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CN106349663A - Preparing method for polylactic acid antibacterial radiation-resistant masterbatch - Google Patents

Preparing method for polylactic acid antibacterial radiation-resistant masterbatch Download PDF

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CN106349663A
CN106349663A CN201610748726.2A CN201610748726A CN106349663A CN 106349663 A CN106349663 A CN 106349663A CN 201610748726 A CN201610748726 A CN 201610748726A CN 106349663 A CN106349663 A CN 106349663A
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quantum dot
polylactic acid
photochromic
graphene quantum
ultrasonic agitation
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陆庚
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Gaoming District Of Foshan City Is Runying Technology Co Ltd
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Gaoming District Of Foshan City Is Runying Technology Co Ltd
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract

The invention discloses a preparing method for polylactic acid antibacterial photochromic masterbatch, the method comprises the steps of 1, pretreating a polylactic acid materials; 2, dissolving half of the pretreated polylactic acid in an organic solvent, adding antibacterial composite aqueous dispersion under ultrasonic stirring, ultrasonic stirring, antibacterial/radiation-resistant masterbatch can be obtained after spraying and drying; wherein the solute in the mixed aqueous dispersion of the antibacterial compound and the nano bamboo charcoal is mixed with the antibacterial compound and the nano bamboo charcoal by weight ratio of 1-3: 3-5; 3, dissolving half of the pretreated polylactic acid in an organic solvent, adding an aqueous dispersion of photochromic compound under ultrasonic stirring, ultrasonic stirring, the photochromic masterbatch can be obtained after spraying and drying; 4, mixing two kinds of masterbatch to get the mixture, the polylactic acid antibacterial photochromic masterbatch can be obtained by granulating process. The polylactic acid masterbatch has excellent antibacterial, anti-radiation and photochromic properties in order to meet the needs of multi-functional polylactic acid masterbatch and to further broaden the application of polylactic acid masterbatch.

Description

A kind of preparation method of polylactic acid antibiotic radiation proof master batch
Technical field
The present invention relates to technical field of composite materials, a kind of more particularly to system of polylactic acid antibiotic radiation proof master batch Preparation Method.
Background technology
Polylactic acid (pla) is a kind of macromolecular compound being main polymerizable raw material with lactic acid, belongs to lactide and gathers One kind of ester, is made using the starch material that reproducible plant resourceses (as Semen Maydiss) are proposed, and starch material was via fermenting Journey makes lactic acid, then is converted into polylactic acid by chemosynthesis, and production process is pollution-free.Poly-lactic acid products can be by nature after using In boundary, microorganism is degradable, ultimately generates carbon dioxide and water, free from environmental pollution, even if polylactic acid burns, its combustion heat value Identical with incinerating stationery, it is the half incinerating conventional plastic (as polyethylene), and incinerate polylactic acid and can never discharge nitrogen The toxic gas such as compound, sulfide pollute environment, and therefore, polylactic acid has good biodegradability and environmentally friendly spy Levy, be a kind of new green material.
In polylactic acid antibacterial product, the addition manner of antibacterial is not added in the form of antibacterial matrices, the system of antibacterial matrices It is first antibacterial and matrix resin mixing to be machined to wire through twin-screw extrusion as process, drying machine high temperature is dried, and makes Grain obtains antibacterial matrices, processes polylactic acid antibacterial matrices using the method, and dehydrator high temperature drying can lead to polylactic acid to occur again Thermal degradation, lead to properties of product decline.And because nano silver antimicrobials are in granular form, granularity is Nano grade, often only The specific part of poly-lactic acid material can be gathered in it is impossible to be evenly distributed on surface, thus the antibacterial effect of impact；On the other hand, Nanometer silver and poly-lactic acid material cannot be combined closely and (particularly when nano-Ag particles content increases, be susceptible to reunite now As), easily come off in use, thus affecting service life and antibacterial effect.Existing poly-lactic acid material function is more single One it is more difficult to meet multi-functional feature.
