CN106084699A - The anophelifuge luminous type 3D print magnetic material that a kind of Graphene is modified - Google Patents
The anophelifuge luminous type 3D print magnetic material that a kind of Graphene is modified Download PDFInfo
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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
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- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses the anophelifuge luminous type 3D print magnetic material that a kind of Graphene is modified, it is made up of the raw material of following weight portion meter: polylactic acid 40 ~ 50 parts, substance law ABS20 ~ 25 part, emulsion method ABS10 ~ 20 part, styrene-acrylonitrile glycidyl methacrylate copolymer 5 ~ 10 parts, butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05 part, compounded mix 5 ~ 10 parts, magnetic composite 15 ~ 30 parts, functional material 1 ~ 3, graphene quantum dot and porous graphene；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polylactic acid, and it is 0.1 ~ 2% that described porous graphene accounts for the percentage by weight of ABS gross weight.The anophelifuge luminous type 3D print magnetic material that this kind of Graphene is modified, not only has more excellent mechanics electric property and magnetic property, and has optimal repelling effect and noctilucence performance, widened the range of application of 3D printed material further.
Description
Technical field
The present invention relates to field of compound material, the anophelifuge luminous type 3D print magnetic material that a kind of Graphene is modified
Material.
Background technology
3D printing technique is also known as a kind of emerging technology of increasing material manufacturing technology, actually rapid shaping field, and it is one
Kind based on mathematical model file, use powdery metal or plastics etc. can jointing material, come by the way of successively printing
The technology of constructed object.Ultimate principle is layered manufacturing, successively increases material and generates the technology of 3D solid.At present, 3D beats
Print technology is applied primarily to product prototype, Making mold and the field such as artistic creation, jewelry-making, substitutes these tradition and depends on
The retrofit technique relied.It addition, 3D printing technique is gradually applied to the necks such as medical science, biological engineering, building, clothing, aviation
Territory, has opened up wide space for innovation.
At present, the magnetic material that currently can be used for 3D printing is the rarest, and magnetic material is in the application of medical field
The most quite varied, and the mechanical mechanics property of existing magnetic 3D printing composite is difficult to optimize with magnetic property simultaneously, should
Problem is still that one of the most challenging problem in this area, is also that the printing composite popularization and application of magnetic 3D urgently need
One of problem to be solved.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the anophelifuge luminous type 3D that the invention provides a kind of Graphene modified beats
Print magnetic material, not only has more excellent mechanics electric property and magnetic property, and has optimal repelling effect and night
Optical property, has widened the range of application of 3D printed material further.
The technical problem to be solved is achieved by the following technical programs:
The anophelifuge luminous type 3D print magnetic material that a kind of Graphene is modified, it is made up of the raw material of following weight portion meter: gather breast
Acid 40 ~ 50 parts, substance law ABS20 ~ 25 part, emulsion method ABS10 ~ 20 part, styrene-acrylonitrile-methyl propenoic acid glycidyl
Ester copolymer 5 ~ 10 parts, butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05 part, compounded mix 5 ~ 10 parts, magnetic composite 15 ~ 30
Part, functional material 1 ~ 3, graphene quantum dot and porous graphene；；Described magnetic composite is by Graphene/croci
Form by weight 3:2 with multi-walled carbon nano-tubes/neodymium iron boron powder；Described compounded mix is by Graphene/SiO2Compounded mix with
Graphene/carbon acid calcium compounded mix forms by weight 3:1；Described functional material is by Graphene/SiO2/ fluorescent material composite
Form by weight 2:1 with anophelifuge granule；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polylactic acid, described many
It is 0.1 ~ 2% that hole Graphene accounts for the percentage by weight of ABS gross weight；
The preparation method of the anophelifuge luminous type 3D print magnetic material that a kind of Graphene is modified, comprises the following steps:
(1) pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300
Mesh powder, is scattered in pure water, and ultrasonic (power 200 ~ 300W) after 1 hour, ultrasonic limit, limit microwave exposure (2500 ~ 3000MHz,
Temperature controls at 80 ~ 90 DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
(2) PLA/ filler master batch is prepared: by compounded mix ultrasonic agitation (300 ~ 500KW ultrasonic vibration and 1000 ~ 1400r/min
Centrifugal speed stirs) it is scattered in pure water, obtain compounded mix solution, standby；Under heating-up temperature (50 ~ 60 DEG C), half is pre-
Processing polylactic acid to be dissolved in organic solvent, obtain PLA solution, be divided into two to obtain first part, second part of PLA solution,
Standby；Under temperature constant state (50 ~ 60 DEG C), ultrasonic (the power 300 ~ 500KW) first in limit high-speed stirred (1000 ~ 1400r/min) limit
Part PLA solution, drips compounded mix solution, ultrasonic agitation 30 ~ 60min；Continue second part of PLA solution of dropping, ultrasonic
Stirring 30 ~ 60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain filler polylactic acid mixed liquor；
What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, and the speed with 200～300ml/min is by filler polylactic acid
Mixed liquor is ejected in spray dryer, is dried to obtain PLA/ filler master batch；The nozzle diameter of described spray dryer be 0.5～
0.7mm, dry air flow rates is 30～35m3/ h, temperature 120～160 DEG C；
(3) PLA/ magnetic powder master batch is prepared: magnetic powder compound material ultrasound is stirred (300 ~ 500KW ultrasonic vibration and 1000 ~ 1400r/
Min centrifugal speed stirs) it is scattered in pure water, obtain magnetic powder complex solution, standby；Under heating-up temperature (50 ~ 60 DEG C), will be another
Half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution, and be divided into two to obtain the 3rd part, the 4th part of polylactic acid
Solution, standby；Under temperature constant state (50 ~ 60 DEG C), limit high-speed stirred (1000 ~ 1400r/min) limit ultrasonic (power 300 ~ 500KW)
3rd part of PLA solution, drips magnetic powder complex solution, ultrasonic agitation 30 ~ 60min；Continue the 4th part of polylactic acid of dropping molten
Liquid, ultrasonic agitation 30 ~ 60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain magnetic powder polylactic acid
Mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, and the speed with 200～300ml/min is by magnetic
Powder polylactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ magnetic powder master batch；The nozzle diameter of described spray dryer
Being 0.5～0.7mm, dry air flow rates is 30～35m3/ h, temperature 120～160 DEG C；
(4) Graphene modified ABS/functional agglomerate is prepared: at room temperature with under the speed conditions of 1000 ~ 1500r/min, to container
In add substance law ABS, emulsion method ABS, functional material and porous graphene successively, high-speed stirred 30 ~ 60min is sufficiently mixed；
The mixture obtained feeding rotating nozzle spray dryer is spray-dried, inlet temperature 185 DEG C, by being spray-dried
Outlet quickly cooling obtains Graphene modified ABS/functional agglomerate；
(5) by PLA/ filler master batch, PLA/ magnetic powder master batch and Graphene modified ABS/functional agglomerate, styrene-acrylonitrile-methyl
Glycidyl acrylate copolymer, butyltriphenylphosphonium bromide phosphine mix, and carry out melted being total to through double screw extruder at 185 DEG C
Mixed, prepare the co-continuous ABS/PLA alloy with magnetic properties, then produce the modification of a kind of Graphene through material strip shaping mechanism
Anophelifuge luminous type 3D print magnetic material.
