CN107266889A - A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point - Google Patents
A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point Download PDFInfo
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- CN107266889A CN107266889A CN201710640167.8A CN201710640167A CN107266889A CN 107266889 A CN107266889 A CN 107266889A CN 201710640167 A CN201710640167 A CN 201710640167A CN 107266889 A CN107266889 A CN 107266889A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention discloses a kind of conductive antibacterial 3D printing PLA silk materials of low melting point, conductive antibacterial MgO/Ag/PBS GO premixes and PLA, coupling agent including fusing point can be reduced, wherein, MgO/Ag/PBS GO premixes account for mass fraction 10 25%, PLA accounts for mass fraction 70 89%, coupling agent accounts for mass fraction 1 5%, and the mass percent sum of above each component content is 100%.The invention also discloses preparation method of the above-mentioned 3D printing with PLA silk materials.A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point of the present invention, solve the problem of existing carboxylated GO, MgO and Ag powder is difficult in melting process to be extruded, be difficult scattered.
Description
Technical field
The invention belongs to 3D printing consumptive material processing technique field, and in particular to a kind of conductive antibacterial 3D printing of low melting point is used
PLA silk materials, the invention further relates to preparation method of the above-mentioned 3D printing with PLA silk materials.
Background technology
3D printing technique, also known as increases material manufacturing technology, it is based on based on mathematical model file, with reference to metal, ceramics
Or under the high temperature such as plastic material can cohesive, the technology of product is prepared by successively printing type, mold design,
It is used widely in the fields such as industrial part manufacture, automobile, space flight and aviation, medical, decoration.At present, 3D printing technique is main
Including Selective Laser Sintering, Stereolithography technology, fusion sediment printing technique etc., wherein fusion sediment printing technique
It is a kind of most widely used most important technology.
In recent years, 3D printing technique turned into the western developed countries such as domestic and international study hotspot, especially America and Europe particularly
Pay attention to the research and development of 3D printing technique, this promotes developing rapidly for 3D printing equipment, material and technology.Domestic 3D printing
Technology starting is relatively late, and major part 3D printing consumptive material is also more from external import at present, is independently ground in spite of a small number of enterprises
Hair, but the domestic printing consumables produced has larger gap in terms of intensity, precision and other corresponding features with foreign countries,
Seriously hinder the fast development and commercial introduction application of domestic 3D printing industry.Meanwhile, 3D printing technique it is fast-developing right
Printing consumables proposes higher requirement, printing consumables certainly will towards highly versatile, mechanical property is good, precision is high, processing characteristics
Good and feature direction is developed.
Filament materials (silk material) are a kind of resin consumptive materials that fusion sediment printing technique is used.At present in fusion sediment printing
PLA (PLA) or acrylnitrile-butadiene-styrene copolymer (ABS) is generally used to be used as printing silk material in technology, its
Middle PLA has biological source and degradability, and preferably intensity and machinability is of greatest concern, but there is also multiple problems, than
Such as toughness is poor, silk thread frangibility, forming temperature are higher in process, meanwhile, have the PLA of antistatic behaviour and biocidal property concurrently
The document and patent of silk material are not yet found.
So far, Chinese patent CN 104356619A disclose a kind of preparation technology of the modified PLA material of 3D printer,
The patent is improved by adding toughener to PLA fragility, toughness is had larger change, but the not conduction to PLA silk materials
Studied with biocidal property.Beaten in addition, Chinese patent CN105903084A discloses a kind of 3D with antibacterial functions coating
Print porous support and preparation method thereof.Fibroin albumen/gentamicin is coated in gold by the patent by way of the electro-deposition of surface
Belong on cobalt-chromium (Co-Cr) porous support surfaces externally and internally, so that support has preferably antibiotic property, but the patent is not directed to
PLA's is antibacterial modified.
The content of the invention
It is an object of the invention to provide a kind of conductive antibacterial 3D printing PLA silk materials of low melting point, existing carboxyl is solved
Change the problem of GO, MgO and Ag powder are difficult in melting process to be extruded, be difficult scattered.
It is a further object to provide preparation method of the above-mentioned 3D printing with PLA silk materials.
The first technical scheme of the present invention is that a kind of conductive antibacterial 3D printing PLA silk materials of low melting point are wrapped
The conductive antibacterial MgO/Ag/PBS-GO premixes that can reduce fusing point and PLA, coupling agent are included, wherein, MgO/Ag/PBS-GO is pre-
Batch mixing accounts for mass fraction 10-25%, PLA and accounts for mass fraction 70-89%, and coupling agent accounts for mass fraction 1-5%, and above each component contains
The mass percent sum of amount is 100%.