Content of the invention
The technical problem to be solved there is provided a kind of preparation method of polylactic acid antibiotic radiation proof master batch.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of the photochromic master batch of polylactic acid antibacterial, it comprises the following steps:
(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, Microwave exposure 30min while ultrasonic；Washing, discharging, it is dried, obtain final product pretreatment polylactic acid；
(2) under heating-up temperature (50 ~ 60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains polylactic acid molten Liquid；Under ultrasonic agitation (500 ~ 800w ultrasonic power, 500 ~ 800rpm mixing speed), Deca concentration is the anti-of 0.1 ~ 3mol/l Bacterium complex and bamboo charcoal nano mix moisture dispersion liquid, ultrasonic agitation (200 ~ 300w ultrasonic power, 200 ~ 300rpm mixing speed) 30 ~ 60min, obtains antibacterial/radioprotective polylactic acid mixed liquor；Then pass to spray dryer stocks in groove, with 200～300ml/ Antibacterial/radioprotective polylactic acid mixed liquor is ejected in spray dryer the speed of min, dry antibacterial/radioprotective master batch；Its In, solute in described antibiotic complex and bamboo charcoal nano mix moisture dispersion liquid is by antibiotic complex and bamboo charcoal nano by weight 1 ~ 3:3 ~ 5 are obtained by mixing；
This antibiotic complex, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters after bake Dry；
This bamboo charcoal nano, through coupling agent pretreatment, specially bamboo charcoal nano is added in dehydrated alcohol, 500 ~ 800rpm stirs Mix 1 ~ 2h；Dropwise Deca accounts for the coupling agent of bamboo charcoal nano mass fraction 2%, continues stirring 1 ~ 2h, filters post-drying；
(3) under heating-up temperature (50 ~ 60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains polylactic acid molten Liquid；Under ultrasonic agitation (500 ~ 800w ultrasonic power, 500 ~ 800rpm mixing speed), Deca concentration is the photic of 0.5 ~ 1g/l Variable color complex aqueous dispersions, ultrasonic agitation (200 ~ 300w ultrasonic power, 200 ~ 300rpm mixing speed) 30 ~ 60min, obtain light Mutagens color polylactic acid mixed liquor；Then pass to stocking in groove of spray dryer, will be photic with the speed of 200～300ml/min Variable color polylactic acid mixed liquor is ejected in spray dryer, dry photochromic master batch；
Described photochromic complex carries out coupling agent pretreatment, particularly as follows: photochromic complex is added in dehydrated alcohol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the coupling agent of photochromic complex mass fraction 2%, continues stirring 1 ~ 2h, Filter post-drying.
(4) mixture mixing the master batch mixing that step (2) (3) is obtained thoroughly acquisition pours the hopper of double screw extruder into In, it is extruded into wire through double screw extruder, after 0 ~ 5 DEG C of bosh cools down, hair-dryer air-dries, described hair-dryer Air outlet temperature is maintained at 10 ~ 20 DEG C, and last pelletize obtains the photochromic master batch of described polylactic acid antibacterial.
Coupling agent is silane coupler, titanate coupling agent or its mixture.
In the present invention, described photochromic complex preparation method is as follows: under nitrogen environment, by concentration be 0.05 ~ The protonic acid solution of 0.5mol/l and the DBSA that concentration is 0.05 ~ 0.5mol/l are mixed with volume ratio 3:1 ~ 3, with When add photochromic powder, add aniline after magnetic agitation 60 ~ 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10； After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；Anti- at 20 DEG C～30 DEG C Answer 12 ~ 36h；Acetone, deionized water wash are vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；Will 1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add the water of volume ratio 4:1 afterwards And ammonia, it is stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 60 ~ 90min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited at 90 DEG C 3h is dried, with To nano polyaniline/photochromic flour complexes/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed in argon Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under atmosphere, remove polyaniline, photochromic powder/porous sio2, that is, photochromic compound Thing.Described photochromic powder is rare earth oxide, and described rare earth oxide is nd2o3、er2o3、pr2o3、ceo2、sm2o3、la2o3、 y2o3、yb2o3At least one of.
