CN106189137A - A kind of 3D print magnetic material of anophelifuge antimicrobial form - Google Patents

A kind of 3D print magnetic material of anophelifuge antimicrobial form Download PDF

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CN106189137A
CN106189137A CN201610612785.7A CN201610612785A CN106189137A CN 106189137 A CN106189137 A CN 106189137A CN 201610612785 A CN201610612785 A CN 201610612785A CN 106189137 A CN106189137 A CN 106189137A
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pla
polylactic acid
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magnetic
graphene
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黎淑娟
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Foshan Gaoming Technology Co Ltd
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Foshan Gaoming Technology Co Ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses the 3D print magnetic material of a kind of anophelifuge antimicrobial form, 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；Described magnetic composite is made up of by weight 3:2 Graphene/croci and multi-walled carbon nano-tubes/neodymium iron boron powder；Described compounded mix is by Graphene/SiO2Compounded mix forms by weight 3:1 with graphene/carbon acid calcium compounded mix；Described functional material is by multi-walled carbon nano-tubes/nanometer silver/SiO2Anti-biotic material and anophelifuge granule form by weight 3:2.The 3D print magnetic material of this anophelifuge antimicrobial form, not only has mechanics electric property and the magnetic property of excellence, and has optimal anophelifuge anti-microbial property, widened the range of application of 3D printed material further.

