CN106220831A - A kind of preparation method of poly-lactic acid material - Google Patents
A kind of preparation method of poly-lactic acid material Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of poly-lactic acid material, it comprises the following steps: antibiotic complex is dispersed in lactic acid by (1), and compound concentration is the solution of 0.1 ~ 2g/L, and ultrasonic agitation 60 ~ 90min obtains 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；(3) by antibacterial lactic acid solution and conduction lactic acid solution by 2:1 volume ratio mixing be placed in 50 ~ 80 DEG C of vacuum drying ovens, vacuum dry 24 ~ 36h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.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.
Description
Technical field
The present invention relates to technical field of composite materials, particularly relate to the preparation method of a kind of poly-lactic acid material.
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 poly-lactic acid material.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of 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) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continue 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
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) 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.
(4) 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 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (3) prepares2Cladding carries silver graphene quantum dot, heats up
To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after be aged 6 hours, clean, be dried, obtain carrying silver-colored/
Titanium dioxide graphene quantum dot.
(5) 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.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and be configured to the graphite that concentration is 0.2 ~ 0.8mg/ml
Alkene dispersion soln, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W ultrasonic power, 600 ~ 800rpm stirs ultrasonic agitation
Mix speed) 80 ~ 100ml graphene dispersion solution, add the load silver/titanium dioxide graphene quantum dot that step (5) prepares, ultrasonic
Stirring 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal,
Clean, dry to obtain antimicrobial composite material.
There is advantages that
The present invention first prepares the graphene quantum dot of load silver/titanium dioxide, and then surface processes, and is finally attached to porous graphite
On alkene, can preferably load and fix Nano silver grain and titanium dioxide, prevent it from reuniting, significantly improve Nano silver grain and
The stability of titanium dioxide, makes Nano silver grain and titanium dioxide have more efficient antibacterial activity；Be compounded with simultaneously silver particles,
Titanium dioxide antibiotic performance, has a more preferable antibacterial effect compared to single silver nano antibacterial agent, 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 porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it 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 5h；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) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.08mol/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 4:2:1.
(3) 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.
(4) 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 (3) 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.
(5) 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.
(6) 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 load silver/titanium dioxide Graphene quantum that step (5) prepares
Point, ultrasonic agitation 30min, then move in the reactor of politef, at 100 DEG C, be incubated 30min；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.6g C60 powder, measure 50 ~ 100ml mass fraction be 98% dense
Sulphuric 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,
Mixed liquor；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 7h；Rapidly join 200ml pure water, filter, then saturating with the bag filter that molecular cut off is 1000
Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation
45min, laser irradiation power is 1.2W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.05mol/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 3:3:2.
(3) 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.
(4) 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 (3) 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.
(5) 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.
(6) 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 the load silver/titanium dioxide graphene quantum dot that step (5) prepares,
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.
Embodiment 3
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and 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 0.5g 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 100ml pure water, filter, then saturating with the bag filter that molecular cut off is 1000
Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation
60min, laser irradiation power is 1W.
(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) 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 (3) 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.
(5) 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.
(6) 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 load silver/titanium dioxide Graphene quantum that step (5) prepares
Point, ultrasonic agitation 30min, then move in the reactor of politef, at 100 DEG C, be incubated 30min；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
Comparative example 1
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps: weigh porous
It is molten that Graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) is configured to the graphene dispersion that concentration is 0.8mg/ml
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml Graphene
Dispersion soln, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/
L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, dries to obtain antimicrobial composite material.
Comparative example 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) compound concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/L
Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, the volume ratio of silver nitrate solution and two citric acid monohydrate trisodiums is 2:1；Afterwards
Add water and the ammonia of volume ratio 3:1, be stirring evenly and then adding into tetraethyl orthosilicate, with the quality of the graphene quantum dot of load silver
Ratio is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；It is centrifuged and successively with acetone and going
Ionized water cleans and obtains precipitation；This is deposited in 90o3h it is dried, to obtain Ag/SiO under C2；
(2) 0.1mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined 1
In mol/L sulfuric acid solution, mix homogeneously；Add the Ag/SiO that step (1) prepares2, it is warming up to 110 DEG C, after reaction 4h, uses dense ammonia
Aqueous solution adjusts pH value to 7, after being aged 6 hours, cleans, is dried, obtains Ag/SiO2/ titanium dioxide；
(3) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.8mg/
The graphene dispersion solution of ml, solvent is water, acetone or dimethyl sulfoxide；(1000W ultrasonic power, 800rpm stirs ultrasonic agitation
Mix speed) 100ml graphene dispersion solution, add the Ag/SiO that step (3) prepares2/ titanium dioxide, ultrasonic agitation 30min, so
After move in the reactor of politef, at 100 DEG C, be incubated 30min；Cooling, centrifugal, clean, dry to obtain antibacterial composite wood
Material.
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 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 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 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 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 poly-lactic acid material the most according to claim 1, it is characterised in that described antibiotic complex is through even
Connection 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 poly-lactic acid material the most according to claim 1, it is characterised in that described conductive filler preparation method
As follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join in 100ml water heating kettle, close in 180 DEG C of baking ovens
Envelope reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C calcine 1h, obtain porous carbon；By CNT, nano aluminum
Powder is dispersed in the aqueous solution of 120ml, immerses porous carbon 1 ~ 2h, allow nano material well in duct, then sucking filtration；Sucking filtration
The filter cake of gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, the most again sucking filtration；Sucking filtration gained again
Filter cake distilled water wash, 120 DEG C of drying, obtain conductive filler under vacuum.
The preparation method of poly-lactic acid material the most according to claim 1, it is characterised in that described antibiotic complex by with
Lower section method prepares:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, drips silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, and dropping continues ultrasonic agitation 60 ~ 120min；Ageing, cleans, and dries to obtain load silver
Graphene quantum dot；
(2) 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, obtains SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(3) 0.1 ~ 0.3mol/L titanium source is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add what step (2) prepared
SiO2Cladding 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, old
Change, clean, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) surface carrying silver/titanium dioxide graphene quantum dot processes；
(5) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) prepares
Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C be incubated 15 ~
30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of poly-lactic acid material the most according to claim 4, it is characterised in that described graphene quantum dot suspends
The preparation method of liquid is as follows: weigh 0.5 ~ 0.8g C60 powder, measures the concentrated sulphuric acid that 50 ~ 100ml mass fraction is 98%, will
C60 powder and concentrated sulphuric acid mix in beaker, and beaker is placed in ice-water bath, stir with the speed of 300 ~ 500rpm simultaneously, obtain mixed
Close liquid；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep
Bath temperature 30 ~ 40 DEG C, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, be then 1000 with molecular cut off
Bag filter is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser
Irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
The preparation method of poly-lactic acid material the most according to claim 4, it is characterised in that described porous graphene is 2 ~ 5
Layer, the porous graphene of hole size about 3 ~ 6nm.
The preparation method of poly-lactic acid material the most according to claim 4, it is characterised in that described load silver/titanium dioxide stone
The surface of ink alkene quantum dot processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL, ultrasonic stirs
Mixing and add 0.1 ~ 0.3g and carry silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~ 30min, moving to liner is poly-four
In the microwave hydrothermal reaction kettle of fluorothene, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W,
60 ~ 90min is reacted at 200 ~ 240 DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
The preparation method of poly-lactic acid material the most according to claim 4, it is characterised in that described titanium source be potassium fluotitanate,
Ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
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