The characteristics of the first technical scheme of the present invention, also resides in：
MgO/Ag/PBS-GO premixes include MgO, Ag, PBS, GO-COOH, wherein, MgO accounts for mass fraction 0.5-5%,
Ag accounts for mass fraction 0.5-3%, PBS and accounts for mass fraction 88-98%, and carboxylated GO accounts for mass fraction 0.5-2%, DCP and accounts for quality
Fraction 0.5-2%, the mass percent sum of above each component content is 100%.
Second of technical scheme of the present invention be, a kind of conductive antibacterial 3D printing PLA silk materials of low melting point
Preparation method, be specially：The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced by preparing first, then using system
The MgO/Ag/PBS-GO premixes got ready are prepared into 3D printing PLA silk materials with PLA melting extrusions.
The characteristics of second of technical scheme of the invention, also resides in：
The preparation method of MgO/Ag/PBS-GO premixes is：It is matrix material from full biological source and degradable PBS
Conductive GO-COOH, is incorporated into PBS, realizes GO-COOH high dispersive, pass through sonic oscillation by material by graft reaction
It will can reduce the MgO of fusing point and the Ag powder of bacteriostasis is uniformly dispersed in the PBS-GO aqueous solution, MgO/Ag/ is made after drying
PBS-GO premixes.
The preparation method of MgO/Ag/PBS-GO premixes is specially：By carboxylated GO and PBS pour into 50-80 DEG C acetone/
In ethanol solution, appropriate DCP is instilled again after carboxylated GO and PBS are completely dissolved, and keeps steady temperature to be stirred for mixing 4-
Obtain the PBS-GO aqueous solution within 12 hours；Then MgO and Ag are added in the PBS-GO aqueous solution, and carry out sonic oscillation and disperse 1-
2 hours, the vacuum drying oven that the MgO/Ag/PBS-GO aqueous solution finally is moved into 50-80 DEG C was fully dried 4-8 hours, dried
Compound crushes in disintegrating machine and finally gives granular MgO/Ag/PBS-GO premixes, and wherein PBS accounts for mass fraction 88-
98%, carboxylated GO account for mass fraction 0.5-2%, and DCP accounts for mass fraction 0.5-2%, and MgO accounts for mass fraction 0.5-5%, and Ag is accounted for
Mass fraction 0.5-3%, the mass percent sum of above each component content is 100%, and acetone/ethanol solution is carboxylated GO
With 3-5 times of PBS cumulative volumes, acetone/ethanol=1/3-1/6 in acetone/ethanol solution.
3D printing PLA silk materials are prepared into using the MgO/Ag/PBS-GO premixes prepared and PLA melting extrusions specific
For：By a certain amount of conductive antibacterial MgO/Ag/PBS-GO premixes for reducing fusing point, coupling agent and fully drying
PLA is premixed in high mixer, and then by it, melting mixing is granulated in double screw extruder, during extrusion mixing, in advance
Extruding pelletization again after batch mixing, coupling agent and the abundant melting mixings of PLA, is finally made granular MgO/Ag/PBS-GO/PLA and answers
Condensation material, wherein, premix, which accounts for mass fraction 10-25%, coupling agent and accounts for mass fraction 1-5%, PLA, accounts for mass fraction 70-
89%, finally, the granular MgO/Ag/PBS-GO/PLA composites dried carry out extrusion drawing by single screw extrusion machine again
Silk, prepares 3D printing PLA silk materials.
Double screw extruder extrudes 160-210 DEG C of processing temperature, rotating speed 60-120r/min.
Single screw extrusion machine extrudes 120-160 DEG C of processing temperature, rotating speed 30-60r/min.
The port mould diameter 3mm or 1.75mm of single screw extrusion machine.
