CN107266889B - 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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- CN107266889B CN107266889B CN201710640167.8A CN201710640167A CN107266889B CN 107266889 B CN107266889 B CN 107266889B CN 201710640167 A CN201710640167 A CN 201710640167A CN 107266889 B CN107266889 B CN 107266889B
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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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- C—CHEMISTRY; METALLURGY
- 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, conduction including fusing point can be reduced antibacterial 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%, coupling agent accounts for mass fraction 1 5%, and the sum of mass percent of the above components content is 100%.The invention also discloses the above-mentioned 3D printing preparation methods of 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 problems, such as that existing carboxylated GO, MgO and Ag powder is difficult in melting process and squeeze out, are not easy to disperse.
Description
Technical field
The invention belongs to 3D printing consumptive material processing technique fields, and in particular to a kind of conductive antibacterial 3D printing use of low melting point
PLA silk materials, the invention further relates to the above-mentioned 3D printing preparation methods of PLA silk materials.
Background technology
3D printing technique, also known as increases material manufacturing technology, it is based on based on digital model file, in conjunction with metal, ceramics
Or under the high temperature such as plastic material can adhesiveness, 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.Currently, 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 had become the western developed countries such as domestic and international research hotspot, especially America and Europe particularly
Pay attention to the research and development of 3D printing technique, this promotes the rapid development of 3D printing equipment, material and technology.Domestic 3D printing
Technology starts to walk relatively late, and major part 3D printing consumptive material is independently ground also mostly from external import in spite of a small number of enterprises at present
Hair, but the domestic printing consumables produced has larger gap in intensity, precision and other corresponding functionality etc. with foreign countries,
Seriously hinder fast development and the commercial introduction application of domestic 3D printing industry.Meanwhile the fast development of 3D printing technique is right
More stringent requirements are proposed for printing consumables, and printing consumables certainly will be towards versatile, mechanical property is good, precision is high, processing performance
Good and functional direction is developed.
Filament materials (silk material) are a kind of resin consumptive materials that fusion sediment printing technique uses.It is printed at present in fusion sediment
Polylactic acid (PLA) or acrylnitrile-butadiene-styrene copolymer (ABS) is generally used to be used as printing silk material in technology,
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 property 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 process of the modified PLA material of 3D printer,
The patent improves the brittleness of PLA by adding toughener, so that toughness is had larger change, but not to the conduction of PLA silk materials
It is studied with biocidal property.It is beaten in addition, Chinese patent CN 105903084A disclose 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, to make holder have preferably antibiotic property, but the patent is not directed to
PLA's is antibacterial modified.
Invention content
The object of the present invention is to provide a kind of conductive antibacterial 3D printing PLA silk materials of low melting point, solve existing carboxyl
Change GO, MgO and Ag powder difficult the problem of squeezing out, being not easy to disperse in melting process.
It is a further object to provide the above-mentioned 3D printing preparation methods of PLA silk materials.
The first technical solution of the present invention is a kind of conductive antibacterial 3D printing PLA silk materials of low melting point,
Conduction including fusing point can be reduced antibacterial MgO/Ag/PBS-GO premixes and PLA, coupling agent, wherein MgO/Ag/PBS-GO
Premix accounts for mass fraction 10-25%, PLA and accounts for mass fraction 70-89%, and coupling agent accounts for mass fraction 1-5%, the above components
The sum of mass percent of content is 100%.
The characteristics of the first technical solution of the present invention, also resides in：
MgO/Ag/PBS-GO premixes include MgO, Ag, PBS, GO-COOH, wherein and 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
Score 0.5-2%, the sum of mass percent of the above components content are 100%.
Second of technical solution of the present invention is a kind of conductive antibacterial 3D printing PLA silk materials of low melting point
Preparation method, 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 solution of the invention, also resides in：
The preparation method of MgO/Ag/PBS-GO premixes is：It is matrix material to select full biological source and degradable PBS
Conductive GO-COOH is introduced into PBS by graft reaction, realizes the high dispersive of GO-COOH, pass through sonic oscillation by material
The Ag powder of the MgO that fusing point can be reduced and bacteriostasis is uniformly dispersed in PBS-GO aqueous solutions, MgO/ is made after dry
Ag/PBS-GO premixes.