In the present invention, described organic solvent is by acetone, butanone, 2 pentanone, propione, Ketocyclopentane, isopropyl methyl first
At least one in ketone, oxolane and dioxane is constituted.
There is advantages that
Scientific matching, the anophelifuge luminous type 3D print magnetic material that prepared described a kind of Graphene is modified is obtained by test of many times
Material not only has more excellent mechanical property and magnetic property, and has optimal repelling effect and noctilucence characteristic, further
Widen the range of application of 3D printed material；Solve in prior art, add fluorescent material, particularly nanoscale fluorescent material, hold
Easily reunite in the composite, reduce its characteristics of luminescence.
Detailed description of the invention
In the present invention,
(1) Graphene is prepared by following methods: taking a certain amount of acid flat band ink, 1000 DEG C process 2 hours, then 8% in atmosphere
H2Nitrogen and hydrogen mixture in 1100 DEG C of in-situ reducing process 1.0 hours, add macrogol ester and the mass ratio of mass ratio 3%
Tetracarboxylic dianhydride's dinaphthyl of 5.0%, is made into, with water, the slurry that concentration is 82.0%, first enters under the ultrasonic assistant that power is 700W
Row 4000 turns/min ball milling 10 hours, then adjust and to 300W ultrasound wave, carry out 2000 turns/min ball milling 5 hours, through height after ball milling
Speed 10000 turns/min of centrifuge separates, lyophilization, it is thus achieved that Graphene solid.
(2) quantum dot calcium carbonate, its preparation method refers to a kind of microemulsion disclosed in Chinese patent CN103570051B
System prepares the method for nano calcium carbonate quantum dot, the most first prepares the nano-calcium carbonate microemulsion of 1 ~ 3nm, more rotated
Evaporate and be dried and prepare quantum dot calcium carbonate powder.
(3) Graphene/SiO2Compounded mix preparation method is as follows: by Graphene ultrasonic agitation (700KW ultrasonic vibration and
1300r/min centrifugal speed stirs) it is scattered in ethanol；Add a certain proportion of (4:1) water and ammonia afterwards, after stirring
The mass ratio adding tetraethyl orthosilicate and Graphene is 1.6:1, and regulation pH value is 9, and reaction temperature is 25 DEG C, and reaction 4.2 is little
Time, it is centrifuged and cleans 3 times with acetone and deionized water, deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 2h, to obtain being coated with SiO2Graphene compounded mix.
(4) preparation method of graphene/carbon acid calcium compounded mix is as follows: 1 part of Graphene is added 100ml deionized water
In, prepare graphene dispersing solution after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir；By 73
Part quantum dot calcium carbonate adds in 500ml deionized water, divides under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir
Calcium carbonate dispersion liquid is prepared after dissipating 300min；Lower in graphene dispersing solution, it is slowly added dropwise calcium carbonate dispersion liquid 100kW is ultrasonic,
Ultrasonic 60min, then sucking filtration, drying, prepare graphene/carbon acid calcium compounded mix.
(5) preparation method of Graphene/croci is as follows: added by Graphene in 100ml deionized water,
Graphene dispersing solution is prepared after 800kW ultrasonic vibration and the lower dispersion 200min of 1300r/min centrifugal speed stirring；By brown iron oxide
End adds in 100ml deionized water, makes after disperseing 300min under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir
Obtain ferrum oxide dispersion liquid；Ultrasonic lower toward graphene dispersing solution is slowly added dropwise ferrum oxide dispersion liquid at 200kW, ultrasonic 90min, so
Rear sucking filtration, drying, prepare Graphene/croci.Described Graphene is 1:3 with the mass ratio of ferrum oxide, and ferrum oxide is four
Fe 3 O.
(6) preparation method of multi-walled carbon nano-tubes/neodymium iron boron powder is as follows: multi-walled carbon nano-tubes is added 100ml go from
In sub-water, prepare multi-walled carbon nano-tubes after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir and divide
Dissipate liquid；Neodymium iron boron powder is added in 100ml deionized water, stir at 1300kW ultrasonic vibration and 1500r/min centrifugal speed
Neodymium iron boron dispersion liquid is prepared after lower dispersion 300min；Lower in multi-walled carbon nano-tubes dispersion liquid, it is slowly added dropwise neodymium 200kW is ultrasonic
Ferrum boron dispersion liquid, ultrasonic 90min, then sucking filtration, drying, prepare multi-walled carbon nano-tubes/neodymium iron boron powder.Described multi-wall carbon nano-tube
Pipe is 1:2 with the mass ratio of neodymium iron boron powder.
(7) multi-walled carbon nano-tubes/nanometer silver/SiO2The preparation method of anti-biotic material is as follows: to the 0.01mol L of 200ml-1HNO3Solution adds 0.79g AgNO respectively3, 5g multi-walled carbon nano-tubes, 0.5g dispersant sodium cetanesulfonate, ultrasonic
After dispersion 60min, then magnetic agitation 24h in camera bellows.After having stirred, by 0.3mol L-1NaOH solution be added dropwise over
To this suspension, regulate its pH to 12.Filtering, gained powder sample, with after distilled water cyclic washing 3 times, is dispersed to
In 500ml distilled water, add 1.0ml hole remover propylene glycol, be placed on ultra-violet lamp (125W, λ max=365nm)
Under, irradiate 6 hours.Gained sample filtering separates, and with distilled water wash 4 times.Sample after washing is put in drying baker, 80
It is dried 10 hours at DEG C, grinds, obtain multi-walled carbon nano-tubes/nano silver composite material.Multi-walled carbon nano-tubes/nanometer silver is combined
Material ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) is scattered in ethanol；Add a definite proportion afterwards
(4:1) water of example and ammonia, be stirring evenly and then adding into the quality of tetraethyl orthosilicate and multi-walled carbon nano-tubes/nano silver composite material
Than being 2:1, regulation pH value is 9, and reaction temperature is 25 DEG C, react 5 hours, be centrifuged and use successively acetone and deionized water,
Deionized water cleans 3 times and obtains precipitation；This is deposited in 90o2h it is dried, to obtain multi-walled carbon nano-tubes/nanometer silver/SiO under C2
Anti-biotic material.