The beneficial effects of the invention are as follows：A kind of low melting point of the present invention conductive antibacterial 3D printing PLA silk materials and its preparation
Method, is grafted in the solution using conductive carboxylated graphene oxide (GO) and poly butylene succinate (PBS)
Reaction obtains the conductive PBS-GO materials of high dispersive, then will can reduce the magnesia (MgO) and conduction of fusing point by sonic oscillation
Silver (Ag) powder of bacteriostasis is homogeneous to be dispersed in the PBS-GO aqueous solution, so as to obtain MgO/Ag/PBS-GO premixes after drying,
The premix collection can toughness reinforcing, it is possible to decrease fusing point, conductive and antibacterial in one.By screw extruder by functional premix with
PLA melt blendings prepare MgO/Ag/PBS-GO/PLA silk materials, and the silk material has low fusing point, and good conduction and bacteriostasis will
The workability and feature of 3D printing PLA silk materials are pushed further into, PLA silk materials is expanded and is more widely applied.
Brief description of the drawings
Fig. 1 is the flow chart of 3D printing PLA silk material preparation methods of the present invention；
Fig. 2 is SEM (SEM) figure of MgO/Ag/PBS-GO premixes in the present invention；
Fig. 3 is the SEM figures of MgO/Ag/PBS-GO/PLA silk materials in the present invention；
Fig. 4 is the melting curve figure of MgO/Ag/PBS-GO/PLA silk materials in the present invention；
Fig. 5 is the electric conductivity figure of MgO/Ag/PBS-GO/PLA silk materials in the present invention；
Fig. 6 is the bacteriostasis property figure of MgO/Ag/PBS-GO/PLA pellets in the present invention.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including the conductive antibacterial of fusing point can be reduced
MgO/Ag/PBS-GO premixes and PLA (PLA), coupling agent, wherein, MgO/Ag/PBS-GO premixes account for mass fraction 10-
25%, PLA account for mass fraction 70-89%, and coupling agent accounts for mass fraction 1-5%, the mass percent of above each component content it
With for 100%.
Wherein, MgO/Ag/PBS-GO composites include MgO (magnesia), Ag (silver), PBS (poly-succinic acid-butanediols
Ester), GO-COOH (carboxylated graphene oxide), wherein, MgO accounts for mass fraction 0.5-5%, Ag and accounts for mass fraction 0.5-3%,
PBS accounts for mass fraction 88-98%, and carboxylated GO accounts for mass fraction 0.5-2%, DCP (cumyl peroxide) and accounts for mass fraction
0.5-2%, the mass percent sum of above each component content is 100%.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, be specially：Preparing first can
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point are reduced, then using the premix prepared and PLA melting extrusion systems
The standby 3D printing PLA silk material antibacterial into low melting point conduction.
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced and be by preparing：From full biological source and can
The PBS of degraded is matrix material, and conductive GO-COOH is incorporated into PBS by graft reaction, GO-COOH height is realized
It is scattered, the MgO of fusing point will can be reduced by sonic oscillation and the Ag powder of bacteriostasis is uniformly dispersed in the PBS-GO aqueous solution,
MgO/Ag/PBS-GO premixes are made after drying, are specially：Carboxylated GO and PBS is dissolved in 50-80 DEG C of acetone/ethanol molten
In liquid (acetone/ethanol=1/3~1/6, the volume of acetone/ethanol solution is 3~5 times of carboxylated GO and PBS cumulative volumes), treat
Carboxylated GO and PBS instills appropriate DCP again after being completely dissolved, keep steady temperature to be stirred for mixing and obtain PBS- in 4-12 hours
The GO aqueous solution；Then MgO and Ag are added in the PBS-GO aqueous solution, and carry out sonic oscillation and disperseed 1-2 hours, finally will
The vacuum drying oven that the MgO/Ag/PBS-GO aqueous solution moves to 50-80 DEG C is fully dried 4-8 hours, and dried compound is broken
Crushed in machine and finally give granular MgO/Ag/PBS-GO premixes.Wherein, MgO/Ag/PBS-GO premixes include MgO
(magnesia), which accounts for mass fraction 0.5-5%, Ag (silver) powder and accounts for mass fraction 0.5-3%, GO (carboxylated graphene oxide), accounts for matter
Amount fraction 0.5-2%, DCP (cumyl peroxide) account for mass fraction 0.5-2%, PBS (poly butylene succinate) and account for matter
Fraction 88-98% is measured, the mass percent sum of above each component content is 100%.