Description

A kind of 3D print magnetic material of anophelifuge antimicrobial form
Technical field
The present invention relates to field of compound material, a kind of have the magnetic ABS/PLA composite wood printed for 3D 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 invention provides the 3D print magnetic material of a kind of anophelifuge antimicrobial form Material, not only has mechanics electric property and the magnetic property of excellence, and has optimal anophelifuge anti-microbial property, widen further The range of application of 3D printed material.
The technical problem to be solved is achieved by the following technical programs:
A kind of 3D print magnetic material of anophelifuge antimicrobial form, 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；Described magnetic composite is by Graphene/croci and multi-walled carbon nano-tubes/neodymium iron boron powder 3:2 group by weight Become；Described compounded mix is by Graphene/SiO2Compounded mix forms by weight 3:1 with graphene/carbon acid calcium compounded mix；Institute State functional material by multi-walled carbon nano-tubes/nanometer silver/SiO2Anti-biotic material and anophelifuge granule form by weight 3:2；
The preparation method of the 3D print magnetic material of a kind of anophelifuge antimicrobial form, 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, obtains filler polylactic acid mixed liquor；What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, Filler polylactic acid mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, is dried to obtain PLA/ filler mother Grain；The nozzle diameter of described spray dryer is 0.5～0.7mm, and dry air flow rates is 30～35m3/ h, temperature 120～160 ℃；
(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, obtain magnetic powder polylactic acid mixed liquor；Magnetic powder polylactic acid mixed liquor is passed through the storage of spray dryer In standby groove, magnetic powder polylactic acid mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, is dried to obtain PLA/ Magnetic powder master batch；The nozzle diameter of described spray dryer is 0.5～0.7mm, and dry air flow rates is 30～35m3/ h, temperature 120～160 DEG C；
(4) ABS/ functional agglomerate is prepared: at room temperature with under the speed conditions of 1000 ~ 1500r/min, add successively in container Substance law ABS, emulsion method ABS and functional material, high-speed stirred 30 ~ 60min is sufficiently mixed；The mixture obtained is sent into and rotates Formula nozzle spray drier is spray-dried, inlet temperature 185 DEG C, is quickly cooled down by spray drying exit and obtains ABS/ merit Can master batch；
(5) by PLA/ filler master batch, PLA/ magnetic powder master batch and ABS/ functional agglomerate, styrene-acrylonitrile-Glycidyl methacrylate Glyceride copolymer, butyltriphenylphosphonium bromide phosphine mix, and carry out melt blending through double screw extruder, prepare at 185 DEG C There is the co-continuous ABS/PLA alloy of magnetic properties, then produce the 3D print magnetic material of anophelifuge antimicrobial form through material strip shaping mechanism 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.
In the present invention, described ABS/PLA luminescent composite is made up of the raw material of following weight portion meter: polylactic acid 42 Part, substance law ABS21.78 part, emulsion method ABS17 part, styrene-acrylonitrile-glycidyl methacrylate copolymer 5 Part, butyltriphenylphosphonium bromide phosphine 0.02 part, compounded mix 9.7 parts, magnetic composite 24 parts, functional material 1.5 parts.
In the present invention, described ABS/PLA luminescent composite is made up of the raw material of following weight portion meter: polylactic acid 42 Part, substance law ABS21.78 part, emulsion method ABS17 part, styrene-acrylonitrile-glycidyl methacrylate copolymer 5 Part, butyltriphenylphosphonium bromide phosphine 0.02 part, compounded mix 9.7 parts, magnetic composite 24 parts, functional material 3 parts.
There is advantages that
Obtaining scientific matching by test of many times, prepared described ABS/PLA luminescent composite not only has the mechanics of excellence Performance and magnetic property, and there is optimal anophelifuge antibacterial characteristics, widen the range of application of 3D printed material, anophelifuge further Effect is up to 7 ~ 9 days, and antibiotic rate is up to 99.8%.
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:
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, many walls Carbon nano tube/nanometer silver/SiO2Anti-biotic material and anophelifuge granule form by weight 3:2), high-speed stirred 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 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 antibiotic rate is as follows: escherichia coli: 99.8%, staphylococcus aureus: 99.5%. (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)；Can effective anophelifuge, drug effect is up to 7 ~ 9 days.The stretch-proof of this magnetic composite is strong Degree is 49.02Mpa, 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 antibiotic rate is as follows: escherichia coli: 98.1%, staphylococcus aureus: 98.2%. (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)；Can effective anophelifuge, drug effect is up to 6 ~ 7 days.The stretch-proof of this magnetic composite is strong Degree is 48.78Mpa, 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 antibiotic rate as follows: escherichia coli: 96.8%, staphylococcus aureus: 96.3%.(anti-microbial property is tested: root Detect according to GB/T23763-2009 national standard, select escherichia coli ATCC8739 and staphylococcus aureus ATCC6538P is strain)；Can effective anophelifuge, drug effect is up to 5 ~ 6 days.The tensile strength of this magnetic composite is 47.25Mpa, 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, multi-walled carbon nano-tubes/nanometer silver/SiO2Anti-biotic material and anophelifuge granule form by weight 3:2) and porous graphene (it is 1% that porous graphene accounts for the mass percent of ABS gross mass), high-speed stirred 60min is sufficiently mixed；The mixture that will obtain Send into rotating nozzle spray dryer to be spray-dried, inlet temperature 185 DEG C, quickly cooled down by spray drying exit To 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 (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 antibiotic rate is as follows: escherichia coli: 99.8%, staphylococcus aureus: 99.5%；Can With effective anophelifuge, drug effect is up to 7 ~ 9 days；The tensile strength of this magnetic composite is 95.35Mpa, and notch impact strength is 282J/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 antibiotic rate is as follows: escherichia coli: 99.8%, staphylococcus aureus: 99.5%；Can effective anophelifuge, drug effect is up to 7 ~ 9 days；The stretch-proof of this magnetic composite Intensity is 99.21Mpa, and notch impact strength is 295J/M.
Embodiment 20
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 antibiotic rate is as follows: escherichia coli: 99.8%, staphylococcus aureus: 99.5%；Can effective anophelifuge, drug effect is up to 7 ~ 9 days；The stretch-proof of this magnetic composite Intensity is 97.38Mpa, and notch impact strength is 283J/M.
Comparative example 10
Preparation method based on embodiment 15, difference is: described functional material is pressed by nano silver material and anophelifuge granule Weight ratio 3:2 forms.Prepared magnetic composite can effective anophelifuge, drug effect was up to 7 ~ 9 days；Antibiotic rate is as follows: large intestine Bacillus: 90.8%, staphylococcus aureus: 91.3%.(anti-microbial property is tested: carry out according to GB/T23763-2009 national standard Detection, selecting escherichia coli ATCC8739 and staphylococcus aureus ATCC6538P is strain).
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 (3)