The preparation method of 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, suitable DCP is instilled again after carboxylated GO and PBS are completely dissolved, temperature is kept constant and is stirred for mixing
It closes 4-12 hours and obtains PBS-GO aqueous solutions；Then MgO and Ag are added in PBS-GO aqueous solutions, and carry out sonic oscillation
MgO/Ag/PBS-GO aqueous solutions are finally moved to 50-80 DEG C of vacuum drying oven and fully dried 4-8 hours, done by dispersion 1-2 hours
Mixture after dry is crushed in crusher finally obtains granular MgO/Ag/PBS-GO premixes, and wherein PBS accounts for quality
Score 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 account for mass fraction 0.5-3%, and the sum of mass percent of the above components content is 100%, and acetone/ethanol solution is
3-5 times of carboxylated GO and PBS total volumes, acetone/ethanol=1/3-1/6 in acetone/ethanol solution.
It is specific that 3D printing PLA silk materials with PLA melting extrusions are prepared into using the MgO/Ag/PBS-GO premixes prepared
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
It is multiple that granular MgO/Ag/PBS-GO/PLA is finally made in extruding pelletization again after batch mixing, coupling agent and the abundant melting mixings of PLA
Condensation material, wherein premix accounts for mass fraction 10-25%, coupling agent accounts for mass fraction 1-5%, PLA and accounts for mass fraction 70-
89%, finally, dry granular MgO/Ag/PBS-GO/PLA composite materials are squeezed out using single screw extrusion machine
Wire drawing prepares 3D printing PLA silk materials.
Double screw extruder squeezes out 160-210 DEG C of processing temperature, rotating speed 60-120r/min.
Single screw extrusion machine squeezes out 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 using conductive carboxylated graphene oxide (GO) with poly butylene succinate (PBS) in the solution
The PBS-GO materials of high dispersive conduction are obtained by the reaction, then will can reduce the magnesia (MgO) and conduction of fusing point by sonic oscillation
Silver (Ag) powder of bacteriostasis is uniform to be dispersed in PBS-GO aqueous solutions, to obtain MgO/Ag/PBS-GO premixes after drying,
The premix collection can toughening, fusing point can be reduced, it is conductive and antibacterial in one.By screw extruder by functional premix with
PLA melt blendings prepare MgO/Ag/PBS-GO/PLA silk materials, which has low fusing point, and good conduction and bacteriostasis will
It is pushed further into the workability and functionality of 3D printing PLA silk materials, PLA silk materials is expanded and is more widely applied.
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 scanning electron microscope (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 (b) is the bacteriostasis property figure of MgO/Ag/PBS-GO/PLA pellets in the present invention.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
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 (polylactic acid), 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 the above components content
The sum of be 100%.
Wherein, MgO/Ag/PBS-GO composite materials 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 sum of mass percent of the above components content are 100%.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, specially：Preparing first can
The antibacterial MgO/Ag/PBS-GO premixes of the conduction of fusing point are reduced, then using the premix prepared and PLA melting extrusion systems
The standby 3D printing PLA silk material antibacterial at low melting point conduction.
