CN105860418A - Easy-to-plasticize bacterial inhibition type 3D printing material and preparation method thereof - Google Patents
Easy-to-plasticize bacterial inhibition type 3D printing material and preparation method thereof Download PDFInfo
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- CN105860418A CN105860418A CN201610338523.6A CN201610338523A CN105860418A CN 105860418 A CN105860418 A CN 105860418A CN 201610338523 A CN201610338523 A CN 201610338523A CN 105860418 A CN105860418 A CN 105860418A
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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
- 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
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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
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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Abstract
The invention discloses an easy-to-plasticize bacterial inhibition type 3D printing material and a preparation method thereof. The 3D printing material is prepared from the following components in parts by weight: 120 to 140 parts of ABS, 2 to 8 parts of a light diffusing agent, 2 to 8 parts of an initiator, 10 to 20 parts of a crosslinking agent, 10 to 20 parts of a coupling agent, 10 to 30 parts of clam shell powder, 2 to 8 parts of elemental sulfur, 1 to 4 parts of medical stone powder, 1 to 4 parts of walnut shell ultrafine powder, 1 to 6 parts of limonene, 4 to 20 parts of toosedarin and 0.2 to 0.4 part of auxiliaries. The invention provides a new type of 3D printing material for selection and use of users as required; from the aspect of the 3D printing material, the application and development space of the 3D printing material with the ABS as a main raw material is greatly enlarged, and the significance is outstanding.
Description
Technical field
The invention belongs to 3D and print field, be specifically related to a kind of 3D printing material and preparation method thereof.
Background technology
The development maked rapid progress along with 3D printing technique, the concept that 3D prints gradually is known by the public.FDM technology is profit
With ABS, polycarbonate (PC), polyphenylsulfone (PPSF), PLA and other thermoplastic are subject to
To adding the filament being hot extruded into as semi-molten state, by the mode being deposited on the basis of storehouse layer by layer, from 3D CAD data
Directly construction prototype.This technology is commonly used to plastotype, assembling, functional test and conceptual design.Additionally, FDM
Technology can apply to draw a design and quickly manufacture.
ABS material, ABS, original name is acrylonitrile-butadiene-styrene copolymer, is domestic fusion sediment (FDM) formula
The essential core of wire rod.From the properties of material, from the perspective of hot junction, the relatively easy printing of ABS plastic.Nothing
Which type of extruder is opinion use, all can extruded material the most glidingly.ABS resilient enough, be suitable for making furnishings or
Ornament, as long as printing with suitable temperature, allows material layer by layer firmly stick, and the intensity of ABS will become at a relatively high.
ABS has flexibility, also only can bend even if bearing pressure, will not fracture.
But on the one hand this material has the characteristic of contract on cooling, can from heating plate local shedding, unsettled, cause and ask
Topic.If it addition, the object height printed is the highest, the most also can flood peel off.Therefore, ABS prints to have lacked and adds
Hot plate.It is uncomfortable that abnormal smells from the patient when on the other hand printing allows people have very much.
Along with development in science and technology and social progress, 3D printed product starts to be not limited only to industrial design, building, engineering and construction
(AEC), automobile, Aero-Space, dentistry and medical industries, education, GIS-Geographic Information System, civil engineering, gun etc.
Field, also begins to come into daily life, in order to make some living utensils or ornament, but at present in life
Application be still embodied in the purposes that the shape of printed product is brought, and the art that its color and shape are formed
Designs etc., the application and development printing 3D there is also the biggest space, simultaneously intensity in degradable rate, toughness and all
Need to be further improved.
Summary of the invention
Goal of the invention: the problem existed for prior art, first technical problem to be solved by this invention is to provide easily
Mould antibacterial type 3D printed material.Second to be solved by this invention technical problem is that this easily moulds antibacterial type 3D printed material
Preparation method.
Technical scheme: for solving above-mentioned technical problem, the invention provides one and easily mould antibacterial type 3D printed material, press
Include that following components is made according to parts by weight: ABS 120～140 parts；Light diffusing agent 2～8 parts；Initiator 2～8 parts；
Cross-linking agent 10～20 parts；Coupling agent 10～20 parts；Concha Meretricis Seu Cyclinae powder 10～30 parts；Elemental sulfur 2～8 parts；Medical stone powder 1～
4 parts；Walnut shell ultrafine powder 1～4 parts；Limonene 1～6 parts；Plant toosedarin 4～20 parts；Auxiliary agent 0.2～0.4 part.
It is further preferred that also include feather powder 2～8 parts according to parts by weight.
Preferably, described light diffusing agent is organosilicon light diffusing agent.
Preferably, described initiator is thermal initiator.
Preferably, described initiator is the mixture of light trigger and thermal initiator.
Preferably, according to parts by weight, described initiator includes that following components is made: light trigger 1～3 parts；Thermal initiation
Agent 1～5 parts.