Then, 3D printing PLA is prepared into using the MgO/Ag/PBS-GO premixes and PLA melting extrusions that prepare
Material is specially：By a certain amount of conductive antibacterial MgO/Ag/PBS-GO premixes for reducing fusing point, coupling agent with fully doing
Dry PLA is premixed in high mixer, then by its in double screw extruder melting mixing granulate, double screw extruder squeeze
Go out processing temperature for 160-210 DEG C, rotating speed is 60-120r/min.During extrusion mixing, premix, coupling agent and PLA fill
Extruding pelletization again after point melting mixing, is finally made granular MgO/Ag/PBS-GO/PLA composites, wherein, premix
Account for mass fraction 10-25%, coupling agent and account for mass fraction 1-5%, PLA and account for mass fraction 70-89%.Finally, dry particle
The MgO/Ag/PBS-GO/PLA composites of shape carry out extrusion wire drawing by single screw extrusion machine again, prepare 3D printing with PLA
Material, the extrusion processing temperature of single screw extrusion machine is 120-160 DEG C, and rotating speed is 30-60r/min, in order to meet current 3D printing
Equipment requirement, controls silk material a diameter of 3mm or 1.75mm, and its Single screw extrusion port mould diameter is 3mm or 1.75mm.
Embodiment 1
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including the MgO/Ag/ that mass fraction is 21%
The coupling agent that PLA that PBS-GO premixes and mass fraction are 75%, mass fraction are 4%.MgO/Ag/PBS-GO premix bags
The MgO that mass fraction is 5% is included, mass fraction is 3% Ag, and mass fraction is 88% PBS, and mass fraction is 2% carboxylic
Base GO, mass fraction is 2% DCP.
The preparation method of the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point of the present invention, as shown in figure 1, being specially：
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced by preparing first, by mass fraction for 2% carboxylated GO with
Mass fraction for 88% PBS pour into 75 DEG C acetone/ethanol solution (acetone/ethanol=1/5, acetone/ethanol solution be carboxyl
Change GO and PBS cumulative volumes 5 times) in, instill the DCP that mass fraction is 2% again after carboxylated GO and PBS are completely dissolved, protect
Hold steady temperature be stirred for mixing obtain the PBS-GO aqueous solution within 8 hours；Then by mass fraction be 5% MgO and mass fraction
It is added to for 3% Ag in the PBS-GO aqueous solution, and carries out sonic oscillation and disperseed 1.5 hours, finally by MgO/Ag/PBS-GO water
The vacuum drying oven that solution moves to 70 DEG C is fully dried 5 hours, and dried compound crushes in disintegrating machine and finally gives particle
The MgO/Ag/PBS-GO premixes of shape, are illustrated in figure 2 the SEM (SEM) of MgO/Ag/PBS-GO premixes
Figure；Then the MgO/Ag/PBS-GO premixes for being 21% by mass fraction, mass fraction are 4% and mass fraction is 75%
Fully dry PLA is premixed in high mixer, and then by it, melting mixing is granulated in double screw extruder, twin-screw extrusion
The extrusion processing temperature of machine is 160 DEG C, and rotating speed is 120r/min, during extrusion mixing, and premix, coupling agent and PLA fill
Extruding pelletization again after point melting mixing, is finally made granular MgO/Ag/PBS-GO/PLA composites, finally, dries
Granular MgO/Ag/PBS-GO/PLA composites carry out extrusion wire drawing by single screw extrusion machine again, prepare 3D printing and use
PLA silk materials, the extrusion processing temperature of single screw extrusion machine is 160 DEG C, and rotating speed is 45r/min, its Single screw extrusion port mould diameter
For 3mm.It is illustrated in figure 3 the SEM figures of MgO/Ag/PBS-GO/PLA silk materials.
Finally, a series of materials have been carried out into melting temperature, electric conductivity and biocidal property to test, has found MgO/Ag/PBS-
The addition of GO composites can make PLA melt processing temperatures reduce by 20 DEG C or so, and resistivity have dropped 5 number magnitudes,
Fungistatic effect is also significantly improved, and corresponding melting temperature is as shown in figure 4, electric conductivity is as shown in figure 5, bacteriostasis property such as Fig. 6 institutes
Show that (Fig. 6 (a) show MgO/Ag/PBS-GO/PLA bacteriostasis property figure, and Fig. 6 (b) show the antibacterial of MgO/PBS-GO/PLA
Performance map).