(8) described Graphene/SiO2/ fluorescent material composite is prepared by following methods: by Graphene ultrasonic agitation
(700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) is scattered in ethanol；Add a certain proportion of (3:1) water afterwards
And ammonia, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.8:1, and regulation pH value is 9, reaction temperature
It is 25 DEG C, reacts 12 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is deposited in
90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material；This is coated with SiO2Core-shell composite material be placed in argon
800 DEG C of heat treatment 1.5h are carried out under gas atmosphere；Core-shell composite material after heat treatment is immersed in ultrasonic 15min in Fluohydric acid.,
Remove the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds 100ml deionized water
In, prepare Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；
50 parts of nanoscale long lad phosphors are added in 500ml deionized water, in the centrifugal speed of 1200kW ultrasonic vibration and 1000r/min
Long lad phosphor dispersion liquid is prepared after the lower dispersion 300min of degree stirring；Ultrasonic lower toward Graphene/SiO at 100kW2In dispersion liquid
It is slowly added dropwise long lad phosphor dispersion liquid, ultrasonic 50min, then sucking filtration, drying, carries out under vacuum environment at 1050 DEG C of heat
Reason 60min, prepares Graphene/SiO2/ long-afterglow fluorescent powder composite material.Described long lad phosphor is long afterglow Sr4Al14O25
Nano-phosphor, mean diameter is the fluorescent material less than 10nm.
(9) preparation method of anophelifuge granule is as follows: by 3 parts of Radix Buddlejae Butterflybush extracts, 5 parts of Herba Cymbopogonis Citrari cream in vacuum mixing machine, and 2
Part Mint flavone extract, 8 parts of Herba Rosmarini Officinalis extracts join in the diatom Rhizoma Panacis Japonici soil of 35 parts, at vacuum condition, 120r/min
Speed under stir 30 minutes, allow each component adsorb in kieselguhr；The polyacrylic acid of 18 parts is added in the kieselguhr obtained
Ester emulsion, vacuum mixing machine stirs 20 minutes under the speed of 300r/min, makes polyacrylate dispersion be coated with by kieselguhr
Coming, formed with kieselguhr as core, polyacrylate is the capsule of shell, makes the granule of a diameter of 1mm in pellet processing machine, then will system
The granule natural drying obtained, after 12 hours, obtains a kind of solid anophelifuge granule.
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ filler master batch: by 9.7 parts of compounded mix ultrasonic agitation (500KW ultrasonic vibration and the centrifugal speed of 1300r/min
Degree stirring) it is scattered in pure water, obtain compounded mix solution, standby；Under heating-up temperature (60 DEG C), by 22 parts of pretreatment polylactic acid
Being dissolved in organic solvent, obtain PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Constant temperature shape
Under state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, dropping is compound fills out
Material solution, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min, obtain filler polylactic acid and mix
Close liquid；What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min by filler polylactic acid
Mixed liquor is ejected in spray dryer, is dried to obtain PLA/ filler master batch；The nozzle diameter of described spray dryer is 0.6mm,
Dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described compounded mix is by Graphene/SiO2Compounded mix and graphene/carbon acid
Calcium compounded mix forms by weight 3:1；
3, preparation PLA/ magnetic powder master batch: by the stirring of 15 parts of magnetic powder compound material ultrasounds (500KW ultrasonic vibration and 1300r/min from
Heart speed stirs) it is scattered in pure water, obtain magnetic powder complex solution, standby；Under heating-up temperature (60 DEG C), by 22 parts of pretreatment
Polylactic acid is dissolved in organic solvent, obtains PLA solution, and be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；
Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution, dropping
Magnetic powder complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 60min, obtain magnetic powder
Polylactic acid mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min by magnetic
Powder polylactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ magnetic powder master batch；The nozzle diameter of described spray dryer
For 0.6mm, dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described magnetic composite by Graphene/croci and
Multi-walled carbon nano-tubes/neodymium iron boron powder forms by weight 3:2；
4, by PLA/ filler master batch, PLA/ magnetic powder master batch and substance law ABS (21.78 parts, Tao Shi MAGNUM 213), emulsion method
ABS (17 parts, Taiwan very U.S. 747), styrene-acrylonitrile-glycidyl methacrylate copolymer (5 parts, SAN-GMA),
Butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mixes, and carries out melt blending through double screw extruder under 185 degrees Celsius, preparation
Provide the co-continuous ABS/PLA alloy of the characteristic that is magnetic, then use ABS/PLA magnetic through the 3D printing that the manufacture of material strip forming machine is modified
Composite.
Embodiment 2
Preparation method based on embodiment 1, the difference is that only: the magnetic composite adding proportion in step 2 changes 20 into
Part.
Embodiment 3
Preparation method based on embodiment 1, the difference is that only: the magnetic composite adding proportion in step 2 changes 24 into
Part.
Embodiment 4
Preparation method based on embodiment 1, the difference is that only: the magnetic composite adding proportion in step 2 changes 30 into
Part.
Embodiment 5
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ filler master batch: (500KW ultrasonic vibration and 1300r/min centrifugal speed are stirred by compounded mix ultrasonic agitation
Mix) it is scattered in pure water, obtain compounded mix solution, standby；Under heating-up temperature (60 DEG C), 20 parts of pretreatment polylactic acid are dissolved
In organic solvent, obtaining PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Temperature constant state
Under (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, drip compounded mix
Solution, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min；Continue dropping Graphene quantum
Point solution (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), obtains filler polylactic acid mixed liquor；
What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, is mixed by filler polylactic acid with the speed of 300ml/min
Liquid is ejected in spray dryer, is dried to obtain PLA/ filler master batch；The nozzle diameter of described spray dryer is 0.6mm, is dried
Air velocity is at 30m3/ h, temperature 150 DEG C；Described compounded mix is by Graphene/SiO2Compounded mix is multiple with graphene/carbon acid calcium
Close filler to form by weight 3:1；
3, preparation PLA/ magnetic powder master batch: by the stirring of 4.5 parts of magnetic powder compound material ultrasounds (500KW ultrasonic vibration and 1300r/min from
Heart speed stirs) it is scattered in pure water, obtain magnetic powder complex solution, standby；Under heating-up temperature (60 DEG C), by 20 parts of pretreatment
Polylactic acid is dissolved in organic solvent, obtains PLA solution, and be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；
Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution, dropping
Magnetic powder complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping；Continue dropping graphene quantum dot molten
Liquid (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), ultrasonic agitation 60min, obtain the poly-breast of magnetic powder
Acid mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, is gathered by magnetic powder with the speed of 300ml/min
Lactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ magnetic powder master batch；The nozzle diameter of described spray dryer is
0.6mm, dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described magnetic composite is by Graphene/croci and many
Wall carbon nano tube/neodymium iron boron powder forms by weight 3:2；
4, prepare Graphene and change lower ABS masterbatch: at room temperature with under the speed conditions of 1500r/min, add successively in container
Substance law ABS (21.78 parts, Tao Shi MAGNUM 213), emulsion method ABS (17 parts, Taiwan very U.S. 747) and porous graphene are (many
It is 1% that hole Graphene accounts for the mass percent of ABS gross mass), high-speed stirred 60min is sufficiently mixed；The mixture obtained is sent into
Rotating nozzle spray dryer is spray-dried, inlet temperature 185 DEG C, is quickly cooled down by spray drying exit and obtains stone
Ink alkene modified ABS master batch；
5, by PLA/ filler master batch, PLA/ magnetic powder master batch and Graphene modified ABS master batch, styrene-acrylonitrile-methacrylic acid
Glycidyl ester copolymer (5 parts, SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mix, through double screw extruder
Under 185 degrees Celsius, carry out melt blending, prepare the co-continuous ABS/PLA alloy with magnetic properties, then through material strip molding
Machine manufactures modified 3D printing and uses ABS/PLA magnetic composite.