Preferably, one or both the mixture during described coupling agent is titanate coupling agent or silane coupler.
Preferably, described plant toosedarin is Parmelia tinctorum Despr. extract.
Preferably, described plant toosedarin is orcin.
Preferably, according to parts by weight, described auxiliary agent includes that following components is made: plasticizer 0.1～0.2 part；Toughener 0.1～
0.2 part.
Invention also provides for the above-mentioned preparation method easily moulding antibacterial type 3D printed material, comprise the steps:
1) ABS particle high-temperature is melted, add initiator and cross-linking agent mixes, grafting；
2) it is cooled to 20 DEG C～30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize to obtain preparing being grafted and hand over
The ABS powder of connection agent；
3) by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, walnut shell ultrafine powder,
Medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform；
4) by step 3) gains are while continue to be mixed and stirred for uniform, and mixing adds the phase processed through atomization successively
Answer limonene and the plant toosedarin of parts by weight；
5) then add the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；
6) while ultra violet lamp 30～60min, after stirring is cooled to 50 DEG C～55 DEG C, puts in extruder, add
Hot-extrudable, vacuum drying, prepare target product.
As preferably, described step 3) be: by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae of corresponding parts by weight
Powder, elemental sulfur, walnut shell ultrafine powder, feather powder, medical stone powder, coupling agent and auxiliary agent, add hot mixing high-speed stirred
Uniformly.
Beneficial effect: what the present invention provided easily moulds antibacterial type 3D printed material, in the key property with 3D printed material
On the basis of, on the one hand the network structure of material is significantly enhanced, the 3D printed product good toughness made with this material,
Degradable rate is high；On the other hand by initiator, Concha Meretricis Seu Cyclinae powder and the synergism of elemental sulfur, alleviate ABS material and meet
The characteristic of cold events, effectively reduces flood that may be present when ABS material prints and peels off the problem brought, and lifting is moulded
Type quality；When in component, increase has feather powder further, initiator and elemental sulfur and feather powder synergism, can be effective
Incidental local shedding when overcoming ABS material to print, unsettled or flood peel off the problem brought, the most effectively
The printing plastotype quality of improving product；In the 3D printed material that the present invention provides simultaneously, plant toosedarin and medical stone powder
Synergism makes the present invention have excellent antimicrobial and anti-inflammation efficacy concurrently, and can kill fly worm sperm and effectively suppress the numerous of worm's ovum
Growing, cleannes are high, can play simultaneously and preferably remove free radical effect and anti-radiation effect；What is more important, its group
Limonene is divided not only to be effectively improved the abnormal smells from the patient when carrying out high temperature print job of the 3D printed material with ABS as raw material, and
And with medical stone powder, plant toosedarin synergism, there is antioxidation, significantly improve what the present invention provided further
The antioxygenic property of 3D printed material and stability；Plus overall composition synergism so that the 3D made with this material
Printed product is homogeneous, and stress is uniform, it is easy to cutting plastotype, for print further artificial microscopic carvings on the product prepared,
Cutting, plastotype provide more preferable ease for use.
The preparation method easily moulding antibacterial type 3D printed material that the present invention provides simultaneously, by during high-speed stirred
It is stirred cooling under atomization addition limonene and plant toosedarin, and ultra violet lamp, improves obtained further
The stability of 3D printing consumables and non-oxidizability.
Entirety extends service life, it is provided that a kind of 3D printed material new varieties select as required for user,
In terms of 3D printed material, it is greatly enlarged the application development space of 3D printed material with ABS as primary raw material,
Meaning is notable.
Detailed description of the invention
Embodiment 1: one easily moulds antibacterial type 3D printed material, includes that following components is made according to parts by weight: ABS 120
Part；Light diffusing agent 2 parts；Initiator 2 parts；Cross-linking agent 10 parts；Coupling agent 10 parts；Concha Meretricis Seu Cyclinae powder 10 parts；Elemental sulfur 2
Part；Medical stone powder 1 part；Walnut shell ultrafine powder 1 part；Limonene 1 part；Plant toosedarin 4 parts；Auxiliary agent 0.2 part.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein according to parts by weight, initiator includes that following components is made: light trigger 1 part；Thermal initiator 1 part.
Wherein coupling agent is titanate coupling agent.
Wherein plant toosedarin is Parmelia tinctorum Despr. extract.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.1 part；Toughener 0.1 part.