Embodiment 2
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including the MgO/Ag/ that mass fraction is 25%
The coupling agent that PLA that PBS-GO premixes and mass fraction are 70%, mass fraction are 5%.MgO/Ag/PBS-GO premix bags
The MgO that mass fraction is 0.5% is included, mass fraction is 0.5% Ag, and mass fraction is 98% PBS, and mass fraction is
0.5% carboxylated GO, mass fraction is 0.5% DCP.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, be specially：Preparing first can
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point are reduced, by the carboxylated GO and mass fraction that mass fraction is 0.5%
For 98% PBS pour into 75 DEG C acetone/ethanol solution (acetone/ethanol=1/6, acetone/ethanol solution be carboxylated GO with
3 times of PBS cumulative volumes) in, instill the DCP that mass fraction is 0.5% again after carboxylated GO and PBS are completely dissolved, keep permanent
Constant temperature degree is stirred for mixing and obtains the PBS-GO aqueous solution in 4 hours；Then the MgO and mass fraction for being 0.5% by mass fraction be
0.5% Ag is added in the PBS-GO aqueous solution, and carries out sonic oscillation scattered 1 hour, finally that MgO/Ag/PBS-GO is water-soluble
The vacuum drying oven that liquid moves to 50 DEG C is fully dried 4 hours, and dried compound crushes in disintegrating machine and finally gives graininess
MgO/Ag/PBS-GO premixes, the MgO/Ag/PBS-GO premixes for being then 25% by mass fraction, mass fraction are 5%
PLA with mass fraction for 70% abundant drying is premixed in high mixer, then melts it in double screw extruder
Mixing granulation, the extrusion processing temperature of double screw extruder is 210 DEG C, and rotating speed is 60r/min, during extrusion mixing, in advance
Extruding pelletization again after batch mixing, coupling agent and the abundant melting mixings of PLA, is finally made granular MgO/Ag/PBS-GO/PLA and answers
Condensation material, finally, the granular MgO/Ag/PBS-GO/PLA composites dried are extruded by single screw extrusion machine again
Wire drawing, prepares 3D printing PLA silk materials, the extrusion processing temperature of single screw extrusion machine is 120 DEG C, and rotating speed is 40r/min, its list
Screw Extrusion port mould diameter is 1.75mm.
Embodiment 3
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including the MgO/Ag/ that mass fraction is 10%
The coupling agent that PLA that PBS-GO premixes and mass fraction are 89%, mass fraction are 1%.MgO/Ag/PBS-GO premix bags
The MgO that mass fraction is 2% is included, mass fraction is 1% Ag, and mass fraction is 94% PBS, and mass fraction is 1.5%
Carboxylated GO, mass fraction is 1.5% DCP.
The preparation method of the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point of the present invention, as shown in figure 1, being specially：
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced by preparing first, by the carboxylated GO that mass fraction is 1.5%
With mass fraction for 94% PBS pour into 50 DEG C acetone/ethanol solution (acetone/ethanol=1/4, acetone/ethanol solution be carboxylic
4 times of base GO and PBS cumulative volumes) in, it is 1.5% to instill mass fraction again after carboxylated GO and PBS are completely dissolved
DCP, keeps steady temperature to be stirred for mixing and obtains the PBS-GO aqueous solution in 6 hours；Then by mass fraction for 2% MgO and matter
Measure fraction to be added in the PBS-GO aqueous solution for 1% Ag, and carry out sonic oscillation and disperse 2 hours, finally by MgO/Ag/PBS-
The vacuum drying oven that the GO aqueous solution moves to 75 DEG C is fully dried 8 hours, and dried compound is crushed in disintegrating machine and finally given
Granular MgO/Ag/PBS-GO premixes, MgO/Ag/PBS-GO premixes then by mass fraction for 10%, quality point
Number is that the PLA of the 1% abundant drying for being 89% with mass fraction is premixed in high mixer, then by it in double screw extruder
Middle melting mixing granulation, the extrusion processing temperature of double screw extruder is 180 DEG C, and rotating speed is 90r/min, in extrusion mixing process
In, granular MgO/Ag/PBS-GO/ is finally made in extruding pelletization again after premix, coupling agent and the abundant melting mixings of PLA
PLA composites, finally, the granular MgO/Ag/PBS-GO/PLA composites dried enter by single screw extrusion machine again
Row extrusion wire drawing, prepares 3D printing PLA silk materials, the extrusion processing temperature of single screw extrusion machine is 140 DEG C, and rotating speed is 50r/
Min, its Single screw extrusion port mould diameter is 3mm.
