CN112159588A - Low-warpage 3D printing PA/PPO alloy consumable and preparation method thereof - Google Patents
Low-warpage 3D printing PA/PPO alloy consumable and preparation method thereof Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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 a low-warpage 3D printing PA/PPO alloy consumable and a preparation method thereof. According to the invention, based on the research and development of 3D printing consumables, the materials are mixed by a double-screw extruder, and the materials are drawn by a single-screw extruder to prepare the low-warpage 3D printing PA/PPO alloy consumable. The feed comprises the following raw materials in parts by weight: 50-80 parts of PA resin; 20-30 parts of PPO resin; 0-5 parts of a toughening agent; 0-5 parts of a compatilizer; 0.1-1 part of antioxidant; 0-1 part of lubricant. According to the invention, PPO is used as a modifier, nylon is used as a base material, a compatilizer, a flexibilizer, an antioxidant, a lubricant and the like are used for modifying nylon resin, and the low-warpage 3D printing PA/PPO alloy consumable material is prepared by adjusting the synergistic effect of the components in different proportions, and has the advantages of high strength, low shrinkage rate, low warpage, high molding precision, easiness in removing support and the like.
Description
Technical Field
The invention relates to the field of 3D printing high polymer materials, in particular to a low-warpage 3D printing PA/PPO alloy consumable and a preparation method thereof.
Background
One of the rapid prototyping techniques, 3D printing technology, is a technique for building objects by layer-by-layer printing based on a digital model file, also commonly referred to as additive manufacturing. 3D prints and develops to this day, has appeared a great variety of forming technique, including: fused Deposition Modeling (FDM), photocuring modeling (SLA), three-dimensional printing rapid prototyping (3DP), selective laser sintering modeling (SLS), laser cladding modeling (LMD), electron beam melting modeling (EBM), polymer jet modeling (polyjet), and the like.
FDM is the simplest and most common 3D printing technology, typically used in desktop level printing devices. A 3D printer using FDM technology builds parts layer by heating thermoplastic material to a semi-liquid state and extruding along a computer controlled path.
The material technology is one of the cores of the 3D printing technology, the development process of the 3D printing is directly restricted to a certain extent, and the development process of the 3D printing technology shows that a new printing technology appears and the inherent characteristics of the material are required. Due to the fact that the materials are different in physical form, chemical performance and the like, diversification of 3D printing materials and 3D printing forming modes is formed. Common printing materials are polylactic acid (PLA), Acrylonitrile Butadiene Styrene (ABS), Polycarbonate (PC), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), etc., but this type of material is difficult to use in engineering.
The molecular structure of polyphenylene oxide (PPO) determines that the PPO has good thermodynamic performance, the PPO can continuously work in the range of-160-190 ℃, and the creep resistance at high temperature is excellent in thermoplastic engineering plastics. PPO can maintain good mechanical property, electrical property, heat resistance, flame retardance, chemical stability and the like within a wide temperature range. However, pure PPO has the fatal defects of high melt viscosity and poor molding processability, which influences the popularization and application of PPO. More than 90% of the industrially applied PPO is modified PPO.
Polyamide (PA) is an engineering plastic with excellent performance, and has the advantages of good solvent resistance, high mechanical strength, easy processing and the like due to high crystallinity. However, the nylon has a high melting temperature, but a low thermal deformation temperature compared with other high polymer materials, so that most of nylon has a low viscosity after melting, and the requirement of the FDM process cannot be met.
The PPO has the characteristics of low shrinkage rate, low water absorption and high-temperature viscosity, and the common manufacturing process usually selects and blends the PPO and other polymers to prepare the PPO alloy and endow the alloy with new performance, so that the problems of low high-temperature viscosity, high water absorption, easy warping in 3D printing and the like can be solved by selecting and blending the PPO and nylon to research and develop the FDM 3D printing material. The invention discloses a low-warpage 3D printing PA/PPO alloy consumable and a preparation method thereof.
Disclosure of Invention
The invention aims to prepare a novel 3D printing wire by using PPO as a modifier and nylon as a base material. The PPO has the advantages that the PPO has good comprehensive properties of small water absorption, small molding shrinkage, flame retardancy, self-extinguishing property and the like, and the defects of high water absorption, low high-temperature viscosity, overlarge molding shrinkage, easiness in warping and the like of PA are overcome through compatibilization, so that the PPO meets the requirements of 3D printing better. The printed product has excellent printing effect, stable printing process and small printing warping rate.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a low-warpage 3D printing PA/PPO alloy consumable material comprises the following components in parts by mass:
50-80 parts of PA resin;
20-30 parts of PPO resin;
0-5 parts of a toughening agent;
0-5 parts of a compatilizer;
0.1-1 part of antioxidant;
0-1 part of a lubricant;
preferably, in the low warpage 3D printing PA/PPO alloy consumable described above, the PA resin density: 1.14 +/-0.03 g/cm3The tensile strength is more than or equal to 120MPa, the elongation is more than or equal to 40 percent, the bending strength is more than or equal to 150MPa, the bending modulus is more than or equal to 2000MPa, and the notch impact strength is more than or equal to 6KJ/m2。
Preferably, in the low warpage 3D printing PA/PPO alloy consumable material described above, the PA resin is selected from one or a combination of several of PA6, PA66, PA46, PA6T and PA 9T.