The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced by, which preparing, is：Select full biological source and can
The PBS of degradation is basis material, and conductive GO-COOH is introduced into PBS by graft reaction, realizes the height of GO-COOH
Dispersion, PBS-GO aqueous solutions are uniformly dispersed in by sonic oscillation by the Ag powder of the MgO that can reduce fusing point and bacteriostasis
In, MgO/Ag/PBS-GO premixes are made after dry, specially：Carboxylated GO and PBS are dissolved in 50-80 DEG C of acetone/second
Alcoholic solution (acetone/ethanol=1/3~1/6, the volume of acetone/ethanol solution are 3~5 times of carboxylated GO and PBS total volumes)
In, suitable DCP is instilled again after carboxylated GO and PBS are completely dissolved, and is kept constant temperature and is stirred for mixing 4-12 hours
To PBS-GO aqueous solutions；Then MgO and Ag are added in PBS-GO aqueous solutions, and carry out sonic oscillation and disperses 1-2 hours,
It is fully 4-8 hours dry that MgO/Ag/PBS-GO aqueous solutions are finally moved to 50-80 DEG C of vacuum drying oven, the mixture after drying
It is crushed in crusher and finally obtains granular MgO/Ag/PBS-GO premixes.Wherein, MgO/Ag/PBS-GO premixes packet
It includes MgO (magnesia) and accounts for mass fraction 0.5-5%, Ag (silver) powder and account for mass fraction 0.5-3%, GO (carboxylated graphite oxide
Alkene) it accounts for mass fraction 0.5-2%, DCP (cumyl peroxide) and accounts for mass fraction 0.5-2%, PBS (poly-succinic acid-butanediol
Ester) mass fraction 88-98% is accounted for, the sum of mass percent of the above components 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
Dry PLA is premixed in high mixer, and then by it, melting mixing is granulated in double screw extruder, double screw extruder
It is 160-210 DEG C to squeeze out processing temperature, rotating speed 60-120r/min.During extrusion mixing, premix, coupling agent with
Granular MgO/Ag/PBS-GO/PLA composite materials are finally made in extruding pelletization again after the abundant melting mixings of PLA, wherein
Premix accounts for mass fraction 10-25%, coupling agent accounts for mass fraction 1-5%, PLA and accounts for mass fraction 70-89%.Finally, dry
Granular MgO/Ag/PBS-GO/PLA composite materials carry out extrusion wire drawing using single screw extrusion machine, prepare 3D printing
Extrusion processing temperature with PLA silk materials, single screw extrusion machine is 120-160 DEG C, rotating speed 30-60r/min, current in order to meet
3D printing equipment requirement, controls a diameter of 3mm or 1.75mm of silk material, and 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 mass fraction is 21% MgO/
The coupling agent that PLA that Ag/PBS-GO premixes and mass fraction are 75%, mass fraction are 4%.MgO/Ag/PBS-GO is premixed
Material includes the MgO that mass fraction is 5%, the Ag that mass fraction is 3%, the PBS that mass fraction is 88%, mass fraction 2%
Carboxylated GO, mass fraction be 2% DCP.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, as shown in Fig. 1, specifically
For：The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point, the carboxylated for being 2% by mass fraction can be reduced by preparing first
The PBS that GO is 88% with mass fraction pours into 75 DEG C of acetone/ethanol solution (acetone/ethanol=1/5, acetone/ethanol solution
For carboxylated GO and 5 times of PBS total volumes) in, it is 2% to instill mass fraction again after carboxylated GO and PBS are completely dissolved
DCP, keeps constant temperature and is stirred for mixing and obtain PBS-GO aqueous solutions in 8 hours；Then the MgO and matter by mass fraction for 5%
The Ag that amount score is 3% is added in PBS-GO aqueous solutions, and is carried out sonic oscillation and disperseed 1.5 hours, finally by MgO/Ag/
The vacuum drying oven that PBS-GO aqueous solutions move to 70 DEG C is fully 5 hours dry, and the mixture after drying is crushed final in crusher
Granular MgO/Ag/PBS-GO premixes are obtained, the scanning electron microscopy of MgO/Ag/PBS-GO premixes is illustrated in figure 2
Mirror (SEM) figure；Then it is 4% to be with mass fraction by MgO/Ag/PBS-GO premixes that mass fraction is 21%, mass fraction
75% fully dry PLA is premixed in high mixer, and then by it, melting mixing is granulated in double screw extruder, double spiral shells
The extrusion processing temperature of bar extruder is 160 DEG C, rotating speed 120r/min, during extrusion mixing, premix, coupling agent
With extruding pelletization again after the abundant melting mixings of PLA, granular MgO/Ag/PBS-GO/PLA composite materials are finally made, finally,
Dry granular MgO/Ag/PBS-GO/PLA composite materials carry out extrusion wire drawing using single screw extrusion machine, prepare 3D
The extrusion processing temperature of printing PLA silk materials, single screw extrusion machine is 160 DEG C, rotating speed 45r/min, Single screw extrusion mouth
Mode diameter is 3mm.It is illustrated in figure 3 the SEM figures of MgO/Ag/PBS-GO/PLA silk materials.