In the present invention, a kind of preparation method of antimicrobial composite material comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is Water；Ultrasonic agitation (500 ~ 1000w ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, Deca walks Suddenly the half graphene quantum dot suspension that (1) is obtained, continues ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, born The graphene quantum dot of supported with zinc oxide.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005 ~ 0.01g graphite oxide is added to 5 ~ In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ 0.3g loads the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filters, and dries the graphene quantum dot of the load zinc oxide that must be surface-treated.
(4) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation Speed) second half graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction temperature Spend for 45 ~ 60 DEG C, Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min； Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000w ultrasonic power, 300 ~ 500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon (mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added Enter in 1 m sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis- Titanium oxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~ In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ 0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(8) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.2 The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (the ultrasonic work(of 500 ~ 1000w Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone loading zinc oxide that step (3) is obtained Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that black alkene quantum dot and step (7) are obtained 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, clearly Wash, dry to obtain antimicrobial composite material.
The invention has the following beneficial effects:
The present invention first prepares the graphene quantum dot of load zinc oxide and the graphene quantum dot of load silver/titanium dioxide respectively, Then it is surface-treated, is finally attached on porous graphene, can preferably load and fixing Nano silver grain and zinc oxide, prevent Stop its reunion, significantly improve the stability of Nano silver grain and zinc oxide, make Nano silver grain and zinc oxide have more efficient Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously Agent has more preferable antibacterial effect, and antibacterial is lasting；
The photochromic complex that the present invention adopts has photochromic effect, makes product more rich and varied, can be with photograph The shades of colour penetrated the difference of light intensity and change, is a splendid legacy, full of magnificent carriage, increases sentiment and artistic effect；
The bamboo charcoal nano that the present invention adopts contains the multiple beneficial element such as charcoal, hydrogen, oxygen, fine and closely woven porous, can block and absorb each The erosion of the harm ray that kind of electrical equipment produces, makes human body thoroughly exempt the harm of harm ray, bamboo charcoal nano also can produce bear from Son, adsorbs and decomposes various free harmful substances, automatically adjusts humidity, also can produce the far infrared being best suitable for human body.
The present invention is through rational arrange in pairs or groups bamboo charcoal nano, photochromic complex and antimicrobial composite material, functional additive Between synergism so that polylactic acid master batch has an excellent antibacterial shielding property, photochromic and purify air characteristic, Meet the demand of multi-functional polylactic acid master batch, widen the application of polylactic acid master batch further.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, It is not limitation of the invention.
Embodiment 1
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 50ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 30min simultaneously, swashs Photoirradiation power is 2w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml zinc oxide fluid dispersion, Deca step (1) be obtained one Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene of zinc oxide Quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005g graphite oxide is added to the dispersion of 8ml In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to load the Graphene of zinc oxide Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200w, at 240 DEG C, react 60min；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processing.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another Schungite alkene quantum dot suspension, Deca concentration is 0.005mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense Spend for 0.08mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.1g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(6) 0.3mol/l titanium source (titanium source is potassium fluotitanate) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts ph with concentrated ammonia solution It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005g graphite oxide is added to dividing of 10ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.3g to carry silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 200w, at 240 DEG C react 60min；Cooling, filters, dries The load silver/titanium dioxide graphene quantum dot of surface treatment.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, add the graphene quantum dot loading zinc oxide that step (3) is obtained Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min being obtained with step (7), Ran Houyi To the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.7g c60 powder, measure the dense sulfur that 80ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 2g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 45min simultaneously, swashs Photoirradiation power is 1.5w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, Deca step (1) is obtained Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the graphite of zinc oxide Alkene quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.008g graphite oxide is added to dividing of 10ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to load the graphite of zinc oxide Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table The graphene quantum dot of the load zinc oxide that face is processed.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another Schungite alkene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense Spend for 0.05mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(6) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table The load silver/titanium dioxide graphene quantum dot that face is processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) is obtained, then moves to In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g c60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 5h；Rapidly join 100ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 60min simultaneously, swashs Photoirradiation power is 1w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 1mg/ml, solvent is water； Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, the half that Deca step (1) is obtained Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene amount of zinc oxide Sub- point.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.01g graphite oxide is added to the dispersion of 5ml In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.3g to load the Graphene of zinc oxide Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processing.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another Schungite alkene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense Spend for 0.01mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(6) 0.1mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added to In 1 mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 110 DEG C, after reaction 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide Graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.01g graphite oxide is added to the dispersion of 5ml In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to carry silver/titanium dioxide Graphene Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface The load silver/titanium dioxide graphene quantum dot processing.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min that step (7) is obtained, then moves to In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Comparative example 1
A kind of preparation method of antimicrobial composite material, comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 50ml Graphene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration For 0.01mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, add the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, Dry to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of antimicrobial composite material, comprises the following steps: weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan Base sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, Deca concentration is 0.003mol/l silver nitrate solution, controlling reaction temperature is 50 DEG C, and Deca concentration is 0.04mol/l two citric acid monohydrate trisodiums, Continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene antibiosis material that must load silver.
