CN114479339B - ABS alloy material and preparation method and application thereof - Google Patents
ABS alloy material and preparation method and application thereof Download PDFInfo
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- CN114479339B CN114479339B CN202210062938.0A CN202210062938A CN114479339B CN 114479339 B CN114479339 B CN 114479339B CN 202210062938 A CN202210062938 A CN 202210062938A CN 114479339 B CN114479339 B CN 114479339B
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- 239000000956 alloy Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 79
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims abstract description 22
- 238000010146 3D printing Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000007639 printing Methods 0.000 abstract description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 46
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 45
- 239000005038 ethylene vinyl acetate Substances 0.000 description 33
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920013683 Celanese Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000612182 Rexea solandri Species 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses an ABS alloy material and a preparation method and application thereof. The ABS alloy material comprises the following components in parts by weight: 50-70 parts of ABS resin, 15-45 parts of EVA resin, 5-15 parts of SMMA resin and 0-0.8 part of auxiliary agent. The ABS alloy material has higher toughness and glossiness, has higher melt flow rate at low temperature, such as 170-180 ℃, and is suitable for low-temperature printing, such as consumable used as a child 3D printing pen.
Description
Technical Field
The invention belongs to the field of plastics, and relates to an ABS alloy material, a preparation method and application thereof.
Background
The 3D printing technology is a special manufacturing technology which is raised in the later 80 s of the 20 th century, and mainly comprises Fused Deposition Modeling (FDM), photocuring modeling (SLA), selective laser sintering modeling (SLS), layered entity manufacturing (LOM) and other types of technologies. The FDM technology has the advantages of no need of a die, multiple optional materials, flexible manufacturing method, low cost and the like, and is the most widely applied 3D printing technology at present. In the aspect of FDM3D printing materials, more commonly used thermoplastic materials such as polylactic acid (PLA), acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC) and the like are adopted, wherein the ABS material is the most widely applied FDM3D printing thermoplastic material due to good formability and mechanical properties and low price.
However, the ABS processing temperature is generally above 200 ℃, which is not suitable for occasions requiring low-temperature printing, such as children 3D printing pens, and if the printing temperature is too high, the pen head is easy to scald children. In addition, ABS is used as a consumable material for children's 3D printing pens, and generally needs to have better toughness and glossiness to ensure high safety during use and bright color of the product.
There is therefore a need to develop ABS materials that can be printed at low temperatures and that have high toughness and high gloss.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ABS alloy material, a preparation method and application thereof, so that the ABS alloy material has higher melt flow rate at low temperature (such as 170-180 ℃), higher toughness and higher glossiness, and can be used as a consumable for low-temperature 3D printing.
In order to achieve the above object, in a first aspect, the present invention provides an ABS alloy material, which comprises the following components in parts by weight: 50-70 parts of ABS resin, 15-45 parts of EVA (ethylene-vinyl acetate copolymer) resin, 5-15 parts of SMMA (styrene-methyl methacrylate copolymer) resin and 0-0.8 part of auxiliary agent.
The ABS alloy material introduces EVA resin with specific dosage into the ABS resin, so that the ABS alloy material has better meltability at low temperature (such as 170-180 ℃), such as a melt flow rate of more than or equal to 2g/10min (test standard GB/T3682-2000, test condition 170 ℃ and 10 kg); at the same time, SMMA resin with specific dosage is introduced to ensure that the glossiness is more than or equal to 70, thereby being capable of meeting the requirements ofThe children 3D printing pen has the requirements on consumable meltability (the highest printing temperature is 170-180 ℃) and glossiness, and meanwhile, the ABS alloy material also has higher toughness, for example, the notch impact strength (A-type notch) of a cantilever beam is 5kJ/m 2 The above.
Preferably, the melt flow rate of the ABS resin is 30-70g/10min, and the melt flow rate is tested according to the test standard GB/T3682-2000, the test condition is 220 ℃ and 10kg. When the melt flow rate of the ABS resin is less than 30g/10min, the melt flow rate of the obtained ABS alloy material is lower at 170-180 ℃; when the melt flow rate of the ABS resin is more than 70g/10min, the impact strength of the obtained ABS alloy material is lower.
Preferably, the EVA resin has a VA (vinyl acetate) content of 18-28% by weight. When the weight content of VA in the EVA resin is lower than 18%, EVA is easy to crystallize, the compatibility with ABS is poor, and the obtained ABS alloy material has low impact strength; when the weight content of VA in the EVA resin is more than 28%, the glossiness of the obtained ABS alloy material is lower. The weight content of VA in EVA resins can be tested with reference to the following criteria: thermal gravimetric analysis of vinyl acetate content test method in ethylene-vinyl acetate copolymer for GBT31984-2015 photovoltaic module.
