CN117304642A - 3D printing ABS antibacterial degradable composite material and preparation method thereof - Google Patents
3D printing ABS antibacterial degradable composite material and preparation method thereof Download PDFInfo
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- CN117304642A CN117304642A CN202311472209.3A CN202311472209A CN117304642A CN 117304642 A CN117304642 A CN 117304642A CN 202311472209 A CN202311472209 A CN 202311472209A CN 117304642 A CN117304642 A CN 117304642A
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 32
- 238000010146 3D printing Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 59
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 57
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000004626 polylactic acid Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012760 heat stabilizer Substances 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229920001290 polyvinyl ester Polymers 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000008301 phosphite esters Chemical class 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 241001122767 Theaceae Species 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003899 bactericide agent Substances 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 4
- -1 methylene dinaphthyl Chemical group 0.000 claims description 4
- 150000004714 phosphonium salts Chemical group 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 102000003992 Peroxidases Human genes 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 239000000467 phytic acid Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 238000010998 test method Methods 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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)
Abstract
The invention discloses a 3D printing ABS antibacterial degradable composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 80-95 parts of acrylonitrile-butadiene-styrene copolymer and 5-35 parts of polylactic acid; 0.5-5.0 parts of compatilizer; 0.2-5.0 parts of antibacterial agent; 0.2-10.0 parts of auxiliary agent. The ABS/PLA composite material is adopted, and has antibacterial property and degradability under the condition of improving the flowability and interlayer adhesive strength of the ABS, and can be used for producing medical ABS materials.
Description
Technical Field
The invention relates to the field of 3D printing materials; in particular to a 3D printing ABS antibacterial degradable composite material and a preparation method thereof.
Background
The acrylonitrile-butadiene-styrene copolymer (ABS) is a high molecular polymer which is widely used, is a copolymer obtained by copolymerizing three monomers of acrylonitrile (A), butadiene (B) and styrene (S) according to a certain proportion, has the advantages of excellent hot processing performance, high impact strength, good heat stability, high product precision, wide application range and the like, and is one of the most commonly used general plastics. However, when the general ABS resin is applied to the FDM printing process, the defects such as easy filament breakage, difficult extrusion and the like are common. Therefore, the ABS needs to be modified to play a wider role in the FDM process.
In the prior art, for example, patent application number CN201710277826.6 discloses a 3D printing material with antibacterial property, which comprises the following components in parts by weight: 100 parts of ABS resin; 0.1 to 5 parts of antibacterial agent; 1-10 parts of inorganic powder; 0.5-1 part of antioxidant; 0.2 to 1 part of lubricant. The technical defects of the scheme are as follows: only modified from the aspects of antibacterial property and the like, and the degradation and mechanical property of the 3D printing ABS material are not researched
Disclosure of Invention
The invention aims to provide an ABS antibacterial degradable composite material for 3D printing.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a 3D printing ABS antibacterial degradable composite material, which comprises the following components in parts by weight:
preferably, the compatilizer is one or two of maleic anhydride grafting and styrene polymer.
Preferably, the antibacterial agent is composed of one or more of tea polyphenol, alkyl quaternary phosphonium salt organic bactericide, chitosan, peroxidase derivative and the like.
Preferably, the auxiliary agent comprises one or a mixture of more of a coupling agent, a plasticizer, an antioxidant, a dispersing agent, a heat stabilizer and a lubricant.
Preferably, the antioxidant is: at least one of tea polyphenols, 1010 oxidant, and phytic acid.
Preferably, the plasticizer is a synthetic vegetable ester.
Preferably, the heat stabilizer is: at least one of phosphite ester heat stabilizer and calcium-zinc stabilizer.
Preferably, the lubricant is: at least one of zinc stearate, calcium stearate and ethylene bis-stearamide.
Preferably, the dispersing agent is at least one of oxidized polyvinyl ester, sodium methylene dinaphthyl sulfonate and oxidized polyvinyl ester.
Preferably, the coupling agent is vinyltrimethoxysilane.
The invention also provides a preparation method of the composite material, which comprises the following steps:
(1) Putting the materials with the formula amount into a blast drier for drying; premixing according to a certain proportion, mixing in a high-speed mixer, and adding white oil to make the white oil fully and uniformly mixed;
(2) The ABS composite material particles are obtained by granulating and drying after double-screw melt blending extrusion; (3) And adding the obtained particles into a single screw extruder for extrusion, regulating the size of the wire rod by controlling the rotating speed of a tractor to obtain a regular wire rod with stable diameter, and winding by a wire winder to obtain a 3D printing consumable wire coil, namely the ABS antibacterial degradable composite material for 3D printing.