Preferably, in the low-warpage 3D printing PA/PPO alloy consumable material, the PPO resin has the intrinsic viscosity of 35-50dl/g and the melt index of 10-25g/10min (260 ℃/5 Kg).
Preferably, in the low warpage 3D printing PA/PPO alloy consumable described above, the PPO resin is selected from the group consisting of the bluestar LXR035, LXR040 or LXR 045.
Preferably, in the low warpage 3D printing PA/PPO alloy consumable material, the toughening agent is at least one of POE, grafted POE, EPDM, PBE, SEBS, SBS, SIS, SEPS, SOE, ABS high rubber powder, ASA high rubber powder, MBS, ACR, EMA, silicone rubber, ethylene-methyl acrylate-glycidyl methacrylate random copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic anhydride and acrylate difunctional ethylene elastomer, EVA, PU, TPO, TPE, TPV, TPU, TPEE, TPR.
Preferably, in the low warpage 3D printing PA/PPO alloy consumable material, the compatilizer is at least one of an aluminate coupling agent, a silane coupling agent, a titanate coupling agent and a maleic anhydride graft.
Preferably, in the low warpage 3D printing PA/PPO alloy consumable material, the antioxidant is at least one of sulfate, hindered amine, phosphite and hindered phenol.
Preferably, in the low warpage 3D printing PA/PPO alloy consumable material, the lubricant is at least one of waxes, silicones, amides, stearic acid.
The preparation method of the 3D printing consumable comprises the following steps:
(1) weighing the raw materials of each component according to the proportion, and uniformly mixing the raw materials by using a mixer;
(2) putting the mixed materials into a double-screw extruder to be extruded into strips, and preparing PA/PPO alloy consumable material granules through cooling, air drying and grain cutting;
(3) and putting the cut granules into a single-screw extruder of the 3D printing consumables to be extruded into wires, cooling the wires by a water tank, drying the wires by a fan, pulling a brace, and winding the wires into a disc by a winding machine to prepare the low-warpage 3D printing PA/PPO alloy consumables.
Compared with the prior art, the invention has the following beneficial effects: the high-low warpage 3D printing PA/PPO alloy consumable prepared by the invention has the advantages of simple manufacturing process and no waste of raw materials, not only reduces the cost, but also improves the stability of wire diameter control and the stability of the printing process, and can also effectively prevent the warpage phenomenon in the printing process.
Drawings
FIG. 1 shows a comparison of the printing patterns of comparative example 1 and example 2.
Detailed Description
Printing warping degree test: the pyramidal model was printed and tested for warpage at a print area of 100mm x 100mm, where warpage is warpage height x 100%/side length.
The parts by weight hereinafter may refer to unit amounts conventional in the art, such as kilograms, grams, and the like, and may also refer to ratios between the components, such as mass or weight ratios, and the like.
The low-warpage 3D printing PA/PPO alloy consumable, the preparation method and the preparation process thereof are explained in detail in the following by combining with specific preferred embodiments. The low-warpage 3D printing PA/PPO alloy consumable material and the components contained in the preparation method thereof in the following embodiments are selected from the types and content ranges of the low-warpage 3D printing PA/PPO alloy consumable material and the preparation method thereof.
Example 1:
(1) the experimental materials are prepared according to the following component ratio: PA6 resin: 60 parts; PPO resin LXR 045: 30 parts of (1); the toughening agent POE: 5 parts of a mixture; compatilizer PPO-g-MAH: 5 parts of a mixture; antioxidant 1010: 0.1 part; lubricant TAS-2A: 0.2 part.
(2) Drying the weighed raw materials, and mixing for 10min by a high-speed running stirrer to obtain the experimental raw materials with uniform components.
(3) Extruding the obtained raw materials by a double-screw high-temperature melting extruder, setting the temperature of a machine temperature zone to be 290 ℃, drawing the experimental materials into strips, cooling with cold water, air-drying by a blower, and cutting the granules by a granulator to obtain uniform and full granules.