The detailed process that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated and step are as follows:
The antibacterial of test is respectively staphylococcus aureuses and escherichia coli；With reference to minimal inhibitory concentration (minimal Inhibitory concentration, mic) method of testing (xiang cai, shaozao tan, aili yu, jinglin zhang, jiahao liu, wenjie mai, zhenyou jiang. sodium1- naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver nanoparticles with lower cytotoxicity and long-term antibacterial Activity.chemistry-an asian journal. 2012,7 (7): 1664-1670.), first weighed with electronic balance Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with mh meat soup to serial dilute again Release variable concentrations, be added separately in the mh culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/ml, Then shaken cultivation 24h at 37 DEG C, observes as a result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, no The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (mic) for this antibacterial with the antibacterial of not long tube.
Table 1: the anti-microbial property of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, add prepared by each embodiment of 1g and comparative example in bottle Antimicrobial composite material sample and 200ml saline (0.9mass%), and soak 6 respectively in water, 24, sample after 72h, measure it Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Embodiment 4
A kind of preparation method of the photochromic master batch of polylactic acid antibacterial, it comprises the following steps:
(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, Microwave exposure 30min while ultrasonic；Washing, discharging, it is dried, obtain final product pretreatment polylactic acid；
(2) under heating-up temperature (60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution； Under ultrasonic agitation (800w ultrasonic power, 800rpm mixing speed), Deca 3ml concentration is embodiment 2 antibacterial of 0.1mol/l Complex aqueous dispersions, ultrasonic agitation (300w ultrasonic power, 300rpm mixing speed) 60min, obtain antibacterial/radioprotective and gather breast Sour mixed liquor；Then pass to stocking in groove of spray dryer, with the speed of 300ml/min, antibacterial/radioprotective polylactic acid is mixed Close liquid to be ejected in spray dryer, dry antibacterial/radioprotective master batch；Wherein, described antibiotic complex and bamboo charcoal nano mix Solute in Heshui dispersion liquid is by antibiotic complex and bamboo charcoal nano (particle diameter is between 100 ~ 500nm) by weight 1:5 mixing ?；
(3) under heating-up temperature (60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution； Under ultrasonic agitation (800w ultrasonic power, 800rpm mixing speed), Deca 3ml concentration is the photochromic complex of 1g/l Aqueous dispersions, ultrasonic agitation (300w ultrasonic power, 300rpm mixing speed) 60min, obtain photochromic polylactic acid mixed liquor； Then pass to stocking in groove of spray dryer, photochromic polylactic acid mixed liquor is ejected into by spray with the speed of 300ml/min In mist exsiccator, dry photochromic master batch；
(4) mixture mixing the master batch mixing that step (2) (3) is obtained thoroughly acquisition is poured in the hopper of double screw extruder, warp Double screw extruder is extruded into wire, and after 0 ~ 5 DEG C of bosh cools down, hair-dryer air-dries, described hair-dryer air outlet Temperature is maintained at 10 ~ 20 DEG C, and last pelletize obtains the photochromic master batch of described polylactic acid antibacterial.
