CN106317387A - Preparation method of electrostatic prevention and antibiotic polylactic acid material - Google Patents

Preparation method of electrostatic prevention and antibiotic polylactic acid material Download PDF

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CN106317387A
CN106317387A CN201610748815.7A CN201610748815A CN106317387A CN 106317387 A CN106317387 A CN 106317387A CN 201610748815 A CN201610748815 A CN 201610748815A CN 106317387 A CN106317387 A CN 106317387A
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quantum dot
lactic acid
graphene quantum
graphene
silver
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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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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract

The invention discloses a preparation method of electrostatic prevention and antibiotic polylactic acid materials. The method consists of steps 1, spreading the antibiotic composite to the lactic acid to prepare a solution with 0.1-2 g/L concentration; stir the solution with ultrasonic for 60-90 min to get the antibiotic lactic acid solution; 2, spreading the conductive filler to the lactic acid to prepare a solution with 1-2 g/L concentration; stir the solution with ultrasonic for 60-90 min to get the conducting lactic acid solution; 3, mixing the antibiotic lactic acid solution and the conducting lactic acid solution at a volume ratio of 2:1 and then place the mixture at a vacuum drying oven under 50-80 oC to bake the mixture in vacuum for 24-36 h, till the mixed liquor contains no moisture; then the polylactic acid material can be obtained through direct condensation method. Through scientific combination of antibiotic composite and conductive filler, raw materials can have synergistic effects, which makes polylactic acid material possess both the antibiotic characteristic and the electrostatic prevention function, and further broadens the scope of application of polylactic acid material.