Preferably, the EVA resin has a melt flow rate of 20-41g/10min, a melt flow rate test standard GB/T3682-2000, a test condition of 190 ℃ and 2.16kg. When the melt flow rate of the EVA resin is lower than 20g/10min, the melt flow rate and glossiness of the obtained ABS alloy material are lower; when the volume flow rate of the EVA resin is higher than 41g/10min, the impact strength of the obtained ABS alloy material is lower.
Preferably, the weight content of MMA (methyl methacrylate) in the SMMA resin is 50-75%. When the weight content of MMA in the SMMA resin is less than 50%, the gloss of the resulting alloy material is low, and therefore it is preferable that the weight content of MMA in the SMMA resin is 50 to 75% to obtain a high gloss. The weight content of MMA in the SMMA resin can be determined by hydrogen nuclear magnetic resonance.
When the melt flow rate of the ABS resin is 30-70g/10min (GB/T3682-2000, 220 ℃ C., 10 kg), the melt flow rate of the EVA resinWhen the weight content of VA is 18-28%, the melt flow rate of the ABS alloy material is more than or equal to 4g/10min (GB/T3682-2000, 170 ℃ and 10 kg), and the notched impact strength of cantilever beam (A-type notch) is more than or equal to 10kJ/m 2 The glossiness is more than or equal to 75.
The invention is not limited to the types of the auxiliary agents, and the types of the auxiliary agents added can be selected according to actual conditions. Preferably, the auxiliary agent includes at least one of an antioxidant, a lubricant, and the like. More preferably, the antioxidant is 0.1 to 0.3 parts by weight and the lubricant is 0.1 to 0.5 parts by weight. The antioxidant may be selected from hindered antioxidants, etc., but is not limited thereto; the lubricant may be at least one selected from ethylene bis-stearamide, calcium stearate, magnesium stearate, zinc stearate, PE wax, PP wax, etc., but is not limited thereto.
In a second aspect, the invention provides a preparation method of the ABS alloy material, which comprises the following steps: and (3) drying the ABS resin, the EVA resin and the SMMA resin, uniformly mixing with an auxiliary agent, and then carrying out melt extrusion, cooling and drying to obtain the ABS alloy material. Wherein the melting temperature can be selected to be 160-185 ℃, and the screw rotating speed can be selected to be 200-500r/min; the cooling mode can be water cooling, air cooling and the like.
In a third aspect, the present invention provides an application of the ABS alloy material, specifically: the ABS alloy material was used as a 3D printing consumable. The ABS alloy material is used as a consumable material and has higher glossiness and toughness.
Preferably, the ABS alloy material is used as a low-temperature 3D printing consumable, and the highest temperature of low-temperature 3D printing is 170-180 ℃.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the EVA resin and the SMMA resin with specific amounts are added into the ABS resin, so that the obtained ABS alloy material has higher toughness and glossiness, has higher melt flow rate at low temperature, such as 170-180 ℃, and is suitable for low-temperature printing, such as consumable used as a child 3D printing pen.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
The raw materials used in each of the examples and comparative examples are as follows:
ABS resin # 1: ABS DG-417, tianjin, melt flow rate 20g/10min;
ABS resin # 2: ABS DG-MG94, tianjin, melt flow rate of 30g/10min;
ABS resin 3#: ABS HP181, huizhou Le Jin, melt flow rate 50g/10min;
ABS resin # 4: ABS D670, korean Jinhu, melt flow rate of 70g/10min;
EVA resin No. 1: XB1641, celanese Corporation, melt flow rate 28g/10min, va 16% by weight;
EVA resin No. 2: EVA EL18025, LG Chem Ltd., melt flow rate 25g/10min, VA 18% by weight;
EVA resin 3#: EVAFL02020, exxonMobil, melt flow rate 20g/10min, VA 20% by weight;
EVA resin No. 4: EVA EA28025, LG Chem Ltd., melt flow rate 25g/10min, VA 28% by weight;
EVA resin No. 5: EVA UE654-04,USI Corporation with melt flow rate of 30g/10min and VA content of 33% by weight;
EVA resin No. 6: ultra FL 00623, exxonMobil, melt flow rate 5.5g/10min, weight content of VA 23%;
EVA resin # 7: ultra UL 04028CC, exxonMobil, melt flow rate of 41g/10min, VA weight content of 27.5%;
EVA resin 8#: ultra UL 15019CC, exxonMobil, melt flow rate 150g/10min, weight content of VA 19%;
SMMA resin No. 1: MS-500, new Japanese iron for gold, MMA weight content of 50%;
SMMA resin No. 2: MS-600, new Japanese iron for gold, MMA weight content of 60%;
SMMA resin 3#: MS-750, new Japanese iron for gold, MMA 75 wt%;
SMMA resin No. 4: MS-300, new day iron is used for holding gold, and the weight content of MMA is 30%;
an antioxidant: commercially available, the same materials were used in other examples and comparative examples;
and (3) a lubricant: the same materials are commercially available in other examples and comparative examples.