Embodiment 4
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including the MgO/Ag/ that mass fraction is 18%
The coupling agent that PLA that PBS-GO premixes and mass fraction are 80%, mass fraction are 2%.MgO/Ag/PBS-GO premix bags
The MgO that mass fraction is 3.5% is included, mass fraction is 2.5% Ag, and mass fraction is 91% PBS, and mass fraction is 1%
Carboxylated GO, mass fraction be 2% DCP.
The preparation method of the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point of the present invention, as shown in figure 1, being specially：
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced by preparing first, by mass fraction for 1% carboxylated GO with
Mass fraction for 91% PBS pour into 80 DEG C acetone/ethanol solution (acetone/ethanol=1/3, acetone/ethanol solution be carboxyl
Change GO and PBS cumulative volumes 3.5 times) in, instill the DCP that mass fraction is 2% again after carboxylated GO and PBS are completely dissolved,
Keep steady temperature to be stirred for mixing and obtain the PBS-GO aqueous solution in 12 hours；Then by mass fraction for 3.5% MgO and quality
Fraction is added in the PBS-GO aqueous solution for 2.5% Ag, and it is scattered 15 minutes 1 hour to carry out sonic oscillation, finally by MgO/
The vacuum drying oven that the Ag/PBS-GO aqueous solution moves to 60 DEG C is fully dried 7 hours, and dried compound is crushed most in disintegrating machine
Obtain granular MgO/Ag/PBS-GO premixes eventually, then by mass fraction for 18% MgO/Ag/PBS-GO premixes,
Mass fraction is that the PLA of the 2% abundant drying for being 80% with mass fraction is premixed in high mixer, then by it in twin-screw
Melting mixing is granulated in extruder, and the extrusion processing temperature of double screw extruder is 170 DEG C, and rotating speed is 75r/min, mixed in extrusion
During conjunction, granular MgO/Ag/ is finally made in extruding pelletization again after premix, coupling agent and the abundant melting mixings of PLA
PBS-GO/PLA composites, finally, the granular MgO/Ag/PBS-GO/PLA composites dried are squeezed by single screw rod again
Go out machine and carry out extrusion wire drawing, prepare 3D printing PLA silk materials, the extrusion processing temperature of single screw extrusion machine is 130 DEG C, and rotating speed is
30/min, its Single screw extrusion port mould diameter is 1.75mm.
Embodiment 5
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including the MgO/Ag/ that mass fraction is 13%
The coupling agent that PLA that PBS-GO premixes and mass fraction are 84%, mass fraction are 3%.MgO/Ag/PBS-GO premix bags
The MgO that mass fraction is 1% is included, mass fraction is 1.5% Ag, and mass fraction is 96% PBS, and mass fraction is 0.5%
Carboxylated GO, mass fraction be 1% DCP.
The preparation method of the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point of the present invention, as shown in figure 1, being specially：
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced by preparing first, by the carboxylated GO that mass fraction is 0.5%
Pour into 60 DEG C of acetone/ethanol solution for 96% PBS with mass fraction (acetone/ethanol=3/10, acetone/ethanol solution is
4.5 times of carboxylated GO and PBS cumulative volumes) in, it is 1% to instill mass fraction again after carboxylated GO and PBS are completely dissolved
DCP, keeps steady temperature to be stirred for mixing and obtains the PBS-GO aqueous solution in 10 hours；Then by mass fraction for 1% MgO and matter
Measure fraction to be added in the PBS-GO aqueous solution for 1.5% Ag, and carry out sonic oscillation and disperse 45 minutes 1 hour, finally will
The vacuum drying oven that the MgO/Ag/PBS-GO aqueous solution moves to 80 DEG C is fully dried 6 hours, and dried compound is broken in disintegrating machine
It is broken to finally give granular MgO/Ag/PBS-GO premixes, then mass fraction is premixed for 13% MgO/Ag/PBS-GO
Material, the PLA that mass fraction is the 3% abundant drying for being 84% with mass fraction are premixed in high mixer, then by it double
Melting mixing is granulated in screw extruder, and the extrusion processing temperature of double screw extruder is 200 DEG C, and rotating speed is 105r/min,
During extrusion mixing, extruding pelletization again after premix, coupling agent and the abundant melting mixings of PLA is finally made granular
MgO/Ag/PBS-GO/PLA composites, finally, the granular MgO/Ag/PBS-GO/PLA composites dried pass through again
Single screw extrusion machine carries out extrusion wire drawing, prepares 3D printing PLA silk materials, the extrusion processing temperature of single screw extrusion machine is 150
DEG C, rotating speed is 60r/min, and its Single screw extrusion port mould diameter is 3mm.