1. a 3D print magnetic material for anophelifuge antimicrobial form, it is made up of the raw material of following weight portion meter: polylactic acid 40 ~ 50 Part, 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, function material Material 1 ~ 3；Described magnetic composite is by Graphene/croci and multi-walled carbon nano-tubes/neodymium iron boron powder 3:2 by weight Composition；Described compounded mix is by Graphene/SiO2Compounded mix forms by weight 3:1 with graphene/carbon acid calcium compounded mix； Described functional material is by multi-walled carbon nano-tubes/nanometer silver/SiO2Anti-biotic material and anophelifuge granule form by weight 3:2；
The 3D print magnetic material preparation method of described anophelifuge antimicrobial form 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, obtain filler Polylactic acid mixed liquor；What filler polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 200～300ml/min Filler polylactic acid mixed liquor is ejected in spray dryer by degree, 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, obtains magnetic powder polylactic acid mixed liquor；What magnetic powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, with 200～ Magnetic powder polylactic acid mixed liquor is ejected in spray dryer by the speed of 300ml/min, is dried to obtain PLA/ magnetic powder master batch；
(4) ABS/ functional agglomerate is prepared: at room temperature with under the speed conditions of 1000 ~ 1500r/min, add successively in container Substance law ABS, emulsion method ABS and functional material, high-speed stirred 30 ~ 60min is sufficiently mixed；The mixture obtained is sent into and rotates Formula nozzle spray drier is spray-dried, inlet temperature 185 DEG C, is quickly cooled down by spray drying exit and obtains ABS/ merit Can master batch；
(5) by PLA/ filler master batch, PLA/ magnetic powder master batch and ABS/ functional agglomerate, styrene-acrylonitrile-Glycidyl methacrylate Glyceride copolymer, butyltriphenylphosphonium bromide phosphine mix, and carry out melt blending through double screw extruder, prepare at 185 DEG C There is the co-continuous ABS/PLA alloy of magnetic properties, then produce the 3D print magnetic material of anophelifuge antimicrobial form through material strip shaping mechanism Material.
The 3D print magnetic material of anophelifuge antimicrobial form the most according to claim 1, it is characterised in that described ABS/PLA sends out Photoreactivation material is made up of the raw material of following weight portion meter: polylactic acid 42 parts, substance law ABS21.78 part, emulsion method ABS17 part, Styrene-acrylonitrile-glycidyl methacrylate copolymer 5 parts, butyltriphenylphosphonium bromide phosphine 0.02 part, compounded mix 9.7 parts, magnetic composite 24 parts, functional material 1.5 parts.
The 3D print magnetic material of anophelifuge antimicrobial form the most according to claim 1, it is characterised in that described ABS/PLA sends out Photoreactivation material is made up of the raw material of following weight portion meter: polylactic acid 42 parts, substance law ABS21.78 part, emulsion method ABS17 part, Styrene-acrylonitrile-glycidyl methacrylate copolymer 5 parts, butyltriphenylphosphonium bromide phosphine 0.02 part, compounded mix 9.7 parts, magnetic composite 24 parts, functional material 3 parts.
CN201610612785.7A 2016-07-29 2016-07-29 A kind of 3D print magnetic material of anophelifuge antimicrobial form Pending CN106189137A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101946985A (en) * 2010-06-02 2011-01-19 陈欣荣 Element fabric health-improving protective clothing capable of killing and repelling mosquitoes
CN102273742A (en) * 2011-09-01 2011-12-14 丁一 Nano chitin element anionic far-infrared antibacterial, anti-mite and electromagnetic wave preventing student's wear
CN104829970A (en) * 2015-05-14 2015-08-12 赵景歧 Mosquito-repelling wood-plastic magnetic floorboard and preparation method thereof
CN105001586A (en) * 2015-07-14 2015-10-28 暨南大学 Electric conduction compound ABS/PLA material for 3D printing wires as well as preparation method and application of electric conduction compound ABS/PLA material
CN105694190A (en) * 2016-01-27 2016-06-22 苏州翠南电子科技有限公司 Magnetic plastic material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101946985A (en) * 2010-06-02 2011-01-19 陈欣荣 Element fabric health-improving protective clothing capable of killing and repelling mosquitoes
CN102273742A (en) * 2011-09-01 2011-12-14 丁一 Nano chitin element anionic far-infrared antibacterial, anti-mite and electromagnetic wave preventing student's wear
CN104829970A (en) * 2015-05-14 2015-08-12 赵景歧 Mosquito-repelling wood-plastic magnetic floorboard and preparation method thereof
CN105001586A (en) * 2015-07-14 2015-10-28 暨南大学 Electric conduction compound ABS/PLA material for 3D printing wires as well as preparation method and application of electric conduction compound ABS/PLA material
CN105694190A (en) * 2016-01-27 2016-06-22 苏州翠南电子科技有限公司 Magnetic plastic material

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