Preparation method comprises the steps: 1) ABS particle high-temperature is melted, add initiator and cross-linking agent mixes,
Grafting；2) it is cooled to 20 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing graft crosslinking
The ABS powder of agent；3) by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, core
Peach shell superfine powder, medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform；4) by step 3) gained
The while that thing continuing to be mixed and stirred for uniform, successively mixing add through atomization process corresponding parts by weight limonene and
Plant toosedarin；5) then add the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；6) in ultraviolet
While light irradiation 30, after stirring is cooled to 50 DEG C, puts in extruder, add hot-extrudable, vacuum drying, it is prepared into
To target product.After testing, the flexility of material reaches 82.2Mpa, notch impact strength reaches 47.8MJ/m2。
Embodiment 2: one easily moulds antibacterial type 3D printed material, includes that following components is made according to parts by weight: ABS 140
Part；Light diffusing agent 8 parts；Initiator 8 parts；Cross-linking agent 20 parts；Coupling agent 20 parts；Concha Meretricis Seu Cyclinae powder 30 parts；Elemental sulfur 8
Part；Medical stone powder 4 parts；Walnut shell ultrafine powder 4 parts；Limonene 6 parts；Plant toosedarin 20 parts；Auxiliary agent 0.4 part.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein according to parts by weight, initiator includes that following components is made: light trigger 3 parts；Thermal initiator 5 parts.
Wherein coupling agent is silane coupler.
Wherein plant toosedarin is orcin.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.2 part；Toughener 0.2 part.
Preparation method comprises the steps: 1) ABS particle high-temperature is melted, add initiator and cross-linking agent mixes,
Grafting；2) it is cooled to 30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing graft crosslinking
The ABS powder of agent；3) by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, core
Peach shell superfine powder, medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform；4) by step 3) gained
The while that thing continuing to be mixed and stirred for uniform, successively mixing add through atomization process corresponding parts by weight limonene and
Plant toosedarin；5) then add the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；6) in ultraviolet
While light irradiation 60min, after stirring is cooled to 55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, system
For obtaining target product.After testing, the flexility of material reaches 82.4Mpa, notch impact strength reaches
47.9MJ/m2。
Embodiment 3: one easily moulds antibacterial type 3D printed material, includes that following components is made according to parts by weight: ABS 130
Part；Light diffusing agent 5 parts；Initiator 5 parts；Cross-linking agent 15 parts；Coupling agent 15 parts；Concha Meretricis Seu Cyclinae powder 20 parts；Elemental sulfur 5
Part；Medical stone powder 3 parts；Walnut shell ultrafine powder 2 parts；Feather powder 5 parts；Limonene 4 parts；Plant toosedarin 12 parts；
Auxiliary agent 0.3 part.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein according to parts by weight, initiator includes that following components is made: thermal initiator 5 parts.
Wherein coupling agent is the mixture of titanate coupling agent and silane coupler, and ratio is 2:3.
Wherein plant toosedarin is Parmelia tinctorum Despr. extract.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.15 part；Toughener 0.15 part.
Preparation method comprises the steps: 1) ABS particle high-temperature is melted, add initiator and cross-linking agent mixes,
Grafting；2) it is cooled to 25 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing graft crosslinking
The ABS powder of agent；3) by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, core
Peach shell superfine powder, feather powder, medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform；4) will step
Rapid 3), the while that gains continuing to be mixed and stirred for uniform, mixing adds the corresponding parts by weight processed through atomization successively
Limonene and plant toosedarin；5) then add the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；
6) while ultra violet lamp 45min, after stirring is cooled to 52 DEG C, puts in extruder, add hot-extrudable, vacuum
It is dried, prepares target product.After testing, the flexility of material reaches 83.8Mpa, notch impact strength
Reach 48.8MJ/m2。
Embodiment 4: one easily moulds antibacterial type 3D printed material, includes that following components is made according to parts by weight: ABS 125
Part；Light diffusing agent 3 parts；Initiator 3 parts；Cross-linking agent 12 parts；Coupling agent 12 parts；Concha Meretricis Seu Cyclinae powder 15 parts；Elemental sulfur 4
Part；Medical stone powder 2 parts；Walnut shell ultrafine powder 2 parts；Feather powder 4 parts；Limonene 2 parts；Plant toosedarin 8 parts；
Auxiliary agent 0.2 part.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein according to parts by weight, initiator includes that following components is made: thermal initiator 3 parts.
Wherein coupling agent is titanate coupling agent.
Wherein plant toosedarin is Parmelia tinctorum Despr. extract.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.1 part；Toughener 0.1 part.
Preparation method comprises the steps: 1) ABS particle high-temperature is melted, add initiator and cross-linking agent mixes,
Grafting；2) it is cooled to 25 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing graft crosslinking
The ABS powder of agent；3) by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, core
Peach shell superfine powder, feather powder, medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform；4) will step
Rapid 3), the while that gains continuing to be mixed and stirred for uniform, mixing adds the corresponding parts by weight processed through atomization successively
Limonene and plant toosedarin；5) then add the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；
6) while ultra violet lamp 40min, after stirring is cooled to 50 DEG C, puts in extruder, add hot-extrudable, vacuum
It is dried, prepares target product.