The preparation method of described porous graphene is with reference to the embodiment 1 of Chinese patent application CN104555999A；Described stone
The preparation method of ink alkene quantum dot is with reference to the embodiment 5 of Chinese patent CN102190296B.It should be noted that prepare graphite
Alkene quantum dot, is scattered in second further according to actual amount ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed)
In alcohol, this is only a kind of embodiment, it is also possible to obtain by other means.
Embodiment 6
Based on embodiment 5, difference is: it is 0.8% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous
It is 0.5% that Graphene accounts for the mass percent of ABS gross mass.
Embodiment 7
Based on embodiment 5, difference is: it is 1% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous stone
It is 2% that ink alkene accounts for the mass percent of ABS gross mass.
Comparative example 1
Preparation method based on embodiment 1, the difference is that only: described magnetic composite is by Graphene/croci
Form by weight 3:1 with multi-walled carbon nano-tubes/neodymium iron boron powder.
Comparative example 2
Preparation method based on embodiment 1, the difference is that only: described magnetic composite is by Graphene/croci
Form by weight 1:1 with multi-walled carbon nano-tubes/neodymium iron boron powder.
Comparative example 3
Preparation method based on embodiment 1, the difference is that only: described magnetic composite is Graphene/croci.
Comparative example 4
Preparation method based on embodiment 1, the difference is that only: described magnetic composite is multi-walled carbon nano-tubes/neodymium ferrum
Boron powder.
Comparative example 5
Preparation method based on embodiment 1, the difference is that only: described magnetic composite is croci and neodymium iron boron
Powder forms by weight 3:2.
Comparative example 6
1,22 parts of PLA and 9.7 parts of compounded mixs are added in 185 degrees Celsius of lower melt blendings in banbury, prepare PLA/ filler
Master batch.Described compounded mix is by Graphene/SiO2Compounded mix and graphene/carbon acid calcium compounded mix are by weight 3:1 group
Become.
2,22 parts of PLA and 15 parts of magnetic composites are added in banbury in 185 degrees Celsius of lower melt blendings, preparation
PLA/ magnetic powder master batch.Described magnetic composite is pressed weight by Graphene/croci and multi-walled carbon nano-tubes/neodymium iron boron powder
Measure and form than 3:2.
3, PLA/ filler master batch, PLA/ magnetic powder master batch and substance law ABS (21.78 parts, Tao Shi MAGNUM 213), emulsion method
ABS (17 parts, Taiwan very U.S. 747), styrene-acrylonitrile-glycidyl methacrylate copolymer (5 parts, SAN-GMA),
Butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mixes, and carries out melt blending through double screw extruder under 185 degrees Celsius, preparation
Provide the co-continuous ABS/PLA alloy of the characteristic that is magnetic, then use ABS/PLA magnetic through the 3D printing that the manufacture of material strip forming machine is modified
Composite.
Comparative example 7
1,22 parts of PLA and 9.7 parts of compounded mixs are added in 185 degrees Celsius of lower melt blendings in banbury, prepare PLA/ filler
Master batch.Described compounded mix is by Graphene/SiO2Compounded mix and graphene/carbon acid calcium compounded mix are by weight 3:1 group
Become.
2,22 parts of PLA and 15 parts of magnetic composites are added in banbury in 185 degrees Celsius of lower melt blendings, preparation
PLA/ magnetic powder master batch.Described magnetic composite is pressed weight by Graphene/croci and multi-walled carbon nano-tubes/neodymium iron boron powder
Measure and form than 3:2.
3, PLA/ filler master batch, PLA/ magnetic powder master batch and substance law ABS (21.78 parts, Tao Shi MAGNUM 213), emulsion method
ABS (17 parts, Taiwan very U.S. 747), styrene-acrylonitrile-glycidyl methacrylate copolymer (5 parts, SAN-GMA),
Graphene 0.82 part, butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mix, and carry out under 185 degrees Celsius through double screw extruder
Melt blending, prepares the co-continuous ABS/PLA alloy with magnetic properties, then manufactures modified 3D printing through material strip forming machine
Use ABS/PLA magnetic composite.