Wherein, described antibiotic complex, bamboo charcoal nano and photochromic complex be preferably through coupling agent pretreatment, with anti- As a example bacterium complex, specially antibiotic complex is added in dehydrated alcohol, 800rpm stirs 2h；Dropwise Deca accounts for antibacterial The coupling agent of complex mass fraction 2%, continues stirring 1h, filters post-drying.
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by concentration for 0.4mol/l's Protonic acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder (nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
Embodiment 5
A kind of preparation method of the photochromic master batch of polylactic acid antibacterial, it comprises the following steps:
(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, Microwave exposure 30min while ultrasonic；Washing, discharging, it is dried, obtain final product pretreatment polylactic acid；
(2) under heating-up temperature (60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution； Under ultrasonic agitation (800w ultrasonic power, 800rpm mixing speed), Deca 3ml concentration is that embodiment 2 antibacterial of 1mol/l is multiple Compound aqueous dispersions, ultrasonic agitation (300w ultrasonic power, 300rpm mixing speed) 60min, obtain antibacterial/radioprotective polylactic acid Mixed liquor；Then pass to stocking in groove of spray dryer, with the speed of 300ml/min, antibacterial/radioprotective polylactic acid is mixed Liquid is ejected in spray dryer, dry antibacterial/radioprotective master batch；Wherein, described antibiotic complex and bamboo charcoal nano mixing Solute in aqueous dispersions is obtained by mixing by weight 2:3 by antibiotic complex and bamboo charcoal nano；
(3) under heating-up temperature (60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution； Under ultrasonic agitation (800w ultrasonic power, 800rpm mixing speed), Deca 3ml concentration is the photochromic compound of 0.8g/l Thing aqueous dispersions, ultrasonic agitation (300w ultrasonic power, 300rpm mixing speed) 60min, obtain photochromic polylactic acid mixing Liquid；Then pass to stocking in groove of spray dryer, with the speed of 300ml/min, photochromic polylactic acid mixed liquor is ejected into In spray dryer, dry photochromic master batch；
(4) mixture mixing the master batch mixing that step (2) (3) is obtained thoroughly acquisition is poured in the hopper of double screw extruder, warp Double screw extruder is extruded into wire, and after 0 ~ 5 DEG C of bosh cools down, hair-dryer air-dries, described hair-dryer air outlet Temperature is maintained at 10 ~ 20 DEG C, and last pelletize obtains the photochromic master batch of described polylactic acid antibacterial.
Wherein, described antibiotic complex, bamboo charcoal nano and photochromic complex be preferably through coupling agent pretreatment, with anti- As a example bacterium complex, specially antibiotic complex is added in dehydrated alcohol, 800rpm stirs 2h；Dropwise Deca accounts for antibacterial The coupling agent of complex mass fraction 2%, continues stirring 1h, filters post-drying.
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by concentration for 0.4mol/l's Protonic acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder (nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
Embodiment 6
A kind of preparation method of the photochromic master batch of polylactic acid antibacterial, it comprises the following steps:
(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, Microwave exposure 30min while ultrasonic；Washing, discharging, it is dried, obtain final product pretreatment polylactic acid；
(2) under heating-up temperature (60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution； Under ultrasonic agitation (800w ultrasonic power, 800rpm mixing speed), Deca 3ml concentration is that embodiment 2 antibacterial of 3mol/l is multiple Compound aqueous dispersions, ultrasonic agitation (300w ultrasonic power, 300rpm mixing speed) 60min, obtain antibacterial/radioprotective polylactic acid Mixed liquor；Then pass to stocking in groove of spray dryer, with the speed of 300ml/min, antibacterial/radioprotective polylactic acid is mixed Liquid is ejected in spray dryer, dry antibacterial/radioprotective master batch；Wherein, described antibiotic complex and bamboo charcoal nano mixing Solute in aqueous dispersions is obtained by mixing by weight 3:4 by antibiotic complex and bamboo charcoal nano；
(3) under heating-up temperature (60 DEG C), half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution； Under ultrasonic agitation (800w ultrasonic power, 800rpm mixing speed), Deca 3ml concentration is the photochromic compound of 0.5g/l Thing aqueous dispersions, ultrasonic agitation (300w ultrasonic power, 300rpm mixing speed) 60min, obtain photochromic polylactic acid mixing Liquid；Then pass to stocking in groove of spray dryer, with the speed of 300ml/min, photochromic polylactic acid mixed liquor is ejected into In spray dryer, dry photochromic master batch；
(4) mixture mixing the master batch mixing that step (2) (3) is obtained thoroughly acquisition is poured in the hopper of double screw extruder, warp Double screw extruder is extruded into wire, and after 0 ~ 5 DEG C of bosh cools down, hair-dryer air-dries, described hair-dryer air outlet Temperature is maintained at 10 ~ 20 DEG C, and last pelletize obtains the photochromic master batch of described polylactic acid antibacterial.