After testing, the flexility of material reaches 82.9Mpa, notch impact strength reaches 48.4MJ/m2。
Embodiment 5: one easily moulds antibacterial type 3D printed material, includes that following components is made according to parts by weight: ABS 135
Part；Light diffusing agent 6 parts；Initiator 6 parts；Cross-linking agent 18 parts；Coupling agent 18 parts；Concha Meretricis Seu Cyclinae powder 25 parts；Elemental sulfur 6
Part；Medical stone powder 3 parts；Walnut shell ultrafine powder 3 parts；Feather powder 6 parts；Limonene 4 parts；Plant toosedarin 16 parts；
Auxiliary agent 0.4 part.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein according to parts by weight, initiator includes that following components is made: light trigger 2 parts；Thermal initiator 4 parts.
Wherein coupling agent is the mixture of titanate coupling agent and silane coupler.
Wherein plant toosedarin is orcin.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.2 part；Toughener 0.2 part.
Preparation method comprises the steps: 1) ABS particle high-temperature is melted, add initiator and cross-linking agent mixes,
Grafting；2) it is cooled to 25 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing graft crosslinking
The ABS powder of agent；3) by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, core
Peach shell superfine powder, feather powder, medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform；4) will step
Rapid 3), the while that gains continuing to be mixed and stirred for uniform, mixing adds the corresponding parts by weight processed through atomization successively
Limonene and plant toosedarin；5) then add the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；
6) while ultra violet lamp 50min, after stirring is cooled to 55 DEG C, puts in extruder, add hot-extrudable, vacuum
It is dried, prepares target product.After testing, the flexility of material reaches 82.6Mpa, notch impact strength
Reach 48.2MJ/m2。
More than implementing row and the present invention is not constituted restriction, relevant staff is in the scope without departing from the technology of the present invention thought
In, carried out various changes and modifications, and all falls within protection scope of the present invention.
Claims (9)
1. easily mould antibacterial type 3D printed material for one kind, it is characterised in that include that following components is made according to parts by weight:
ABS 120～140 parts；Light diffusing agent 2～8 parts；Initiator 2～8 parts；Cross-linking agent 10～20 parts；Coupling agent 10～
20 parts；Concha Meretricis Seu Cyclinae powder 10～30 parts；Elemental sulfur 2～8 parts；Medical stone powder 1～4 parts；Walnut shell ultrafine powder 1～4 parts；
Limonene 1～6 parts；Plant toosedarin 4～20 parts；Auxiliary agent 0.2～0.4 part.
The most according to claim 1 easily mould antibacterial type 3D printed material, it is characterised in that according to parts by weight also
Including feather powder 2～8 parts.
The most according to claim 1 easily mould antibacterial type 3D printed material, it is characterised in that described light diffusing agent is
Organosilicon light diffusing agent.
The most according to claim 1 easily mould antibacterial type 3D printed material, it is characterised in that described initiator according to
Parts by weight include that following components is made: light trigger 1～3 parts；Thermal initiator 1～5 parts.
The most according to claim 1 easily mould antibacterial type 3D printed material, it is characterised in that described plant toosedarin
For Parmelia tinctorum Despr. extract.
The most according to claim 1 easily mould antibacterial type 3D printed material, it is characterised in that described plant toosedarin
For orcin.
The most according to claim 1 easily mould antibacterial type 3D printed material, it is characterised in that described auxiliary agent is according to weight
Amount number includes that following components is made: plasticizer 0.1～0.2 part；Toughener 0.1～0.2 part.
8. the preparation method easily moulding antibacterial type 3D printed material as described in claim 1～7, it is characterised in that include as
Lower step:
1) ABS particle high-temperature is melted, add initiator and cross-linking agent mixes, grafting；
2) it is cooled to 20 DEG C～30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize to obtain preparing being grafted and hand over
The ABS powder of connection agent；
3) by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, walnut shell ultrafine powder,
Medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform；
4) by step 3) gains are while continue to be mixed and stirred for uniform, and mixing adds the phase processed through atomization successively
Answer limonene and the plant toosedarin of parts by weight；
5) then add the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；
6) while ultra violet lamp 30～60min, after stirring is cooled to 50 DEG C～55 DEG C, puts in extruder, add
Hot-extrudable, vacuum drying, prepare target product.
The preparation method easily moulding antibacterial type 3D printed material the most according to claim 8, it is characterised in that described
Step 3) be: by step 2) the ABS powder that obtains and the Concha Meretricis Seu Cyclinae powder of corresponding parts by weight, elemental sulfur, walnut shell surpass
Micropowder, feather powder, medical stone powder, coupling agent and auxiliary agent, add hot mixing and high-speed stirred is uniform.
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Application publication date: 20160817 |
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