The invention has the following advantages but is not limited to:
the ABS/PLA composite material is adopted, and has antibacterial property and degradability under the condition of improving the flowability and interlayer adhesive strength of the ABS, and can be used for producing medical ABS materials.
The invention is based on the basic principle of compatibility of high polymer materials, and the advantages of one material are fully utilized to make up the defects of the other material in performance by reasonably selecting and combining, and the material has degradability by adding the reinforced composite material mechanical property; by adding the novel antibacterial agent, the antibacterial performance of the material is improved, and the ABS antibacterial degradable composite material with low carbon, environmental protection, good mechanical property and excellent antibacterial performance is obtained.
Detailed description of the preferred embodiments
The specific embodiments of the present invention are explained by way of example, and the described embodiments are intended to be part of the invention, and are intended to be within the scope of the present invention as defined by the appended claims, unless the technology used for the detection is not limited in any way. This section generally describes the materials used in the test of the present invention and the test method. Although many materials and methods of operation are known in the art for accomplishing the objectives of the present invention, the present invention will be described in as much detail herein. It will be apparent to those skilled in the art that in this context, the materials and methods of operation used in the present invention are well known in the art, if not specifically described.
Example 1
3D prints antibiotic degradable composite of ABS:
(1) The components in parts by weight are as follows: 80 parts of acrylonitrile-butadiene-styrene copolymer (ABS); polylactic acid (PLA): 16.8 parts; and (3) a compatilizer: 0.8 parts; 2 parts of an antibacterial agent; auxiliary agent: 0.4 parts.
(2) The compatilizer is styrene polymerized PLA.
(3) The antibacterial agent is Tea Polyphenols (TP), and the Tea Polyphenols have antioxidant effect.
(4) The auxiliary agent comprises the use of a heat stabilizer: 0.1 part of phosphite esters; the lubricant is ethylene bis stearamide and zinc stearate 0.1 parts respectively; the dispersant is oxidized polyvinyl ester 0.1 part.
The preparation method comprises the following steps: putting the ABS into a blast drier, and drying for 2 hours at 80 ℃; placing PLA into a blast drier, and drying at 60 ℃ for 2 hours; premixing the ABS composite material with other auxiliary antibacterial agents according to a proportion, putting the mixture into a high-speed mixer, adding 2 drops of white oil and 3 drops of white oil into the mixture to enable the white oil and the white oil to be fully and uniformly mixed, carrying out melt blending extrusion by using double screws, granulating and drying the mixture to obtain ABS composite material particles, and adding the ABS composite material particles into a single screw extruder for extrusion. And the wire size is regulated by controlling the rotating speed of the tractor so as to obtain a regular wire with stable diameter. And winding by a wire winding machine to obtain the 3D printing consumable wire coil.
Example 2
3D prints antibiotic degradable composite of ABS:
(1) The components in parts by weight are as follows: 95 parts of acrylonitrile-butadiene-styrene copolymer (ABS); polylactic acid (PLA): 25 parts; and (3) a compatilizer: 1 part; 1.5 parts of antibacterial agent; auxiliary agent: 0.6 part.
(2) The compatilizer is styrene polymerized PLA.
(3) The antibacterial agent is an alkyl quaternary phosphonium salt organic bactericide.
(4) The auxiliary agent comprises the use of a heat stabilizer: 0.1 part of phosphite ester, calcium and zinc stabilizer; 0.1 part of antioxidant phytic acid and 0.1 part of lubricant zinc stearate; the dispersant is methylene dinaphthyl sodium sulfonate 0.1 part.
The preparation method comprises the following steps: putting the ABS into a blast drier, and drying for 1.5 hours at 80 ℃; placing PLA into a blast drier, and drying at 65 ℃ for 1.5h; premixing the ABS composite material with other auxiliary antibacterial agents according to a proportion, putting the mixture into a high-speed mixer, adding 2 drops of white oil and 3 drops of white oil into the mixture to enable the white oil and the white oil to be fully and uniformly mixed, carrying out melt blending extrusion by using double screws, granulating and drying the mixture to obtain ABS composite material particles, and adding the ABS composite material particles into a single screw extruder for extrusion. And the wire size is regulated by controlling the rotating speed of the tractor so as to obtain a regular wire with stable diameter. And winding by a wire winding machine to obtain the 3D printing consumable wire coil.
Example 3
3D prints antibiotic degradable composite of ABS:
(1) The components in parts by weight are as follows: 95 parts of acrylonitrile-butadiene-styrene copolymer (ABS); polylactic acid (PLA): 10 parts; and (3) a compatilizer: 1 part; 2 parts of an antibacterial agent; auxiliary agent: 0.8 parts.