(4) And melting and extruding the obtained granules in a 3D printing single-screw consumable extruder, wherein the temperature of 6 sections of temperature zones is 290 ℃, 285 ℃, 280 ℃, 285 ℃ and 290 ℃.
(5) The material strips which are extruded, mixed and melted by the machine head are cooled by a cold water tank, wherein the temperature of cooling water is set to be 55 ℃.
(6) And (3) the cooled and solidified material wire is subjected to the processes of traction, diameter measurement and wire storage, and the diameter of the wire is adjusted through the rotating speed of the screw and the running speed of the traction machine, wherein the diameter of the wire is 1.75 +/-0.05 mm. The screw speed was 90rpm and the tractor speed was 120 rpm.
(7) And winding the consumables with qualified wire diameter into a disc, wherein the winding length is 220m, and the weight of each disc of wire is 1 kg.
(8) And carrying out vacuum packaging on the wound consumable material by using a vacuum packaging machine to obtain the consumable material.
Example 2:
(1) the experimental materials are prepared according to the following component ratio: PA66 resin: 65 parts of (1); PPO resin LXR 035: 25 parts of (1); toughening agent SEBS: 4 parts of a mixture; compatilizer PPO-g-MAH: 6 parts of (1); antioxidants 1010, 168: 0.2 and 0.1 part; lubricant TAS-2A: 0.1 part. Drying the high molecular raw materials, and uniformly mixing the high molecular raw materials by a stirrer.
(2) Drying the high molecular raw materials, uniformly mixing the high molecular raw materials by a stirrer, putting the mixture into a double-screw extruder for extrusion, setting the heating area at 280-300 ℃, extruding the mixture at the temperature, cooling the mixture by cooling water, air-drying the mixture by a fan, and granulating the mixture by a machine to prepare PA/PPO alloy granules.
(3) And melting and extruding the obtained granules in a 3D printing single-screw consumable extruder, wherein the temperature of 6 sections of temperature zones is 280 ℃, 285 ℃ and 280 ℃.
(4) Cooling the extruded strand, drawing, measuring the diameter and storing the strand, setting the rotation speed of a screw at 120rpm, setting the rotation speed of a drawing machine at 160rpm, and controlling the diameter of the strand within the range of 1.75 +/-0.05 mm.
(5) And (3) winding the consumables with qualified wire diameter into a disc, wherein the winding length is 222m, and the weight of each disc of wire is 1 kg.
(6) And carrying out vacuum packaging on the wound consumable material by using a vacuum packaging machine to obtain the consumable material.
Example 3:
(1) the experimental materials are prepared according to the following component ratio: PA9T resin: 70 parts of (B); PPO resin LXR 040: 15 parts of (1); the toughening agent POE: 9 parts of (1); compatilizer PPO-g-MAH: 6 parts of (1); antioxidants 627, 317: 0.1 and 0.2 part; lubricant EBS: 0.2 part.
(2) And (3) mixing the weighed raw materials at a high speed for 10min to obtain the experimental raw materials with uniform components.
(3) Extruding the obtained raw materials by a double-screw high-temperature melting extruder, setting the temperature of a machine temperature zone to be 270-300 ℃, drawing the experimental materials into strips, cooling with cold water, air-drying by a blower, and granulating by the machine to obtain uniform and full granules.
(4) And melting and extruding the obtained granules in a 3D printing single-screw consumable extruder, wherein the temperature of 6 sections of temperature zones is 280 ℃, 285 ℃, 290 ℃, 285 ℃ and 280 ℃. (5) The material strips which are extruded, mixed and melted by the machine head are cooled by a cold water tank, wherein the temperature of cooling water is set to be 50 ℃.
(6) And (3) the cooled and solidified material wire is subjected to the processes of traction, diameter measurement and wire storage, the diameter of the wire is adjusted through the rotating speed of the screw and the running speed of the traction machine, and the diameter range of the wire is 1.75 +/-0.05 mm. The screw speed was 90rpm and the tractor speed was 120 rpm.
(7) And (3) winding the consumables with qualified wire diameter into a disc, wherein the winding length is 222m, and the weight of each disc of wire is 1 kg.
(8) And carrying out vacuum packaging on the wound consumable material by using a vacuum packaging machine to obtain the consumable material.
Comparative example 1:
(1) in example 2, the PPO resin was removed.
Comparative example 2:
(2) in example 2, the compatibilizer PPO-g-MAH was removed.
And (4) relevant performance test:
the processing characteristics and product properties provided by the above examples 1-3 and comparative examples 1, 2 are shown in table 1.