Embodiment 1 ~ 7 and comparative example 1 ~ 7 are carried out mechanical mechanics property and magnetism testing, and result is as follows:
| Tensile strength Mpa | Notch impact strength J/M | Saturation magnetization emu/g | |
| Embodiment 1 | 49.55 | 135 | 20.94 |
| Embodiment 2 | 50.24 | 134 | 21.50 |
| Embodiment 3 | 56.71 | 139 | 27.22 |
| Embodiment 4 | 49.33 | 132 | 20.72 |
| Embodiment 5 | 94.52 | 285 | 21.26 |
| Embodiment 6 | 98.65 | 292 | 20.88 |
| Embodiment 7 | 96.22 | 280 | 21.31 |
| Comparative example 1 | 47.72 | 114 | 13.78 |
| Comparative example 2 | 47.21 | 115 | 9.18 |
| Comparative example 3 | 47.79 | 114 | 5.82 |
| Comparative example 4 | 46.80 | 116 | 5.04 |
| Comparative example 5 | 46.90 | 117 | 2.58 |
| Comparative example 6 | 41.56 | 102 | 15.19 |
| Comparative example 7 | 56.75 | 125 | 15.25 |
Embodiment 8
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ filler master batch: by 9.7 parts of compounded mix ultrasonic agitation (500KW ultrasonic vibration and the centrifugal speed of 1300r/min
Degree stirring) it is scattered in pure water, obtain compounded mix solution, standby；Under heating-up temperature (60 DEG C), by 22 parts of pretreatment polylactic acid
Being dissolved in organic solvent, obtain PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Constant temperature shape
Under state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, dropping is compound fills out
Material solution, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min, obtain filler polylactic acid and mix
Close liquid；What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min by filler polylactic acid
Mixed liquor is ejected in spray dryer, is dried to obtain PLA/ filler master batch；The nozzle diameter of described spray dryer is 0.6mm,
Dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described compounded mix is by Graphene/SiO2Compounded mix and graphene/carbon acid
Calcium compounded mix forms by weight 3:1；
3, preparation PLA/ magnetic powder master batch: by the stirring of 15 parts of magnetic powder compound material ultrasounds (500KW ultrasonic vibration and 1300r/min from
Heart speed stirs) it is scattered in pure water, obtain magnetic powder complex solution, standby；Under heating-up temperature (60 DEG C), by 22 parts of pretreatment
Polylactic acid is dissolved in organic solvent, obtains PLA solution, and be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；
Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution, dropping
Magnetic powder complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 60min, obtain magnetic powder
Polylactic acid mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min by magnetic
Powder polylactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ magnetic powder master batch；The nozzle diameter of described spray dryer
For 0.6mm, dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described magnetic composite by Graphene/croci and
Multi-walled carbon nano-tubes/neodymium iron boron powder forms by weight 3:2；
4, at room temperature with under the speed conditions of 1500r/min, add successively in container substance law ABS (21.78 parts, Tao Shi
MAGNUM 213), emulsion method ABS (17 parts, Taiwan very U.S. 747) and multi-walled carbon nano-tubes/nanometer silver/SiO2Anti-biotic material
(0.42 part), high-speed stirred 60min is sufficiently mixed；The mixture obtained feeding rotating nozzle spray dryer is sprayed
It is dried, inlet temperature 185 DEG C, is quickly cooled down by spray drying exit and obtain ABS/ antibacterial matrices；
5, by PLA/ filler master batch, PLA/ magnetic powder master batch and ABS/ antibacterial matrices, styrene-acrylonitrile-Glycidyl methacrylate
Glyceride copolymer (5 parts, SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB), mixing, through double screw extruder in
Carry out melt blending under 185 degrees Celsius, prepare the co-continuous ABS/PLA alloy with magnetic properties, then through material strip forming machine
Manufacture antimicrobial form 3D printing and use ABS/PLA magnetic composite.
Prepared magnetic composite antibiotic rate is as follows: escherichia coli: 98.2%, staphylococcus aureus: 98.5%.
(anti-microbial property is tested: detect according to GB/T23763-2009 national standard, selects escherichia coli ATCC8739 and golden yellow
Staphylococcus A TCC6538P is strain).The tensile strength of this magnetic composite is 49.58Mpa, and notch impact strength is
135J/M。
Embodiment 9
Preparation method based on embodiment 8, difference is: multi-walled carbon nano-tubes/nanometer silver/SiO2The interpolation of anti-biotic material
Ratio changes 0.525 part into.Prepared magnetic composite antibiotic rate is as follows: escherichia coli: 99.9%, staphylococcus aureus:
99.8%.(anti-microbial property test: detect according to GB/T23763-2009 national standard, select escherichia coli ATCC8739 and
Staphylococcus aureus ATCC6538P is strain).The tensile strength of this magnetic composite is 49.55Mpa, notch shock
Intensity is 137J/M.
Embodiment 10
Preparation method based on embodiment 8, difference is: multi-walled carbon nano-tubes/nanometer silver/SiO2The interpolation of anti-biotic material
Ratio changes 0.63 part into.Prepared magnetic composite antibiotic rate is as follows: escherichia coli: 98.9%, staphylococcus aureus:
98.8%.(anti-microbial property test: detect according to GB/T23763-2009 national standard, select escherichia coli ATCC8739 and
Staphylococcus aureus ATCC6538P is strain).The tensile strength of this magnetic composite is 49.51Mpa, notch shock
Intensity is 135J/M.
Embodiment 11
Preparation method based on embodiment 8, difference is: multi-walled carbon nano-tubes/nanometer silver/SiO2The interpolation of anti-biotic material
Ratio changes 0.84 part into.Prepared magnetic composite antibiotic rate is as follows: escherichia coli: 97.1%, staphylococcus aureus:
96.8%.(anti-microbial property test: detect according to GB/T23763-2009 national standard, select escherichia coli ATCC8739 and
Staphylococcus aureus ATCC6538P is strain).The tensile strength of this magnetic composite is 48.58Mpa, notch shock
Intensity is 139J/M.
Embodiment 12
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ filler master batch: (500KW ultrasonic vibration and 1300r/min centrifugal speed are stirred by compounded mix ultrasonic agitation
Mix) it is scattered in pure water, obtain compounded mix solution, standby；Under heating-up temperature (60 DEG C), 20 parts of pretreatment polylactic acid are dissolved
In organic solvent, obtaining PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Temperature constant state
Under (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, drip compounded mix
Solution, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min；Continue dropping Graphene quantum
Point solution (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), obtains filler polylactic acid mixed liquor；
What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, is mixed by filler polylactic acid with the speed of 300ml/min
Liquid is ejected in spray dryer, is dried to obtain PLA/ filler master batch；The nozzle diameter of described spray dryer is 0.6mm, is dried
Air velocity is at 30m3/ h, temperature 150 DEG C；Described compounded mix is by Graphene/SiO2Compounded mix is multiple with graphene/carbon acid calcium
Close filler to form by weight 3:1；
3, preparation PLA/ magnetic powder master batch: by the stirring of 4.5 parts of magnetic powder compound material ultrasounds (500KW ultrasonic vibration and 1300r/min from
Heart speed stirs) it is scattered in pure water, obtain magnetic powder complex solution, standby；Under heating-up temperature (60 DEG C), by 20 parts of pretreatment
Polylactic acid is dissolved in organic solvent, obtains PLA solution, and be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；
Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution, dropping
Magnetic powder complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping；Continue dropping graphene quantum dot molten
Liquid (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), ultrasonic agitation 60min, obtain the poly-breast of magnetic powder
Acid mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, is gathered by magnetic powder with the speed of 300ml/min
Lactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ magnetic powder master batch；The nozzle diameter of described spray dryer is
0.6mm, dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described magnetic composite is by Graphene/croci and many
Wall carbon nano tube/neodymium iron boron powder forms by weight 3:2；
4, prepare Graphene and change lower ABS/ antibacterial matrices: at room temperature with under the speed conditions of 1500r/min, in container successively
Add substance law ABS (21.78 parts, Tao Shi MAGNUM 213), emulsion method ABS (17 parts, Taiwan very U.S. 747), multi-wall carbon nano-tube
Pipe/nanometer silver/SiO2(porous graphene accounts for the mass percent of ABS gross mass for anti-biotic material (0.42 part) and porous graphene
It is 1%), high-speed stirred 60min is sufficiently mixed；The mixture obtained feeding rotating nozzle spray dryer is carried out spray dried
Dry, inlet temperature 185 DEG C, quickly cooled down by spray drying exit and obtain Graphene modified ABS master batch；
5, by PLA/ filler master batch, PLA/ magnetic powder master batch and Graphene modified ABS/antibacterial matrices, styrene-acrylonitrile-methyl
Glycidyl acrylate copolymer (5 parts, SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mix, through twin screw
Extruder carries out melt blending under 185 degrees Celsius, prepares the co-continuous ABS/PLA alloy with magnetic properties, then through material
ABS/PLA magnetic composite is used in the antimicrobial form 3D printing that bar forming machine manufactures Graphene modified.