(2) The compatilizer is maleic anhydride grafted polymer.
(3) The antibacterial agent is an alkyl quaternary phosphonium salt organic bactericide.
(4) The auxiliary agent comprises 0.1 part of vinyltrimethoxysilane serving as a coupling agent; 0.1 part of plasticizer synthetic vegetable ester; 0.1 part of phosphite ester, calcium and zinc stabilizer; the lubricant is zinc stearate and calcium stearate 0.1 part each; the dispersing agent is methylene dinaphthyl sodium sulfonate and oxidized polyvinyl ester 0.1 part each.
The preparation method comprises the following steps: putting the ABS into a blast drier, and drying for 2 hours at 80 ℃; placing PLA into a blast drier, and drying for 2 hours at 65 ℃; premixing the ABS composite material with other auxiliary antibacterial agents according to a proportion, putting the mixture into a high-speed mixer, adding 2 drops of white oil and 3 drops of white oil into the mixture to enable the white oil and the white oil to be fully and uniformly mixed, carrying out melt blending extrusion by using double screws, granulating and drying the mixture to obtain ABS composite material particles, and adding the ABS composite material particles into a single screw extruder for extrusion. And the wire size is regulated by controlling the rotating speed of the tractor so as to obtain a regular wire with stable diameter. And winding by a wire winding machine to obtain the 3D printing consumable wire coil.
Comparative example 1
An acrylonitrile-butadiene-styrene copolymer (ABS) is taken as a main raw material, and is mixed with a compatilizer, an antibacterial agent and an auxiliary agent according to a certain proportion, and a 3D printing wire is prepared according to the method of the embodiment.
(1) The components in parts by weight are as follows: 80 parts of acrylonitrile-butadiene-styrene copolymer (ABS); and (3) a compatilizer: 0.8 parts; 2 parts of an antibacterial agent; auxiliary agent: 0.4 parts.
(2) The compatilizer is styrene polymerized PLA.
(3) The antibacterial agent is tea polyphenols (TeaPolyphenols, TP).
(4) The auxiliary agent comprises the use of a heat stabilizer: 0.1 part of phosphite esters; the lubricant is ethylene bis stearamide and zinc stearate 0.1 parts respectively; the dispersant is oxidized polyvinyl ester 0.1 part.
Comparative example 1 differs from example 3 in that polylactic acid (PLA) was not added in comparative example 1, unlike example 3.
Comparative example 2
An acrylonitrile-butadiene-styrene copolymer (ABS) was used as a main raw material, which was mixed with polylactic acid (PLA), a compatibilizer, and an auxiliary agent in a certain ratio, and a 3D printing wire was prepared in the same manner as in example 3.
(1) The components in parts by weight are as follows: 80 parts of acrylonitrile-butadiene-styrene copolymer (ABS); polylactic acid (PLA): 16.8 parts; and (3) a compatilizer: 0.8 parts; 2 parts of an antibacterial agent; auxiliary agent: 0.4 parts.
(2) The compatilizer is styrene polymerized PLA.
(3) The auxiliary agent comprises the use of a heat stabilizer: 0.1 part of phosphite esters; the lubricant is ethylene bis stearamide and zinc stearate 0.1 parts respectively; the dispersant is oxidized polyvinyl ester 0.1 part.
Comparative example 2 differs from example 3 in that no antibacterial agent was added in comparative example 1.
Performance test:
1. mechanical property test of 3D printing ABS antibacterial degradable composite material
The 3D printing materials prepared in examples 1 to 3 and comparative examples 1 and 2 were printed into test bars using a 3D printer. Tensile strength and flexural strength were tested with reference to the method in ASTM D-638; the mass flow rate of the plastic melt was determined with reference to GB/T3628-2000. The test results are shown in Table 1.
TABLE 1.3 mechanical test results of antibacterial materials for 3D printing
As can be seen from the experimental data in Table 1, the 3D printing ABS antibacterial degradable composite materials prepared in the embodiments 1-3 have excellent mechanical properties, and comparative example 1 shows that the bonding strength between ABS wire layers can be increased by adding PLA; the addition of the compatilizer for the two-phase compatibilization of PLA and ABS can increase the compatibility of materials and improve the comprehensive mechanical properties, and comparative example 2 shows that the addition of the antibacterial agent has little influence on the mechanical properties of wires.
2. Antibacterial property test of 3D printing ABS antibacterial degradable composite material
The 3D printing materials prepared in examples 1 to 3 and comparative example 2 were printed into test bars using a 3D printer. The bacteriostasis rate of the sample was calculated with reference to GB4789-2016 and the test results are shown in Table 2.