Claims (9)
1. the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point, it is characterised in that including the conductive antibacterial of fusing point can be reduced
MgO/Ag/PBS-GO premixes and PLA, coupling agent, wherein, MgO/Ag/PBS-GO premixes account for mass fraction 10-25%,
PLA accounts for mass fraction 70-89%, and coupling agent accounts for mass fraction 1-5%, and the mass percent sum of above each component content is
100%.
2. the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point according to claim 1, it is characterised in that described
MgO/Ag/PBS-GO premixes include MgO, Ag, PBS, GO-COOH, wherein, MgO accounts for mass fraction 0.5-5%, Ag and accounts for quality
Fraction 0.5-3%, PBS account for mass fraction 88-98%, and carboxylated GO accounts for mass fraction 0.5-2%, DCP and accounts for mass fraction 0.5-
2%, the mass percent sum of above each component content is 100%.
3. the preparation method of the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point, it is characterised in that be specially：Make first
It is standby to reduce the conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point, then using the MgO/Ag/PBS-GO premixs prepared
Material is prepared into 3D printing PLA silk materials with PLA melting extrusions.
4. a kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point according to claim 3, its feature
It is, the preparation method of the MgO/Ag/PBS-GO premixes is：It is matrix material from full biological source and degradable PBS
Conductive GO-COOH, is incorporated into PBS, realizes GO-COOH high dispersive, pass through sonic oscillation by material by graft reaction
It will can reduce the MgO of fusing point and the Ag powder of bacteriostasis is uniformly dispersed in the PBS-GO aqueous solution, MgO/Ag/ is made after drying
PBS-GO premixes.
5. a kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point according to claim 4, its feature
It is, the preparation method of the MgO/Ag/PBS-GO premixes is specially：Carboxylated GO and PBS are poured into the third of 50-80 DEG C
In ketone/ethanol solution, appropriate DCP is instilled again after carboxylated GO and PBS are completely dissolved, keeps steady temperature to be stirred for mixing
Obtain the PBS-GO aqueous solution within 4-12 hours；Then MgO and Ag are added in the PBS-GO aqueous solution, and carry out sonic oscillation and disperseed
1-2 hours, the vacuum drying oven that the MgO/Ag/PBS-GO aqueous solution finally is moved into 50-80 DEG C was fully dried 4-8 hours, after drying
Compound in disintegrating machine crush finally give granular MgO/Ag/PBS-GO premixes, wherein PBS accounts for mass fraction
88-98%, carboxylated GO account for mass fraction 0.5-2%, and DCP accounts for mass fraction 0.5-2%, MgO and accounts for mass fraction 0.5-5%,
Ag accounts for mass fraction 0.5-3%, and the mass percent sum of above each component content is 100%, and acetone/ethanol solution is carboxyl
Acetone/ethanol=1/3-1/6 in change GO and PBS cumulative volumes 3-5 times, acetone/ethanol solution.
6. a kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point according to claim 3, its feature
It is, it is described that 3D printing PLA silk materials tool is prepared into using the MgO/Ag/PBS-GO premixes prepared and PLA melting extrusions
Body is：By a certain amount of conductive antibacterial MgO/Ag/PBS-GO premixes for reducing fusing point, coupling agent and fully drying
PLA is premixed in high mixer, and then by it, melting mixing is granulated in double screw extruder, during extrusion mixing, in advance
Extruding pelletization again after batch mixing, coupling agent and the abundant melting mixings of PLA, is finally made granular MgO/Ag/PBS-GO/PLA and answers
Condensation material, wherein, premix, which accounts for mass fraction 10-25%, coupling agent and accounts for mass fraction 1-5%, PLA, accounts for mass fraction 70-
89%, finally, the granular MgO/Ag/PBS-GO/PLA composites dried carry out extrusion drawing by single screw extrusion machine again
Silk, prepares 3D printing PLA silk materials.
7. a kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point according to claim 6, its feature
It is, the double screw extruder extrudes 160-210 DEG C of processing temperature, rotating speed 60-120r/min.
8. a kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point according to claim 6, its feature
It is, the single screw extrusion machine extrudes 120-160 DEG C of processing temperature, rotating speed 30-60r/min.
9. a kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point according to claim 6, its feature
It is, the port mould diameter 3mm or 1.75mm of the single screw extrusion machine.
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