Finally, a series of materials are carried out melting temperature, electric conductivity and biocidal property to test, finds MgO/Ag/PBS-
The addition of GO composite materials can make PLA melt processing temperatures reduce by 20 DEG C or so, and resistivity has dropped 5 number magnitudes,
Fungistatic effect also significantly improves, corresponding melting temperature as shown in figure 4, electric conductivity as shown in figure 5, bacteriostasis property such as Fig. 6 institutes
Show that (Fig. 6 (a) show the bacteriostasis property figure of MgO/Ag/PBS-GO/PLA, and Fig. 6 (b) show the suppression of MgO/PBS-GO/PLA
Bacterium performance map).
Embodiment 2
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including mass fraction is 25% MgO/
The coupling agent that PLA that Ag/PBS-GO premixes and mass fraction are 70%, mass fraction are 5%.MgO/Ag/PBS-GO is premixed
Material includes the MgO that mass fraction is 0.5%, the Ag that mass fraction is 0.5%, the PBS that mass fraction is 98%, and mass fraction is
0.5% carboxylated GO, the DCP that mass fraction is 0.5%.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, specially：Preparing first can
The antibacterial MgO/Ag/PBS-GO premixes of the conduction of fusing point are reduced, carboxylated GO and quality that mass fraction is 0.5% are divided
Number 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 total volumes) in, it instills the DCP that mass fraction is 0.5% again after carboxylated GO and PBS are completely dissolved, keeps permanent
Constant temperature degree is stirred for mixing and obtains PBS-GO aqueous solutions in 4 hours；Then it is by MgO and mass fraction that mass fraction is 0.5%
0.5% Ag is added in PBS-GO aqueous solutions, and is carried out sonic oscillation and disperseed 1 hour, finally that MgO/Ag/PBS-GO is water-soluble
The vacuum drying oven that liquid moves to 50 DEG C is fully 4 hours dry, and the mixture after drying is crushed in crusher finally obtains graininess
MgO/Ag/PBS-GO premixes, then by mass fraction be 25% MgO/Ag/PBS-GO premixes, mass fraction 5%
The fully dry PLA for being 70% with mass fraction is premixed in high mixer, then melts it in double screw extruder
The extrusion processing temperature of mixing granulation, double screw extruder is 210 DEG C, and rotating speed is 60 r/min, during extrusion mixing, in advance
It is multiple that granular MgO/Ag/PBS-GO/PLA is finally made in extruding pelletization again after batch mixing, coupling agent and the abundant melting mixings of PLA
Condensation material, finally, dry granular MgO/Ag/PBS-GO/PLA composite materials are squeezed out using single screw extrusion machine
Wire drawing prepares 3D printing PLA silk materials, and the extrusion processing temperature of single screw extrusion machine is 120 DEG C, rotating speed 40r/min,
Single 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 mass fraction is 10% MgO/
The coupling agent that PLA that Ag/PBS-GO premixes and mass fraction are 89%, mass fraction are 1%.MgO/Ag/PBS-GO is premixed
Material includes the MgO that mass fraction is 2%, the Ag that mass fraction is 1%, the PBS that mass fraction is 94%, and mass fraction is
1.5% carboxylated GO, the DCP that mass fraction is 1.5%.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, as shown in Fig. 1, specifically
For：The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point, the carboxyl for being 1.5% by mass fraction can be reduced by preparing first
Change the PBS that GO and mass fraction are 94% to pour into 50 DEG C of acetone/ethanol solution (acetone/ethanol=1/4, acetone/ethanol are molten
Liquid is 4 times of carboxylated GO and PBS total volumes) in, after carboxylated GO is completely dissolved with PBS instilling mass fraction again is
1.5% DCP, keeps constant temperature and is stirred for mixing and obtain PBS-GO aqueous solutions in 6 hours；Then it is 2% by mass fraction
The Ag that MgO and mass fraction are 1% is added in PBS-GO aqueous solutions, and is carried out sonic oscillation and disperseed 2 hours, finally by MgO/
The vacuum drying oven that Ag/PBS-GO aqueous solutions move to 75 DEG C is fully 8 hours dry, and the mixture after drying is crushed most in crusher
Obtain granular MgO/Ag/PBS-GO premixes eventually, then by mass fraction be 10% MgO/Ag/PBS-GO premixes,
Mass fraction be 1% be 89% with mass fraction fully dry PLA 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 180 DEG C, and rotating speed 90r/min is being squeezed out
In mixed process, granular MgO/Ag/ is finally made in extruding pelletization again after premix, coupling agent and the abundant melting mixings of PLA
PBS-GO/PLA composite materials, finally, dry granular MgO/Ag/PBS-GO/PLA composite materials are squeezed using single screw rod
Go out machine and carry out 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, Single screw extrusion port mould diameter are 3mm.