Description

A kind of preparation method of anti-electrostatic antibiotic poly-lactic acid material
Technical field
The present invention relates to technical field of composite materials, particularly relate to the system of a kind of anti-electrostatic antibiotic poly-lactic acid material Preparation Method.
Background technology
Polylactic acid (PLA) is a kind of macromolecular compound being polymerized for primary raw material with lactic acid, belongs to lactide and gathers The one of ester, the starch material using reproducible plant resources (such as Semen Maydis) to be proposed makes, and starch material is 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, and its combustion heat value Identical with incinerating stationery, it is the half incinerating conventional plastic (such as polyethylene), and incinerates polylactic acid and can never discharge nitrogen The toxic gas such as compound, sulfide pollutes environment, and therefore, polylactic acid has good biodegradability and environmentally friendly spy Levy, be a kind of novel green material.
In polylactic acid antibacterial product, the addition manner of antibacterial does not use the form of antibacterial matrices to add, the system of antibacterial matrices Being first to mix antibacterial and matrix resin to be machined to wire through twin-screw extrusion as process, drying machine high temperature is dried, and makes Grain obtains antibacterial matrices, uses the method processing polylactic acid antibacterial matrices, and dehydrator high temperature drying can cause polylactic acid again to occur Thermal degradation, cause properties of product to decline.And owing to nano silver antimicrobials is 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 affected；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), the most easily come off, thus affect service life and antibacterial effect.Existing poly-lactic acid material function is more single One, it is more difficult to meet multi-functional feature.
Summary of the invention
The technical problem to be solved there is provided the preparation method of a kind of anti-electrostatic antibiotic poly-lactic acid material.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of anti-electrostatic antibiotic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by antibiotic complex, compound concentration is the solution of 0.1 ~ 2g/L, and (500 ~ 800W surpasses ultrasonic agitation Acoustical power, 500 ~ 800rpm mixing speed) 60 ~ 90min, obtain antibacterial lactic acid solution；
This antibiotic complex, through coupling agent pretreatment, is specially and joins in dehydrated alcohol by antibiotic complex, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters after bake Dry；
(2) being dispersed in lactic acid by conductive filler, compound concentration is the solution of 1 ~ 2g/L, ultrasonic agitation (the ultrasonic merit of 500 ~ 800W Rate, 500 ~ 800rpm mixing speed) 60 ~ 90min, obtain conduction lactic acid solution；
(3) antibacterial lactic acid solution and conduction lactic acid solution are placed in 50 ~ 80 DEG C of vacuum drying ovens, very by the mixing of 2:1 volume ratio Empty dry 24 ~ 36h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
Described conductive filler is by porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder 4:2:1:2:2 in mass ratio Mixing composition；
Described conductive filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join 100ml In water heating kettle, in 180 DEG C of baking ovens seal reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C calcine 1h, obtain Porous carbon；CNT, nanometer aluminium powder are dispersed in the aqueous solution of 120ml, immerse porous carbon 1 ~ 2h, make nano material abundant Enter in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, so After sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, 120 DEG C of drying, obtain conductive filler under vacuum.
In the present invention, the preparation method of a kind of antimicrobial composite material comprises the following steps:
(1) preparing 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, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing 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, dropping step Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~ In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min； Ageing, cleans, and dries to load the graphene quantum dot of 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 (being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25 DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo 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) prepares2Cladding carries silver 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) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 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), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(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 merit of 500 ~ 1000W Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone of the load zinc oxide that step (3) prepares Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that ink alkene quantum dot and step (7) prepare 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal, clearly Wash, dry to obtain antimicrobial composite material.
There is advantages that
The present invention the most first prepares graphene quantum dot and the graphene quantum dot of load silver/titanium dioxide of load zinc oxide, Then surface processes, and is finally attached on porous graphene, can preferably load and fix Nano silver grain and zinc oxide, anti- Only it is reunited, and significantly improves the stability of Nano silver grain and zinc oxide, makes 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 a more preferable antibacterial effect, antibacterial persistently；
Conductive filler used in the present invention makes the conductive structure of ink finer and close, forms good interlayer UNICOM structure, conduction Passage is more smooth and easy, thus improves conductivity and stability further, overcomes again pure carbon black conductive ink electric conductivity not Stable defect；
The present invention passes through scientific compatibility antibiotic complex, conductive filler, mutual synergism between raw material so that poly-lactic acid material Not only antibacterial characteristics, also has electrostatic-proof function, has widened the range of application of poly-lactic acid material further.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, It it 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash Photoirradiation power is 2W.
(2) weighing 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, dropping step (1) prepare one Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene of zinc oxide Quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005g graphite oxide joins the dispersion of 8mL In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.2g load zinc oxide Graphene Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another Schungite alkene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense Degree is 0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding Carry the graphene quantum dot of silver.
(6) 0.3mol/L titanium source (titanium source is potassium fluotitanate) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts pH with concentrated ammonia solution Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005g graphite oxide joins dividing of 10mL In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.3g load silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries The load silver/titanium dioxide graphene quantum dot that surface processes.
(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 of the load zinc oxide that step (3) prepares Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min prepared with step (7), then moves To the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash Photoirradiation power is 1.5W.
(2) weighing 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, dropping step (1) prepares Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table The load silver/titanium dioxide graphene quantum dot that face processes.
(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) prepare 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) prepares, then moves to In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 5h；Rapidly join 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 60min, swash Photoirradiation power is 1W.