Prepared magnetic composite antibiotic rate is as follows: escherichia coli: 98.4%, staphylococcus aureus: 98.6%.
(anti-microbial property is tested: detect according to GB/T23763-2009 national standard, selects escherichia coli ATCC8739 and golden yellow
Staphylococcus A TCC6538P is strain).The tensile strength of this magnetic composite is 94.63Mpa, and notch impact strength is
284J/M。
The preparation method of described porous graphene is with reference to the embodiment 1 of Chinese patent application CN104555999A；Described stone
The preparation method of ink alkene quantum dot is with reference to the embodiment 5 of Chinese patent CN102190296B.It should be noted that prepare graphite
Alkene quantum dot, is scattered in second further according to actual amount ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed)
In alcohol, this is only a kind of embodiment, it is also possible to obtain by other means.
Embodiment 13
Based on embodiment 12, difference is: it is 0.8% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous
It is 0.5% that Graphene accounts for the mass percent of ABS gross mass.Prepared magnetic composite antibiotic rate is as follows: escherichia coli:
98.3%, staphylococcus aureus: 98.6%.(anti-microbial property is tested: detect according to GB/T23763-2009 national standard,
Selecting escherichia coli ATCC8739 and staphylococcus aureus ATCC6538P is strain).The stretch-proof of this magnetic composite is strong
Degree is 98.53Mpa, and notch impact strength is 293J/M.
Embodiment 14
Based on embodiment 12, difference is: it is 1% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous stone
It is 2% that ink alkene accounts for the mass percent of ABS gross mass.Prepared magnetic composite antibiotic rate is as follows: escherichia coli:
98.4%, staphylococcus aureus: 98.2%.(anti-microbial property is tested: detect according to GB/T23763-2009 national standard,
Selecting escherichia coli ATCC8739 and staphylococcus aureus ATCC6538P is strain).The stretch-proof of this magnetic composite is strong
Degree is 96.30Mpa, and notch impact strength is 281J/M.
Comparative example 8
Preparation method based on embodiment 8, difference is: the anti-biotic material added is nanometer silver.Prepared magnetic
Composite antibiotic rate is as follows: escherichia coli: 93.2%, staphylococcus aureus: 93.8%.(anti-microbial property is tested: according to GB/
T23763-2009 national standard detects, and selecting escherichia coli ATCC8739 and staphylococcus aureus ATCC6538P is bacterium
Kind).The tensile strength of this magnetic composite is 47.58Mpa, and notch impact strength is 133J/M.
Comparative example 9
Preparation method based on embodiment 8, difference is: the anti-biotic material added is multi-walled carbon nano-tubes/nanometer silver.
Prepared magnetic composite antibiotic rate is as follows: escherichia coli: 95.5%, staphylococcus aureus: 96.1%.(anti-microbial property
Test: detect according to GB/T23763-2009 national standard, selects escherichia coli ATCC8739 and staphylococcus aureus
ATCC6538P is strain).The tensile strength of this magnetic composite is 48.66Mpa, and notch impact strength is 135J/M.
Embodiment 15
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ filler master batch: by 9.7 parts of compounded mix ultrasonic agitation (500KW ultrasonic vibration and the centrifugal speed of 1300r/min
Degree stirring) it is scattered in pure water, obtain compounded mix solution, standby；Under heating-up temperature (60 DEG C), by 22 parts of pretreatment polylactic acid
Being dissolved in organic solvent, obtain PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Constant temperature shape
Under state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, dropping is compound fills out
Material solution, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min, obtain filler polylactic acid and mix
Close liquid；What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min by filler polylactic acid
Mixed liquor is ejected in spray dryer, is dried to obtain PLA/ filler master batch；The nozzle diameter of described spray dryer is 0.6mm,
Dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described compounded mix is by Graphene/SiO2Compounded mix and graphene/carbon acid
Calcium compounded mix forms by weight 3:1；
3, preparation PLA/ magnetic powder master batch: by the stirring of 15 parts of magnetic powder compound material ultrasounds (500KW ultrasonic vibration and 1300r/min from
Heart speed stirs) it is scattered in pure water, obtain magnetic powder complex solution, standby；Under heating-up temperature (60 DEG C), by 22 parts of pretreatment
Polylactic acid is dissolved in organic solvent, obtains PLA solution, and be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；
Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution, dropping
Magnetic powder complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 60min, obtain magnetic powder
Polylactic acid mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min by magnetic
Powder polylactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ magnetic powder master batch；The nozzle diameter of described spray dryer
For 0.6mm, dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described magnetic composite by Graphene/croci and
Multi-walled carbon nano-tubes/neodymium iron boron powder forms by weight 3:2；
4, ABS/ functional agglomerate is prepared: at room temperature with under the speed conditions of 1500r/min, in container, add substance law successively
ABS (21.78 parts, Tao Shi MAGNUM 213), emulsion method ABS (17 parts, Taiwan very U.S. 747) and functional material (1.5 parts, graphite
Alkene/SiO2/ fluorescent material composite and anophelifuge granule form by weight 2:1), high-speed stirred 60min is sufficiently mixed；To obtain
Mixture send into rotating nozzle spray dryer be spray-dried, inlet temperature 185 DEG C, fast by spray drying exit
Quickly cooling but obtains ABS/ functional agglomerate；
5, by PLA/ filler master batch, PLA/ magnetic powder master batch and ABS/ functional agglomerate, styrene-acrylonitrile-Glycidyl methacrylate
Glyceride copolymer (5 parts, SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mix, through double screw extruder in
Carry out melt blending under 185 degrees Celsius, prepare the co-continuous ABS/PLA alloy with magnetic properties, then through material strip forming machine
Produce anophelifuge luminous type 3D print magnetic material.
Prepared magnetic composite can effective anophelifuge, drug effect was up to 7 ~ 9 days；And uniformity of luminance is preferable, long remaining
Brightness is for up to 10h.The tensile strength of this magnetic composite is 49.68Mpa, and notch impact strength is 135J/M.
Embodiment 16
Preparation method based on embodiment 15, difference is: the adding proportion of described functional material is 3 parts.Prepared
Magnetic composite can effective anophelifuge, drug effect is up to 6 ~ 7 days；And uniformity of luminance is general, long afterglow is for up to 8h.This magnetic
The tensile strength of property composite is 48.62Mpa, and notch impact strength is 136J/M.