The low-warpage 3D printing PA/PPO alloy consumable material, the preparation method and the preparation process provided by the embodiment of the invention are described in detail above. The principle and embodiments of the present invention are explained herein by using specific embodiments, the description of the embodiments is only for the purpose of facilitating understanding of the method and the core concept of the present invention, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
TABLE 1, examples and comparative examples comparison
The following conclusions are drawn from the test data of table 1: compared with the embodiment 2, the modification of the PPO material is not carried out in the comparative example 1, the problems occur in the 3D printing process, the layer-to-layer adhesion is poor, the warping phenomenon occurs, the warping degree is high, and the quality of the 3D printed product is affected. In comparative example 2, compared with example 2, the prepared material without the addition of the compatibilizer has poor interface mixing of two components, mutual fusion cannot be realized, so that the 3D printing warping phenomenon is not completely solved, and the 3D printing effect is poor.
From fig. 1 it can be concluded that the left PA print is poorly 3D printed, that the bottom is not in a horizontal plane, and that warping occurs. The right PA/PPO printing piece has a smooth printing surface, no warping phenomenon and good printing effect due to the addition of the PPO modified material.
TABLE 2 test performance of examples
The standard sample pieces used for testing are printed and formed by the consumable material prepared by the invention through a 3D printer, and then testing is carried out.
As can be seen from the average values of the properties of the materials prepared in the above examples 1-3 in Table 2, the low warpage 3D printing PA/PPO alloy consumable material of the present invention has excellent mechanical properties and processability.
Claims (10)
1. A low-warpage 3D printing PA/PPO alloy consumable is characterized by comprising the following components in parts by weight:
50-80 parts of PA resin;
20-30 parts of PPO resin;
0-5 parts of a toughening agent;
0-5 parts of a compatilizer;
0.1-1 part of antioxidant;
0-1 part of lubricant.
2. A low warpage 3D printing PA/PPO alloy consumable of claim 1, characterized in that: density of the PA resin: 1.14 +/-0.03 g/cm3The tensile strength is more than or equal to 120MPa, the elongation is more than or equal to 40 percent, the bending strength is more than or equal to 150MPa, the bending modulus is more than or equal to 2000MPa, and the notch impact strength is more than or equal to 6KJ/m2。
3. A low warpage 3D printing PA/PPO alloy consumable of claim 1, characterized in that: the PA resin is selected from one or a combination of several of PA6, PA66, PA46, PA6T and PA 9T.
4. A low warpage 3D printing PA/PPO alloy consumable of claim 1, characterized in that: the PPO resin is selected from Lanxingxi LXR035, LXR040 or LXR 045; the PPO resin has the intrinsic viscosity of 35-50dl/g, the melt index of 10-25g/10min and the temperature of 260 ℃/5 Kg.
5. A low warpage 3D printing PA/PPO alloy consumable of claim 1, characterized in that: the toughening agent is selected from at least one of POE, grafted POE, EPDM, PBE, SEBS, SBS, SIS, SEPS, SOE, ABS high rubber powder, ASA high rubber powder, MBS, ACR, EMA, silicon rubber, ethylene-methyl acrylate-glycidyl methacrylate random copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic anhydride and acrylate difunctional ethylene elastomer, EVA, PU, TPO, TPE, TPV, TPU, TPEE and TPR.
6. A low warpage 3D printing PA/PPO alloy consumable of claim 1, characterized in that: the compatilizer is at least one of aluminate coupling agent, silane coupling agent, titanate coupling agent and maleic anhydride graft.
7. A low warpage 3D printing PA/PPO alloy consumable of claim 1, characterized in that: the antioxidant is at least one of sulfate, hindered amine, phosphite and hindered phenol.
8. A low warpage 3D printing PA/PPO alloy consumable of claim, characterized in that: the lubricant is at least one of wax, silicone, amide and stearic acid.
9. A method of preparing a low warpage 3D printed PA/PPO alloy consumable material as claimed in any one of claims 1 to 8, wherein: the method comprises the following steps:
(1) drying the PA resin and the PPO resin;
(2) adding a compatilizer, an antioxidant, a lubricant and a toughening agent into the PA resin and the PPO resin, uniformly mixing, melting and blending in a double-screw extruder, extruding, and granulating to obtain granules;
(3) drying the granulated granules;
(4) and adding the dried granules into a single-screw extruder for melt extrusion, and performing wire drawing molding to obtain the low-warpage 3D printing PA/PPO alloy consumable.
10. The preparation method of the low-warpage 3D printing PA/PPO alloy consumable material according to claim 9, characterized in that: in the step (1) and the step (3), the drying temperature is 100 ℃, and the drying time is 3-5 h; in the step (2), the processing temperature of the double-screw extruder is 280-300 ℃; in the step (4), the single-screw extrusion temperature parameters are as follows: 280 ℃ and 300 ℃; the diameter of the PA/PPO alloy wire is controlled to be 1.75 +/-0.05 mm.
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