Wherein, described antibiotic complex, bamboo charcoal nano and photochromic complex be preferably through coupling agent pretreatment, with anti- As a example bacterium complex, specially antibiotic complex is added in dehydrated alcohol, 800rpm stirs 2h；Dropwise Deca accounts for antibacterial The coupling agent of complex mass fraction 2%, continues stirring 1h, filters post-drying.
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by concentration for 0.4mol/l's Protonic acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder (nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
Comparative example 3
Based on the preparation method of embodiment 6, difference is: is not added with antibiotic complex；Described photochromic complex is nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3.
Comparative example 4
Based on the preparation method of embodiment 6, difference is: is not added with photochromic complex and bamboo charcoal nano.
Embodiment 4 ~ 6 and comparative example 3, the antibacterial and deodouring of 4 poly-lactic acid materials and purifying formaldehyde performance are tested, result As follows:
Air purification effect test is as follows: contrast, using concentration of formaldehyde indoor in front and back and electromagnetic radiation etc., is adsorbed with characterizing it Ability.In 10 square metres of vacant room between, place following article: 1. make 10, the clamping plate of furniture, surface Wu Bao Dress；2. 5 barrels are painted, bung is opened；3. television set 1, opening；4. electric fan 1, opening.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation Art scheme, all should fall within the scope and spirit of the invention.

Claims (9)

1. a kind of preparation method of polylactic acid antibiotic radiation proof master batch, it comprises the following steps:
(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, Microwave exposure 30min while ultrasonic；Washing, discharging, it is dried, obtain final product pretreatment polylactic acid；
(2) at the heating temperature, half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution；Ultrasonic Under stirring, Deca concentration is the antibiotic complex of 0.1 ~ 3mol/l and bamboo charcoal nano mix moisture dispersion liquid, ultrasonic agitation 30 ~ 60min, obtains antibacterial/radioprotective polylactic acid mixed liquor；Then pass to spray dryer stocks in groove, with 200～300ml/min Speed antibacterial/radioprotective polylactic acid mixed liquor is ejected in spray dryer, dry antibacterial/radioprotective master batch；Wherein, Solute in described antibiotic complex and bamboo charcoal nano mix moisture dispersion liquid by antibiotic complex and bamboo charcoal nano by weight 1 ~ 3:3 ~ 5 are obtained by mixing；
(3) at the heating temperature, half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution；Ultrasonic Under stirring, Deca concentration is the photochromic complex aqueous dispersions of 0.5 ~ 1g/l, and ultrasonic agitation 30 ~ 60min obtains photochromic Polylactic acid mixed liquor；Then pass to stocking in groove of spray dryer, will be photochromic poly- with the speed of 200～300ml/min Lactic acid mixed liquor is ejected in spray dryer, dry photochromic master batch；
(4) mixture mixing the master batch mixing that step (2) (3) is obtained thoroughly acquisition is poured in the hopper of double screw extruder, warp Double screw extruder is extruded into wire, and after 0 ~ 5 DEG C of bosh cools down, hair-dryer air-dries, described hair-dryer air outlet Temperature is maintained at 10 ~ 20 DEG C, and last pelletize obtains the photochromic master batch of described polylactic acid antibacterial.
2. the preparation method of polylactic acid antibiotic radiation proof master batch according to claim 1 is it is characterised in that described antibacterial is multiple Compound, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, and 500 ~ 800rpm stirs 1 ~ 2h； Dropwise Deca accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters post-drying.