Embodiment 17
Preparation method based on embodiment 15, difference is: the adding proportion of described functional material is 0.5 part.Prepared
Magnetic composite can effective anophelifuge, drug effect is up to 5 ~ 6 days；And uniformity of luminance is general, long afterglow is for up to 8h.Should
The tensile strength of magnetic composite is 47.38Mpa, and notch impact strength is 135J/M.
Embodiment 18
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ filler master batch: (500KW ultrasonic vibration and 1300r/min centrifugal speed are stirred by compounded mix ultrasonic agitation
Mix) it is scattered in pure water, obtain compounded mix solution, standby；Under heating-up temperature (60 DEG C), 20 parts of pretreatment polylactic acid are dissolved
In organic solvent, obtaining PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Temperature constant state
Under (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, drip compounded mix
Solution, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min；Continue dropping Graphene quantum
Point solution (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), obtains filler polylactic acid mixed liquor；
What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, is mixed by filler polylactic acid with the speed of 300ml/min
Liquid is ejected in spray dryer, is dried to obtain PLA/ filler master batch；The nozzle diameter of described spray dryer is 0.6mm, is dried
Air velocity is at 30m3/ h, temperature 150 DEG C；Described compounded mix is by Graphene/SiO2Compounded mix is multiple with graphene/carbon acid calcium
Close filler to form by weight 3:1；
3, preparation PLA/ magnetic powder master batch: by the stirring of 4.5 parts of magnetic powder compound material ultrasounds (500KW ultrasonic vibration and 1300r/min from
Heart speed stirs) it is scattered in pure water, obtain magnetic powder complex solution, standby；Under heating-up temperature (60 DEG C), by 20 parts of pretreatment
Polylactic acid is dissolved in organic solvent, obtains PLA solution, and be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；
Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution, dropping
Magnetic powder complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping；Continue dropping graphene quantum dot molten
Liquid (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), ultrasonic agitation 60min, obtain the poly-breast of magnetic powder
Acid mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, is gathered by magnetic powder with the speed of 300ml/min
Lactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ magnetic powder master batch；The nozzle diameter of described spray dryer is
0.6mm, dry air flow rates is at 30m3/ h, temperature 150 DEG C；Described magnetic composite is by Graphene/croci and many
Wall carbon nano tube/neodymium iron boron powder forms by weight 3:2；
4, prepare Graphene and change lower ABS/ functional agglomerate: at room temperature with under the speed conditions of 1500r/min, in container successively
Add substance law ABS (21.78 parts, Tao Shi MAGNUM 213), emulsion method ABS (17 parts, Taiwan very U.S. 747), functional material
(1.5 parts, Graphene/SiO2/ fluorescent material composite and anophelifuge granule form by weight 2:1) and porous graphene (porous
It is 1% that Graphene accounts for the mass percent of ABS gross mass), high-speed stirred 60min is sufficiently mixed；The mixture obtained is sent into rotation
Rotatable nozzle spray drier is spray-dried, inlet temperature 185 DEG C, is quickly cooled down by spray drying exit and obtains graphite
Alkene modified ABS/functional agglomerate；
5, by PLA/ filler master batch, PLA/ magnetic powder master batch and Graphene modified ABS/functional agglomerate, styrene-acrylonitrile-methyl
Glycidyl acrylate copolymer (5 parts, SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mix, through twin screw
Extruder carries out melt blending under 185 degrees Celsius, prepares the co-continuous ABS/PLA alloy with magnetic properties, then through material
Bar shaping mechanism produces anophelifuge luminous type 3D print magnetic material.
Prepared magnetic composite can effective anophelifuge, drug effect was up to 7 ~ 9 days；And uniformity of luminance is preferable, long remaining
Brightness is for up to 10h.The tensile strength of this magnetic composite is 95.27Mpa, and notch impact strength is 285J/M.
The preparation method of described porous graphene is with reference to the embodiment 1 of Chinese patent application CN104555999A；Described stone
The preparation method of ink alkene quantum dot is with reference to the embodiment 5 of Chinese patent CN102190296B.It should be noted that prepare graphite
Alkene quantum dot, is scattered in second further according to actual amount ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed)
In alcohol, this is only a kind of embodiment, it is also possible to obtain by other means.
Embodiment 19
Based on embodiment 18, difference is: it is 0.8% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous
It is 0.5% that Graphene accounts for the mass percent of ABS gross mass.Prepared magnetic composite can effective anophelifuge, drug effect is up to
7 ~ 9 days；And uniformity of luminance is preferable, long afterglow is for up to 10h.The tensile strength of this magnetic composite is
98.21Mpa, notch impact strength is 292J/M.
Embodiment 19
Based on embodiment 18, difference is: it is 1% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous stone
It is 2% that ink alkene accounts for the mass percent of ABS gross mass.Prepared magnetic composite can effective anophelifuge, drug effect is up to 7 ~ 9
My god；And uniformity of luminance is preferable, long afterglow is for up to 10h.The tensile strength of this magnetic composite is 97.27Mpa, lacks
Mouth impact strength is 280J/M.
Comparative example 10
Preparation method based on embodiment 15, difference is: described functional material is pressed by phosphor material powder and anophelifuge granule
Weight ratio 2:1 forms.Prepared magnetic composite can effective anophelifuge, drug effect was up to 7 ~ 9 days；And uniformity of luminance is relatively
Difference, long afterglow is for up to 6h.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained
Art scheme, all should fall within the scope and spirit of the invention.
Claims (8)
1. the anophelifuge luminous type 3D print magnetic material that Graphene is modified, it is made up of the raw material of following weight portion meter: gather
Lactic acid 40 ~ 50 parts, substance law ABS20 ~ 25 part, emulsion method ABS10 ~ 20 part, styrene-acrylonitrile-Glycidyl methacrylate are sweet
Grease copolymer 5 ~ 10 parts, butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05 part, compounded mix 5 ~ 10 parts, magnetic composite 15 ~ 30
Part, functional material 1 ~ 3, graphene quantum dot and porous graphene；Described magnetic composite by Graphene/croci and
Multi-walled carbon nano-tubes/neodymium iron boron powder forms by weight 3:2；Described compounded mix is by Graphene/SiO2Compounded mix and stone
Ink alkene/Calcium Carbonate Composite Fillers forms by weight 3:1；Described functional material is by Graphene/SiO2/ fluorescent material composite and
Anophelifuge granule forms by weight 2:1；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polylactic acid, described porous
It is 0.1 ~ 2% that Graphene accounts for the percentage by weight of ABS gross weight；
The anophelifuge luminous type 3D print magnetic material preparation method of described a kind of Graphene modification is as follows:
(1) pretreatment polylactic acid raw material: polylactic acid raw material is ground into 300 mesh powder, is scattered in pure water, after ultrasonic 1 hour,
Ultrasonic limit, limit microwave exposure 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
(2) prepare PLA/ filler master batch: compounded mix ultrasonic agitation be scattered in pure water, obtain compounded mix solution, standby；?
