank and a second water cooling tank respectively to obtain an extruded wire;
E. and (3) rolling the water-cooled extruded wire into a bundle by using a wire winder to obtain the PLA/TPU3D printing wire, wherein the frequency of a tractor in the wire winder is 15 HZ.
F. And D, performing 3D printing test on the 1.75 +/-0.05 mm extruded wire obtained in the step D, wherein the printing temperature is 190 ℃, observing the smoothness degree of the printing process, judging whether materials are accumulated at the nozzle of the 3D printer or not, judging whether a wire drawing phenomenon exists or not, and printing the appearance of a product (the surface is smooth and uniform, the appearance is attractive or not, and the dimensional stability) and observing results are shown in Table 1.
G. And D, performing injection molding on the PLA/TPU blended particles obtained in the step C, and performing a tensile property test (GB/T1040.2-2006), a bending strength test (GB/T1446-2006) and an impact property test (GB/T1943-2008) on injection molding splines respectively, wherein the test results are shown in Table 1.
Example 4
1. The utility model provides an elastomer PLA/TPU3D prints wire rod which characterized in that:
(1) the formula comprises the following components in percentage by weight:
PLA 84％
TPU 10％
5 percent of compatilizer
Polymer processing aid FR 82500.5%
1010/1680.5％
The compatilizer is prepared by free radical polymerization of 91.3 percent of ACR, 8 percent of glycidyl methacrylate, 0.6 percent of Lauroyl Peroxide (LPO), 1010/1680.1 percent and 50 percent of DMF through a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd;
(2) the preparation method comprises the following steps:
A. a compatilizer preparation stage: ACR was dried in vacuo. Weighing the dried ACR, the dried glycidyl methacrylate, the dried Lauroyl Peroxide (LPO), the antioxidant and the DMF according to the weight percentage formula. Placing the weighed components in a reaction kettle prepared by a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd, keeping the rotating speed at 1000rpm/min, reacting for 180min, and controlling the reaction temperature at 200 ℃; and drying the prepared product in a vacuum drying box, and then cutting and granulating.
PLA/TPU blending stage: the PLA, TPU and compatibilizer are vacuum dried separately. Weighing dry PLA, TPU, compatilizer and polymer processing aids FR8250 and 1010/168 according to the weight percentage formula. Placing the weighed components in a high-speed kneader, keeping the rotating speed at 100rpm/min, and stirring at high speed for 30 min.
And C, extruding and granulating PLA/TPU blended particles: adding uniformly mixed PLA, TPU, compatilizer and (fluoro) polymer processing aids FR8250 and 1010/168 into a feed inlet of a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48: 1, the parameters of the double-screw extruder are as follows: the temperature of the first zone is 145 ℃, the temperature of the second zone is 155 ℃, the temperature of the third zone is 170 ℃, the temperature of the fourth zone is 175 ℃, the temperature of the fifth zone is 180 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 190 ℃, the temperature of the eighth zone is 185 ℃, the temperature of a machine head is 185 ℃, the rotating speed is 180rpm/min, and PLA/TPU blended particles are obtained after traction and grain cutting;
PLA/TPU3D prints wire preparation stage: adding the PLA/TPU blended particles into a single-screw extruder of a 3D wire production line, wherein the extrusion temperature is 145 ℃ in a first area, 160 ℃ in a second area, 170 ℃ in a third area, 190 ℃ in a fourth area, 185 ℃ in a machine head, and the rotating speed is 80rpm/min, and cooling the PLA/TPU wire extruded by a die orifice of the single-screw extruder through a first water cooling tank and a second water cooling tank respectively to obtain an extruded wire;
E. and (3) rolling the water-cooled extruded wire into a bundle by using a wire winder to obtain the PLA/TPU3D printing wire, wherein the frequency of a tractor in the wire winder is 15 HZ.
F. And D, performing 3D printing test on the 1.75 +/-0.05 mm extruded wire obtained in the step D, wherein the printing temperature is 190 ℃, observing the smoothness degree of the printing process, judging whether materials are accumulated at the nozzle of the 3D printer or not, judging whether a wire drawing phenomenon exists or not, and printing the appearance of a product (the surface is smooth and uniform, the appearance is attractive or not, and the dimensional stability) and observing results are shown in Table 1.
G. And D, performing injection molding on the PLA/TPU blended particles obtained in the step C, and performing a tensile property test (GB/T1040.2-2006), a bending strength test (GB/T1446-2006) and an impact property test (GB/T1943-2008) on injection molding splines respectively, wherein the test results are shown in Table 1.
Comparative example 1
(1) The formula comprises the following components in percentage by weight:
PLA 88.5％
TPU 10％
1010/1680.5％
(2) the preparation method comprises the following steps: the preparation is as in example 3, except for the proportions of the components.
Comparative example 2
(1) The formula comprises the following components in percentage by weight:
PLA 89.4％
TPU 10％
polymer processing aid FR 82500.1%
1010/1680.5％
(2) The preparation method comprises the following steps: the preparation was as in example 3, except for the component proportions.
Comparative example 3
(1) The formula comprises the following components in percentage by weight:
PLA 84.5％
TPU 10％
5 percent of compatilizer
1010/1680.5％
(2) The preparation method comprises the following steps: the preparation was as in example 3, except for the component proportions.