(2) weighing 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 dropping step (1) prepares Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene amount of zinc oxide Sub-point.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.01g graphite oxide joins the dispersion of 5mL In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.3g load zinc oxide Graphene Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another Schungite alkene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense Degree is 0.01mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding 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 joined In 1 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver 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) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.01g graphite oxide joins the dispersion of 5mL In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.1g load 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 Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface The load silver/titanium dioxide graphene quantum dot 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 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare 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) prepares, then moves to In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 1
The preparation method of a kind 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 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, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration For 0.01mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding 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) prepares2Cladding carries silver graphene quantum dot, Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean, Dry to obtain antimicrobial composite material.
Comparative example 2
The preparation method of a kind 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, dropping concentration is 0.003mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and dropping concentration is 0.04mol/L bis-citric acid monohydrate trisodium, Continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene antibiosis material of silver.
Detailed process and step that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated are as follows:
The antibacterial of test is respectively staphylococcus aureus 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 weigh with electronic balance Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material MH meat soup to the most serial dilute 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 its result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, nothing The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of the longest tube.
Table 1: embodiment 1 ~ 3 and the anti-microbial property of comparative example 1,2 antimicrobial composite material
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, adds prepared by each embodiment of 1g and comparative example in bottle Antimicrobial composite material sample and 200mL saline (0.9mass%), and in water, soak 6 respectively, 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 material
Embodiment 4
A kind of preparation method of anti-electrostatic antibiotic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by embodiment 2 antibiotic complex, compound concentration is the solution of 0.5g/L, ultrasonic agitation (600W Ultrasonic power, 600rpm mixing speed) 90min, obtain antibacterial lactic acid solution；This antibiotic complex is through coupling agent pretreatment, tool Body is for join in dehydrated alcohol by antibiotic complex, and 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex mass fraction 2% Coupling agent, continue stirring 1h, filter post-drying；
(2) being dispersed in lactic acid by conductive filler, compound concentration is the solution of 2g/L, ultrasonic agitation (600W ultrasonic power, 600rpm mixing speed) 90min, obtain conduction lactic acid solution；Described conductive filler is by porous carbon, CNT, white carbon black, Graphene With nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing composition；Described conductive filler preparation method is as follows: by 5g cellulose, 12mg Polystyrolsulfon acid potassium and 30ml water join in 100ml water heating kettle, seal reaction 10h in 180 DEG C of baking ovens, cleaned dry After, under the air atmosphere of 900 DEG C, calcine 1h, obtain porous carbon；CNT, nanometer aluminium powder are dispersed in the water-soluble of 120ml In liquid, immerse porous carbon 2h, allow nano material well in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml In white carbon black and graphene aqueous solution, 60min, the most again sucking filtration；The filter cake distilled water wash of sucking filtration gained again, very The lower 120 DEG C of drying of empty condition, obtain conductive filler.
(3) antibacterial lactic acid solution and conduction lactic acid solution are placed in 60 DEG C of vacuum drying ovens, very by the mixing of 2:1 volume ratio Empty dry 30h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
Embodiment 5
A kind of preparation method of anti-electrostatic antibiotic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by embodiment 2 antibiotic complex, compound concentration is the solution of 1.2g/L, ultrasonic agitation (600W Ultrasonic power, 600rpm mixing speed) 90min, obtain antibacterial lactic acid solution；This antibiotic complex is through coupling agent pretreatment, tool Body is for join in dehydrated alcohol by antibiotic complex, and 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex mass fraction 2% Coupling agent, continue stirring 1h, filter post-drying；
(2) being dispersed in lactic acid by conductive filler, compound concentration is the solution of 1.6g/L, ultrasonic agitation (600W ultrasonic power, 600rpm mixing speed) 90min, obtain conduction lactic acid solution；Described conductive filler is by porous carbon, CNT, white carbon black, Graphene With nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing composition；Described conductive filler preparation method is as follows: by 5g cellulose, 12mg Polystyrolsulfon acid potassium and 30ml water join in 100ml water heating kettle, seal reaction 10h in 180 DEG C of baking ovens, cleaned dry After, under the air atmosphere of 900 DEG C, calcine 1h, obtain porous carbon；CNT, nanometer aluminium powder are dispersed in the water-soluble of 120ml In liquid, immerse porous carbon 2h, allow nano material well in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml In white carbon black and graphene aqueous solution, 60min, the most again sucking filtration；The filter cake distilled water wash of sucking filtration gained again, very The lower 120 DEG C of drying of empty condition, obtain conductive filler.
(3) antibacterial lactic acid solution and conduction lactic acid solution are placed in 60 DEG C of vacuum drying ovens, very by the mixing of 2:1 volume ratio Empty dry 30h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
Embodiment 6
A kind of preparation method of anti-electrostatic antibiotic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by embodiment 2 antibiotic complex, compound concentration is the solution of 2g/L, and (600W surpasses ultrasonic agitation Acoustical power, 600rpm mixing speed) 90min, obtain antibacterial lactic acid solution；This antibiotic complex is through coupling agent pretreatment, specifically For joining in dehydrated alcohol by antibiotic complex, 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex mass fraction 2% Coupling agent, continues stirring 1h, filters post-drying；
(2) being dispersed in lactic acid by conductive filler, compound concentration is the solution of 1g/L, ultrasonic agitation (600W ultrasonic power, 600rpm mixing speed) 90min, obtain conduction lactic acid solution；Described conductive filler is by porous carbon, CNT, white carbon black, Graphene With nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing composition；Described conductive filler preparation method is as follows: by 5g cellulose, 12mg Polystyrolsulfon acid potassium and 30ml water join in 100ml water heating kettle, seal reaction 10h in 180 DEG C of baking ovens, cleaned dry After, under the air atmosphere of 900 DEG C, calcine 1h, obtain porous carbon；CNT, nanometer aluminium powder are dispersed in the water-soluble of 120ml In liquid, immerse porous carbon 2h, allow nano material well in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml In white carbon black and graphene aqueous solution, 60min, the most again sucking filtration；The filter cake distilled water wash of sucking filtration gained again, very The lower 120 DEG C of drying of empty condition, obtain conductive filler.
(3) antibacterial lactic acid solution and conduction lactic acid solution are placed in 60 DEG C of vacuum drying ovens, very by the mixing of 2:1 volume ratio Empty dry 30h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
Comparative example 3
Preparation method based on embodiment 6, difference is: be not added with antibiotic complex.
Comparative example 4
Preparation method based on embodiment 6, difference is: be not added with conductive filler.
Testing the antibiotic antistatic performance of embodiment 4 ~ 6 and comparative example 3,4 poly-lactic acid material, result is as follows:
Embodiment described above only have expressed embodiments of the present invention, therefore it describes more concrete and detailed, but can not be And it is interpreted as the restriction to the scope of the claims of the present invention, as long as using the technical side that the form of equivalent or equivalent transformation is obtained Case, all should fall within the scope and spirit of the invention.