Under heating-up temperature, half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution, be divided into two first
Part, second part of PLA solution, standby；Under temperature constant state, the ultrasonic first part of PLA solution in high-speed stirred limit, limit, dropping is compound
Filler solution, ultrasonic agitation 30 ~ 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 30 ~ 60min；Continue dropping
Graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain filler polylactic acid mixed liquor；Filler polylactic acid mixed liquor is passed through
Spray dryer stock in groove, filler polylactic acid mixed liquor is ejected into spray dryer by the speed with 200～300ml/min
In, it is dried to obtain PLA/ filler master batch；
(3) prepare PLA/ magnetic powder master batch: magnetic composite ultrasonic agitation be scattered in pure water, obtain magnetic composite solution,
Standby；At the heating temperature, being dissolved in organic solvent by second half pretreatment polylactic acid, obtain PLA solution, one is divided into
Two obtain the 3rd part, the 4th part of PLA solution, standby；Under temperature constant state, the ultrasonic 3rd part of PLA solution in high-speed stirred limit, limit,
Dropping magnetic composite solution, ultrasonic agitation 30 ~ 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 30 ~
60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain magnetic powder polylactic acid mixed liquor；Magnetic powder is gathered
What lactic acid mixed liquor was passed through spray dryer stocks in groove, and magnetic powder polylactic acid mixed liquor is sprayed by the speed with 200～300ml/min
It is mapped in spray dryer, is dried to obtain PLA/ magnetic powder master batch；
(4) Graphene modified ABS/functional agglomerate is prepared: at room temperature with under the speed conditions of 1000 ~ 1500r/min, to container
In add substance law ABS, emulsion method ABS, functional material and porous graphene successively, high-speed stirred 30 ~ 60min is sufficiently mixed；
The mixture obtained feeding rotating nozzle spray dryer is spray-dried, inlet temperature 185 DEG C, by being spray-dried
Outlet quickly cooling obtains Graphene modified ABS/functional agglomerate；
(5) by ABS/ functional agglomerate modified to PLA/ filler master batch, PLA/ magnetic powder master batch and Graphene, styrene-acrylonitrile-first
Base glycidyl acrylate copolymer, butyltriphenylphosphonium bromide phosphine mix, and melt at 185 DEG C through double screw extruder
It is blended, prepares the co-continuous ABS/PLA alloy with magnetic properties, then it is modified to produce a kind of Graphene through material strip shaping mechanism
Anophelifuge luminous type 3D print magnetic material.
The anophelifuge luminous type 3D print magnetic material that a kind of Graphene the most according to claim 1 is modified, it is characterised in that
Described Graphene is prepared by following methods: taking a certain amount of acid flat band ink, 1000 DEG C process 2 hours, then at 8%H in atmosphere2
Nitrogen and hydrogen mixture in 1100 DEG C of in-situ reducing process 1.0 hours, add macrogol ester and the mass ratio of mass ratio 3%
Tetracarboxylic dianhydride's dinaphthyl of 5.0%, is made into, with water, the slurry that concentration is 82.0%, first enters under the ultrasonic assistant that power is 700W
Row 4000 turns/min ball milling 10 hours, then adjust and to 300W ultrasound wave, carry out 2000 turns/min ball milling 5 hours, through height after ball milling
Speed 10000 turns/min of centrifuge separates, lyophilization, it is thus achieved that Graphene solid.
The anophelifuge luminous type 3D print magnetic material that a kind of Graphene the most according to claim 2 is modified, it is characterised in that
Graphene/SiO2Compounded mix preparation method is as follows: Graphene ultrasonic agitation be scattered in ethanol；Add certain proportion afterwards
Water and ammonia, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.6:1, and regulation pH value is 9, reaction
Temperature is 25 DEG C, reacts 4.2 hours, is centrifuged and cleans 3 times to obtain with acetone and deionized water, deionized water successively sinking
Form sediment；This is deposited in 90o2h it is dried, to obtain being coated with SiO under C2Graphene compounded mix.
The anophelifuge luminous type 3D print magnetic material that a kind of Graphene the most according to claim 2 is modified, it is characterised in that
The preparation method of graphene/carbon acid calcium compounded mix is as follows: is added by 1 part of Graphene in 100ml deionized water, surpasses at 800kW
Graphene dispersing solution is prepared after acoustic vibration and the lower dispersion 200min of 1300r/min centrifugal speed stirring；By 73 parts of quantum dot carbonic acid
Calcium adds in 500ml deionized water, makes after disperseing 300min under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir
Obtain calcium carbonate dispersion liquid；Ultrasonic lower toward graphene dispersing solution is slowly added dropwise calcium carbonate dispersion liquid at 100kW, ultrasonic 60min, so
Rear sucking filtration, drying, prepare graphene/carbon acid calcium compounded mix.
The anophelifuge luminous type 3D print magnetic material that a kind of Graphene the most according to claim 2 is modified, it is characterised in that
The preparation method of Graphene/croci is as follows: added by Graphene in 100ml deionized water, at 800kW ultrasonic vibration and
Graphene dispersing solution is prepared after the lower dispersion 200min of 1300r/min centrifugal speed stirring；Croci is added 100ml go from
In sub-water, after disperseing 300min under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir, prepare ferrum oxide dispersion liquid；
Ultrasonic lower toward graphene dispersing solution is slowly added dropwise ferrum oxide dispersion liquid at 200kW, ultrasonic 90min, then sucking filtration, drying, system
Obtain Graphene/croci.
6. Graphene described in is 1:3 with the mass ratio of ferrum oxide, and ferrum oxide is ferroso-ferric oxide.
The anophelifuge luminous type 3D print magnetic material that a kind of Graphene the most according to claim 2 is modified, it is characterised in that
The preparation method of multi-walled carbon nano-tubes/neodymium iron boron powder is as follows: added by multi-walled carbon nano-tubes in 100ml deionized water,
Multi-walled carbon nano-tubes dispersion liquid is prepared after 800kW ultrasonic vibration and the lower dispersion 200min of 1300r/min centrifugal speed stirring；By neodymium
Ferrum boron powder adds in 100ml deionized water, disperses under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir
Neodymium iron boron dispersion liquid is prepared after 300min；Lower divide toward multi-walled carbon nano-tubes dispersion liquid is slowly added dropwise neodymium iron boron 200kW is ultrasonic
Dissipate liquid, ultrasonic 90min, then sucking filtration, drying, prepare multi-walled carbon nano-tubes/neodymium iron boron powder.
8. multi-walled carbon nano-tubes described in is 1:2 with the mass ratio of neodymium iron boron powder.
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