Embodiment 4
A kind of conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, including mass fraction is 18% MgO/
The coupling agent that PLA that Ag/PBS-GO premixes and mass fraction are 80%, mass fraction are 2%.MgO/Ag/PBS-GO is premixed
Material includes the MgO that mass fraction is 3.5%, the Ag that mass fraction is 2.5%, the PBS that mass fraction is 91%, and mass fraction is
1% carboxylated GO, the DCP that mass fraction is 2%.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, as shown in Fig. 1, specifically
For：The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point, the carboxylated for being 1% by mass fraction can be reduced by preparing first
The PBS that GO is 91% with mass fraction pours into 80 DEG C of acetone/ethanol solution (acetone/ethanol=1/3, acetone/ethanol solution
For carboxylated GO and 3.5 times of PBS total volumes) in, it is 2% to instill mass fraction again after carboxylated GO and PBS are completely dissolved
DCP, keep constant temperature and be stirred for mixing and obtain PBS-GO aqueous solutions in 12 hours；Then the MgO for being 3.5% by mass fraction
The Ag for being 2.5% with mass fraction is added in PBS-GO aqueous solutions, and carries out sonic oscillation dispersion 15 minutes 1 hour, finally
MgO/Ag/PBS-GO aqueous solutions are moved to 60 DEG C of vacuum drying oven fully to dry 7 hours, the mixture after drying is in crusher
MgO/Ag/PBS-GO that is broken to finally obtain granular MgO/Ag/PBS-GO premixes, being then 18% by mass fraction
Premix, mass fraction be 2% be 80% with mass fraction fully dry PLA premixed in high mixer, then by it
Melting mixing is granulated in double screw extruder, and the extrusion processing temperature of double screw extruder is 170 DEG C, rotating speed 75r/
Min, during extrusion mixing, particle is finally made in extruding pelletization again after premix, coupling agent and the abundant melting mixings of PLA
The MgO/Ag/PBS-GO/PLA composite materials of shape, finally, dry granular MgO/Ag/PBS-GO/PLA composite materials are again
Extrusion wire drawing is carried out by single screw extrusion machine, prepares 3D printing PLA silk materials, the extrusion processing temperature of single screw extrusion machine is
130 DEG C, rotating speed 30/min, 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 mass fraction is 13% MgO/Ag/
The coupling agent that PLA that PBS-GO premixes and mass fraction are 84%, mass fraction are 3%.MgO/Ag/PBS-GO premix packets
Include the MgO that mass fraction is 1%, the Ag that mass fraction is 1.5%, the PBS that mass fraction is 96%, mass fraction 0.5%
Carboxylated GO, mass fraction be 1% DCP.
A kind of preparation method of the conductive antibacterial 3D printing PLA silk materials of low melting point of the present invention, as shown in Fig. 1, specifically
For：The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point, the carboxyl for being 0.5% by mass fraction can be reduced by preparing first
Change the PBS that GO and mass fraction are 96% to pour into 60 DEG C of acetone/ethanol solution (acetone/ethanol=3/10, acetone/ethanol are molten
Liquid is 4.5 times of carboxylated GO and PBS total volumes) in, after carboxylated GO is completely dissolved with PBS instilling mass fraction again is
1% DCP, keeps constant temperature and is stirred for mixing and obtain PBS-GO aqueous solutions in 10 hours；Then it is 1% by mass fraction
The Ag that MgO and mass fraction are 1.5% is added in PBS-GO aqueous solutions, and carries out sonic oscillation dispersion 45 minutes 1 hour, most
The vacuum drying oven that MgO/Ag/PBS-GO aqueous solutions are moved to 80 DEG C afterwards is fully dried 6 hours, and the mixture after drying is in crusher
In be crushed finally obtain granular MgO/Ag/PBS-GO premixes, then by mass fraction be 13% MgO/Ag/PBS-
GO premixes, mass fraction be 3% be 84% with mass fraction fully dry PLA premixed in high mixer, then will
Its melting mixing in double screw extruder is granulated, and the extrusion processing temperature of double screw extruder is 200 DEG C, rotating speed 105r/
Min, during extrusion mixing, particle is finally made in extruding pelletization again after premix, coupling agent and the abundant melting mixings of PLA
The MgO/Ag/PBS-GO/PLA composite materials of shape, finally, dry granular MgO/Ag/PBS-GO/PLA composite materials are again
Extrusion wire drawing is carried out by single screw extrusion machine, prepares 3D printing PLA silk materials, the extrusion processing temperature of single screw extrusion machine is