The test standard of the melt flow rate of each ABS resin raw material is GB/T3682-2000, and the test condition is 220 ℃ and 10kg; the melt flow rate of each EVA resin raw material is tested according to GB/T3682-2000, and the test condition is 190 ℃ and 2.16kg.
Examples and comparative examples
The compositions of the ABS alloy materials are shown in tables 1-2 (the "-" in the tables represents the content of 0), and the preparation methods thereof comprise the following steps: and (3) drying the ABS resin, the EVA resin and the SMMA resin, uniformly mixing the ABS resin, the EVA resin and the SMMA resin with an antioxidant and a lubricant in a mixing device, carrying out melt blending extrusion in a mechanical device, carrying out water cooling, granulating, and drying to obtain the corresponding ABS alloy material, wherein the melting temperature is 160-185 ℃ and the screw speed is 200-500r/min. The steps of the preparation process and other process parameters of the ABS materials of each example and the comparative example are identical except for the different formulas.
The performance test is carried out on the ABS alloy materials of each example and comparative example, and the specific method is as follows:
notched Izod impact Strength: GB/T1843-2008, type A notch;
melt flow rate of GB/T3682-2000, 170 ℃/10kg;
gloss level: sheets of 1 x 100mm were extruded with hake and then tested for 60 ° gloss with a gloss meter.
TABLE 1 compositions and Properties of examples 1 to 10ABS alloy materials
Table 2 ABS alloy materials compositions and properties of examples 11 to 16 and comparative examples 1 to 3
As can be seen from tables 1 and 2, the ABS alloy material of the invention has higher melt flow rate, toughness and glossiness, the melt flow rate is more than 2g/10min (170 ℃/10 kg), and the notched impact strength (A-type notch) of the cantilever beam is 5kJ/m 2 The glossiness is above 70. Pure ABS resin, such as comparative example 1, could not be melted at a low temperature of 170 ℃. Too little SMMA resin, such as comparative example 2, can result in significantly lower gloss of the ABS alloy material; excessive amounts of SMMA resin, as in comparative example 3, can result in lower impact strength of the ABS alloy material.
As is clear from comparison of examples 4 with examples 2 and 5 to 6, the lower melt flow rate of the ABS resin results in lower melt flow rate of the ABS alloy material, and in order to ensure smoother 3D printing process for children, the melt flow rate of the ABS resin is preferably 30 to 70g/10min (220 ℃/10 kg). Comparing examples 2, 8, 9 and 11-13, it is clear that the lower melt flow rate of the EVA resin results in lower melt flow rate and gloss of the ABS alloy material; the higher melt flow rate of EVA resin can lead to lower impact strength of cantilever beam notch of the ABS alloy material. Comparing examples 2, 7-10 and 12, it is clear that lower VA weight content in EVA resin can result in lower notched Izod impact strength of ABS alloy material; the higher VA weight content in EVA resin can result in lower glossiness of the ABS alloy material. Comparing examples 2 and 14 to 16, it is evident that a lower MMA content in the SMMA resin results in a lower gloss of the ABS alloy material.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The ABS alloy material is characterized by comprising the following components in parts by weight: 50-70 parts of ABS resin, 15-45 parts of EVA resin, 5-15 parts of SMMA resin and 0-0.8 part of auxiliary agent; the weight content of vinyl acetate in the EVA resin is 18-28%; the melt flow rate of the EVA resin is 20-41g/10min, and the melt flow rate is tested according to the test standard GB/T3682-2000, and the test condition is 190 ℃ and 2.16kg.
2. The ABS alloy material according to claim 1 wherein the ABS resin has a melt flow rate of 30-70g/10min, melt flow rate test standard GB/T3682-2000, test conditions 220 ℃ and 10kg.
3. The ABS alloy material of claim 1 wherein the SMMA resin comprises 50 to 75% by weight of methyl methacrylate.
4. The ABS alloy material of claim 1 wherein the auxiliary comprises at least one of an antioxidant and a lubricant.
5. A method for producing the ABS alloy material according to any one of claims 1 to 4, comprising the steps of: and (3) drying the ABS resin, the EVA resin and the SMMA resin, uniformly mixing with an auxiliary agent, and then carrying out melt extrusion, cooling and drying to obtain the ABS alloy material.
6. Use of an ABS alloy material according to any one of claims 1 to 4 as a 3D printing consumable.
7. Use of an ABS alloy material according to claim 6 wherein the ABS alloy material is used as a low temperature 3D printing consumable, the highest temperature of the low temperature 3D printing being 170-180 ℃.
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