3. the preparation method of polylactic acid antibiotic radiation proof master batch according to claim 1 is it is characterised in that described light-induced variable Color complex carries out coupling agent pretreatment, particularly as follows: photochromic complex is added in dehydrated alcohol, 500 ~ 800rpm stirs 1~2h；Dropwise Deca accounts for the coupling agent of photochromic complex mass fraction 2%, continues stirring 1 ~ 2h, filters post-drying.
4. the preparation method of the polylactic acid antibiotic radiation proof master batch according to claim 1 or 3 is it is characterised in that described light Mutagens color complex preparation method is as follows: under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/l and concentration is The DBSA of 0.05 ~ 0.5mol/l is mixed with volume ratio 3:1 ~ 3, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~ Aniline is added, the color-change powder of light and aniline mass ratio are 1:5 ~ 10 after 120min；After continuously stirred 60 ~ 90min, dropwise Deca mistake Ammonium sulfate, aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are for several times After be vacuum dried, nano polyaniline/photochromic flour complexes of milling to obtain；1 ~ 10g nano polyaniline/photochromic powder is combined Thing ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into positive silicic acid second Ester, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Carry out centrifugation and use acetone and deionization successively Water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/photochromic flour complexes/sio2； By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove Polyaniline, photochromic powder/porous sio2, i.e. photochromic complex.
5. the preparation method of polylactic acid antibiotic radiation proof master batch according to claim 4 is it is characterised in that described antibacterial is multiple Compound is obtained by the following method:
(1) prepare graphene quantum dot suspension: 100rpm speed stirring graphene quantum dot suspension, laser irradiation 30 simultaneously ~ 60min, laser irradiation power is 1 ~ 2w；
(2) weigh Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~ 100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that Deca step (1) is obtained, continue ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface treatment of the graphene quantum dot of load zinc oxide；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, Deca silver nitrate is molten Liquid, controlling reaction temperature is 45 ~ 60 DEG C, Deca two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly Wash, dry the graphene quantum dot that must load silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3 Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried to obtain sio2The stone of the load silver of cladding Black alkene quantum dot；
(6) 0.1 ~ 0.3mol/l titanium source is added in 1mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2 Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, is aged, clearly Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, the graphene quantum dot of load zinc oxide that addition step (3) is obtained and step (7) are obtained Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~ It is incubated 15 ~ 30min at 120 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
6. the preparation method of polylactic acid antibiotic radiation proof master batch according to claim 5 is it is characterised in that described Graphene The preparation method of quantum dot suspension is as follows: weighs 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm Stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change into Water-bath, keeps 30 ~ 40 DEG C of bath temperature, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then use molecular cut off Bag filter for 1000 is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, Laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
7. the preparation method of polylactic acid antibiotic radiation proof master batch according to claim 5 is it is characterised in that black alkene is 2 ~ 5 Layer, hole size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
8. polylactic acid antibiotic radiation proof master batch according to claim 5 preparation method it is characterised in that described load silver-colored/ The surface treatment of titanium dioxide graphene quantum dot particularly as follows: be added to the dispersion of 5 ~ 10ml by 0.005 ~ 0.01g graphite oxide In agent, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to carry silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves To liner for, in the microwave hydrothermal reaction kettle of politef, being placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power For 200 ~ 400w, at 200 ~ 240 DEG C, react 60 ~ 90min；Cooling, filters, dries the load silver/titanium dioxide stone that must be surface-treated Black alkene quantum dot.
9. the preparation method of polylactic acid antibiotic radiation proof master batch according to claim 5 is it is characterised in that described load oxygen The surface treatment of graphene quantum dot changing zinc particularly as follows: be added to the dispersant of 5 ~ 10ml by 0.005 ~ 0.01g graphite oxide In, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to load the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to interior Serve as a contrast as, in the microwave hydrothermal reaction kettle of politef, being placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, and dries the Graphene amount of the load zinc oxide that must be surface-treated Sub- point.
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Application publication date: 20170125