150 DEG C, rotating speed 60r/min, Single screw extrusion port mould diameter is 3mm.
Claims (7)
1. a kind of conductive antibacterial 3D printing PLA silk materials of low melting point, which is characterized in that the conduction including that can reduce fusing point is antibacterial
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 sum of the mass percent of the above components content is
100%；
The MgO/Ag/PBS-GO premixes include MgO, Ag, PBS, GO-COOH, DCP, wherein MgO accounts for mass fraction 0.5-
5%, Ag account for mass fraction 0.5-3%, and PBS accounts for mass fraction 88-98%, and carboxylated GO accounts for mass fraction 0.5-2%, and DCP is accounted for
Mass fraction 0.5-2%, the sum of mass percent of the above components content are 100%；
The preparation method of the MgO/Ag/PBS-GO premixes is：It is matrix material to select full biological source and degradable PBS
Conductive GO-COOH is introduced into PBS by graft reaction, realizes the high dispersive of GO-COOH, pass through sonic oscillation by material
The Ag powder of the MgO that fusing point can be reduced and bacteriostasis is uniformly dispersed in PBS-GO aqueous solutions, MgO/Ag/ is made after dry
PBS-GO premixes.
2. the method for preparing the conductive antibacterial 3D printing PLA silk materials of a kind of low melting point as described in claim 1, feature exist
In specially：The conductive antibacterial MgO/Ag/PBS-GO premixes of fusing point can be reduced by preparing first, and then use prepares
MgO/Ag/PBS-GO premixes are prepared into 3D printing PLA silk materials with PLA melting extrusions.
3. the conductive antibacterial 3D printing preparation method of PLA silk materials of a kind of low melting point according to claim 1, 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, suitable DCP is instilled again after carboxylated GO and PBS are completely dissolved, temperature is kept constant and is stirred for mixing
Obtain PBS-GO aqueous solutions within 4-12 hours；Then MgO and Ag are added in PBS-GO aqueous solutions, and carry out sonic oscillation dispersion
1-2 hours, MgO/Ag/PBS-GO aqueous solutions are finally moved to 50-80 DEG C of vacuum drying oven and are fully dried 4-8 hours, after dry
Mixture in crusher be crushed finally obtain 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 sum of mass percent of the above components content is 100%, and acetone/ethanol solution is carboxyl
Change GO and PBS total volumes 3-5 times, acetone/ethanol=1/3-1/6 in acetone/ethanol solution.
4. the conductive antibacterial 3D printing preparation method of PLA silk materials of a kind of low melting point according to claim 2, 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
It is multiple that granular MgO/Ag/PBS-GO/PLA is finally made in extruding pelletization again after batch mixing, coupling agent and the abundant melting mixings of PLA
Condensation material, wherein premix accounts for mass fraction 10-25%, coupling agent accounts for mass fraction 1-5%, PLA and accounts for mass fraction 70-
89%, finally, dry granular MgO/Ag/PBS-GO/PLA composite materials carry out extrusion drawing using single screw extrusion machine
Silk prepares 3D printing PLA silk materials.
5. the conductive antibacterial 3D printing preparation method of PLA silk materials of a kind of low melting point according to claim 4, feature
It is, the double screw extruder squeezes out 160-210 DEG C of processing temperature, rotating speed 60-120r/min.
6. the conductive antibacterial 3D printing preparation method of PLA silk materials of a kind of low melting point according to claim 4, feature
It is, the single screw extrusion machine squeezes out 120-160 DEG C of processing temperature, rotating speed 30-60r/min.
7. the conductive antibacterial 3D printing preparation method of PLA silk materials of a kind of low melting point according to claim 4, feature
It is, the port mould diameter 3mm or 1.75mm of the single screw extrusion machine.
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