TABLE 1 results of elastomer PLA/TPU material performance testing
Examples 1-4 it can be seen that the prepared elastomer PLA/TPU3D printing wire is applied in the field of fused extrusion deposition modeling (FDM)3D printing technology, and has good mechanical properties, smooth printing process, no wire drawing, smooth and uniform product surface, beautiful appearance, and stable size. Compared with the comparative examples 1 and 3, the self-made compatilizer is added in the example 3, so that the PLA/TPU interface bonding force is effectively enhanced, and the mechanical property is integrally improved; example 3 compared with comparative example 1 and comparative example 2, the addition of the (fluoro) polymer processing aid PPA can effectively improve or eliminate the wire drawing phenomenon caused by easy material accumulation of a nozzle in the 3D printing process of a PLA/TPU3D wire, and the surface of a 3D printed product is smooth and uniform.
Claims (6)
1. An elastomeric PLA/TPU3D printing wire, characterized by:
(1) the paint consists of the following components in percentage by weight:
PLA 84～98％
TPU 1～10％
1 to 5 percent of compatilizer
0.01-1% of PPA (fluorine) polymer processing aid
0.1 to 0.5 percent of antioxidant
The compatilizer is prepared by free radical polymerization of ACR, glycidyl methacrylate, Lauroyl Peroxide (LPO), an antioxidant and DMF (dimethyl formamide) through a MAS (Multi-agent System) type normal-pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemical technology Limited company;
(2) the preparation method comprises the following steps:
A. a compatilizer preparation stage: according to the formula of the weight percentage, ACR, glycidyl methacrylate, Lauroyl Peroxide (LPO), an antioxidant and DMF are weighed. Placing the weighed components in a reaction kettle prepared by a MAS type normal pressure microwave synthesis reaction workstation of Shanghai New Instrument microwave chemistry Co., Ltd, and keeping the rotating speed of 300-1000 rpm/min, reacting for 120-180 min, and controlling the reaction temperature at 180-200 ℃; and drying the prepared product in a vacuum drying box, and then cutting and granulating.
PLA/TPU blending stage: the PLA and TPU were vacuum dried separately. Weighing the dried PLA, the dried TPU, the dried compatibilizer, the (fluorine) polymer processing aid PPA and the antioxidant according to the weight percentage formula. Placing the weighed components in a high-speed kneader, keeping the rotating speed at 500-6000 rpm/min, and stirring at high speed for 5-60 min.
And C, extruding and granulating PLA/TPU blended particles: adding the uniformly mixed PLA, TPU, compatilizer, (fluoro) polymer processing aid PPA and antioxidant into a feed inlet of a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48: 1, the parameters of the double-screw extruder are as follows: the temperature of the first zone is 145-155 ℃, the temperature of the second zone is 155-165 ℃, the temperature of the third zone is 165-170 ℃, the temperature of the fourth zone is 170-175 ℃, the temperature of the fifth zone is 175-180 ℃, the temperature of the sixth zone is 180-185 ℃, the temperature of the seventh zone is 185-190 ℃, the temperature of the eighth zone is 185-190 ℃, the temperature of a machine head is 175-190 ℃, the rotating speed is 50-350 rpm/min, and PLA/TPU blended particles are obtained after traction and particle cutting;
PLA/TPU3D printing wire preparation stage: adding PLA/TPU blended particles into a single-screw extruder of a 3D wire production line, wherein the extrusion temperature is 145-150 ℃ in a first area, 150-160 ℃ in a second area, 160-170 ℃ in a third area, 170-190 ℃ in a fourth area, 180-190 ℃ at a head, and the rotating speed is 20-200 rpm/min, and cooling PLA/TPU wires extruded by a die orifice of the single-screw extruder through a first water cooling tank and a second water cooling tank respectively to obtain extruded wires;
E. and (3) rolling the water-cooled extruded wire into a bundle by using a wire winder to obtain a PLA/TPU3D printed wire, wherein the frequency of a tractor in the wire winder is 8-35 HZ.
2. An elastomeric PLA/TPU3D printing wire according to claim 1, wherein: the compatilizer comprises the following components in percentage by weight:
ACR 90～95.5％
4-8% of glycidyl methacrylate
0.4 to 1% of Lauroyl Peroxide (LPO)
0.1 to 1 percent of antioxidant
DMF 40～50％。
3. An elastomeric PLA/TPU3D printing wire according to claim 1, wherein: the (fluorine) polymer processing aid PPA is a polymer processing aid FR8250, a polymer processing aid FR8120 and a polymer processing aid FR8170 of Shanghai Shangri plastic Co., Ltd.
4. An elastomeric PLA/TPU3D printing wire according to claim 1, wherein: the antioxidant is at least one compound selected from phenolic antioxidants 1076 and 1010 or phosphite antioxidants 168.
5. Use of an elastomeric PLA/TPU3D printing wire according to any one of claims 1-4, characterized in that: the elastomer 3D printing wire is applied to the technical field of fused extrusion deposition modeling (FDM)3D printing.
6. Use of a preparation process in an elastomeric PLA/TPU3D printing wire according to any one of claims 1-4, characterized in that: the preparation method of the elastomer 3D printing wire is applied to the technical field of fused extrusion deposition modeling (FDM)3D printing.
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