Claims (8)

1. a preparation method for anti-electrostatic antibiotic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by antibiotic complex, compound concentration is the solution of 0.1 ~ 2g/L, ultrasonic agitation 60 ~ 90min, Antibacterial lactic acid solution；
(2) being dispersed in lactic acid by conductive filler, compound concentration is the solution of 1 ~ 2g/L, and ultrasonic agitation 60 ~ 90min obtains conduction Lactic acid solution；Described conductive filler is by porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder 4:2:1:2:2 in mass ratio Mixing composition；
(3) antibacterial lactic acid solution and conduction lactic acid solution are placed in 50 ~ 80 DEG C of vacuum drying ovens, very by the mixing of 2:1 volume ratio Empty dry 24 ~ 36h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
The preparation method of anti-electrostatic antibiotic poly-lactic acid material the most according to claim 1, it is characterised in that described antibacterial multiple Compound, through coupling agent pretreatment, is specially and joins in dehydrated alcohol by antibiotic complex, and 500 ~ 800rpm stirs 1 ~ 2h； Dropwise dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters post-drying.
The preparation method of anti-electrostatic antibiotic poly-lactic acid material the most according to claim 1, it is characterised in that described conduction is filled out Preparation method for material is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join in 100ml water heating kettle, 180 DEG C baking oven seals reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C, calcine 1h, obtain porous carbon；Carbon is received Mitron, nanometer aluminium powder are dispersed in the aqueous solution of 120ml, immerse porous carbon 1 ~ 2h, allow nano material well in duct, so Rear sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, the most again sucking filtration；Again The filter cake distilled water wash of secondary sucking filtration gained, 120 DEG C of drying, obtain conductive filler under vacuum.
The preparation method of anti-electrostatic antibiotic poly-lactic acid material the most according to claim 1, it is characterised in that described antibacterial multiple Compound prepares by the following method:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing 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 dropping step (1) prepares, continue ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly Wash, dry to load the graphene quantum dot of 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, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3 Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2 Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes；
(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 the load zinc oxide that addition step (3) prepares and step (7) prepare Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~ 15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of anti-electrostatic antibiotic poly-lactic acid material the most according to claim 4, it is characterised in that described Graphene The preparation method of quantum dot suspension is as follows: weigh 0.5 ~ 0.8g C60 powder, and measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, mixes C60 powder and concentrated sulphuric acid in beaker, and 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, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change into Water-bath, keeps bath temperature 30 ~ 40 DEG C, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then use molecular cut off Be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, Laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2W.
The preparation method of anti-electrostatic antibiotic poly-lactic acid material the most according to claim 4, it is characterised in that ink alkene is 2 ~ 5 Layer, hole size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
The preparation method of anti-electrostatic antibiotic poly-lactic acid material the most according to claim 4, it is characterised in that described load silver/ The surface of titanium dioxide graphene quantum dot processes particularly as follows: 0.005 ~ 0.01g graphite oxide joins the dispersion of 5 ~ 10mL In agent, ultrasonic agitation also adds 0.1 ~ 0.3g load silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves To the microwave hydrothermal reaction kettle that liner is politef, seal and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power It is 200 ~ 400W, at 200 ~ 240 DEG C, reacts 60 ~ 90min；Cooling, filter, dry surface process load silver/titanium dioxide stone Ink alkene quantum dot.
The preparation method of anti-electrostatic antibiotic poly-lactic acid material the most according to claim 4, it is characterised in that described load oxygen The surface of the graphene quantum dot changing zinc processes particularly as follows: 0.005 ~ 0.01g graphite oxide joins the dispersant of 5 ~ 10mL In, ultrasonic agitation and add 0.1 ~ 0.3g load zinc oxide graphene quantum dot, continue ultrasonic agitation 10 ~ 30min, move in In the lining microwave hydrothermal reaction kettle for politef, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load zinc oxide Graphene amount Sub-point.
CN201610748815.7A 2016-08-29 2016-08-29 Preparation method of electrostatic prevention and antibiotic polylactic acid material Pending CN106317387A (en)

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