Table 2.3 results of antibacterial property test of antibacterial material for 3D printing
| Coliform bacteria inhibition rate | Antibacterial rate of staphylococcus | Pseudomonas aeruginosa antibacterial rate | |
| Example 1 | 99.87％ | 99.69％ | 98.43％ |
| Example 2 | 99.94％ | 99.47％ | 97.88％ |
| Example 3 | 99.72％ | 98.94％ | 98.71％ |
| Comparative example 2 | 9.64％ | 10.15％ | 6.89％ |
As is clear from Table 2, in examples 1 to 3, the antibacterial ratio of Escherichia coli was > 99%, the antibacterial ratio of Staphylococcus aureus was > 98%, and the antibacterial ratio of Pseudomonas aeruginosa was more than 97%, which proves that the antibacterial agent can have good antibacterial effect only when added into the material.
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (9)
1. The utility model provides a 3D prints antibiotic degradable composite of ABS which characterized in that: the composite material consists of the following components in parts by weight:
80-95 parts of acrylonitrile-butadiene-styrene copolymer;
5-35 parts of polylactic acid;
0.5-5.0 parts of compatilizer;
0.2-5.0 parts of antibacterial agent;
0.2-10.0 parts of auxiliary agent.
2. The composite material of claim 1, wherein: the compatilizer is one or two of maleic anhydride grafting and styrene polymer.
3. The composite material of claim 1, wherein: the antibacterial agent is composed of one or more of tea polyphenol, alkyl quaternary phosphonium salt organic bactericide, chitosan and peroxidase derivative.
4. The composite material of claim 1, wherein: the auxiliary agent is at least one of a coupling agent, a plasticizer, an antioxidant, a dispersing agent, a heat stabilizer and a lubricant.
5. The composite material of claim 4, wherein: the heat stabilizer is as follows: at least one of phosphite ester heat stabilizer and calcium-zinc stabilizer.
6. The composite material of claim 4, wherein: the lubricant is as follows: at least one of zinc stearate, calcium stearate and ethylene bis-stearamide.
7. The composite material of claim 4, wherein: the dispersing agent is at least one of oxidized polyvinyl ester, sodium methylene dinaphthyl sulfonate and oxidized polyvinyl ester.
8. The composite material of claim 4, wherein: the coupling agent is vinyl trimethoxy silane.
9. A method of preparing a composite material according to any one of claims 1 to 8, comprising the steps of:
(1) Putting the materials with the formula amount into a blast drier for drying; premixing according to a certain proportion, mixing in a high-speed mixer, and adding white oil to make the white oil fully and uniformly mixed;
(2) The ABS composite material particles are obtained by granulating and drying after double-screw melt blending extrusion;
(3) And adding the obtained particles into a single screw extruder for extrusion, regulating the size of the wire rod by controlling the rotating speed of a tractor to obtain a regular wire rod with stable diameter, and winding by a wire winder to obtain a 3D printing consumable wire coil, namely the ABS antibacterial degradable composite material for 3D printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311472209.3A CN117304642B (en) | 2023-11-07 | 2023-11-07 | 3D printing ABS antibacterial degradable composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311472209.3A CN117304642B (en) | 2023-11-07 | 2023-11-07 | 3D printing ABS antibacterial degradable composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117304642A true CN117304642A (en) | 2023-12-29 |
| CN117304642B CN117304642B (en) | 2024-06-25 |
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| CN106893280A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of biodegradable 3D printing alloy material and preparation method |
| CN106893281A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of biodegradable 3D printing reinforcing material and preparation method |
| WO2021135570A1 (en) * | 2019-12-31 | 2021-07-08 | 金发科技股份有限公司 | Abs/polyester alloy composition and a preparation method therefor |
| WO2023088239A1 (en) * | 2021-11-17 | 2023-05-25 | 金发科技股份有限公司 | Flame-retardant high-toughness pla alloy material, and preparation method therefor and use thereof |
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| CN106893280A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of biodegradable 3D printing alloy material and preparation method |
| CN106893281A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of biodegradable 3D printing reinforcing material and preparation method |
| WO2021135570A1 (en) * | 2019-12-31 | 2021-07-08 | 金发科技股份有限公司 | Abs/polyester alloy composition and a preparation method therefor |
| WO2023088239A1 (en) * | 2021-11-17 | 2023-05-25 | 金发科技股份有限公司 | Flame-retardant high-toughness pla alloy material, and preparation method therefor and use thereof |
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