CN106084704A - A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch - Google Patents
A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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Abstract
The invention discloses a kind of polylactic acid antibacterial except the preparation method of formaldehyde master batch, it comprises the following steps: (1) pretreatment polylactic acid raw material；(2) half pretreatment polylactic acid is dissolved in organic solvent, under ultrasonic agitation, drips antibiotic complex aqueous dispersions, ultrasonic agitation, be spray-dried to obtain antibacterial matrices；(3) half pretreatment polylactic acid is dissolved in organic solvent, under ultrasonic agitation, drips kieselguhr/inorganic oxide aqueous dispersions, ultrasonic agitation, be spray-dried except formaldehyde master batch；(4) mixing two kinds of master batch mixing thoroughly acquisition mixture, it is antibacterial except formaldehyde master batch that pelletize obtains polylactic acid.The present invention is through kieselguhr/inorganic oxide and the antimicrobial composite material of reasonably arranging in pairs or groups, synergism between functional additive, polylactic acid master batch is made to have excellent antibacterial and deodoriging properties and anti-formaldehyde characteristic, meet the demand of multi-functional polylactic acid master batch, widen the application of polylactic acid master batch further.
Description
Technical field
The present invention relates to technical field of composite materials, particularly relate to a kind of polylactic acid antibacterial except the system of formaldehyde master batch
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
Polylactic acid can be gathered in antibacterial except the specific part of formaldehyde master batch, it is impossible to be evenly distributed on surface, thus the antibacterial effect affected；
On the other hand, nanometer silver and polylactic acid are antibacterial cannot combine closely (particularly when nano-Ag particles content increases except formaldehyde master batch
Time, it is susceptible to agglomeration), the most easily come off, thus affect service life and antibacterial effect.Existing poly-
Lactic acid antibacterial except formaldehyde master batch function more single, it is more difficult to meet multi-functional feature.
Summary of the invention
It is antibacterial except the preparation method of formaldehyde master batch that the technical problem to be solved there is provided a kind of polylactic acid.
The technical problem to be solved is achieved by the following technical programs:
A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch, and 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,
Ultrasonic limit, limit microwave exposure 30min；Washing, discharging, it is dried, obtains 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), dropping concentration is 0.1 ~ 0.5mol/L's
Antibiotic complex aqueous dispersions, ultrasonic agitation (200 ~ 300W ultrasonic power, 200 ~ 300rpm mixing speed) 30 ~ 60min, obtain anti-
Bacterium polylactic acid mixed liquor；Then pass to spray dryer stocks in groove, and the speed with 200～300ml/min is by antibacterial poly-breast
Acid mixed liquor is ejected in spray dryer, is dried to obtain antibacterial matrices；
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；
(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), dropping concentration is the diatom of 1 ~ 2g/L
Soil/inorganic oxide aqueous dispersions, ultrasonic agitation (200 ~ 300W ultrasonic power, 200 ~ 300rpm mixing speed) 30 ~ 60min,
Formaldehyde polylactic acid mixed liquor must be removed；Then pass to spray dryer stocks in groove, and the speed with 200～300ml/min will be removed
Formaldehyde polylactic acid mixed liquor is ejected in spray dryer, is dried except formaldehyde master batch；
Described kieselguhr/inorganic oxide carries out coupling agent pretreatment, particularly as follows: kieselguhr/inorganic oxide joins anhydrous
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the coupling agent of kieselguhr/inorganic oxide mass fraction 2%, continues
Stirring 1 ~ 2h, filters post-drying.
Described kieselguhr/inorganic oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%,
TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%,
Na2O8%, MnO2 7%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls particle diameter
Between 10 ~ 300nm；Kieselguhr being dispersed in the aqueous solution of 120ml, adds inorganic oxide, 100 ~ 200W is ultrasonic 100 ~
300rpm stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxygen
Compound；Wherein said kieselguhr is 1 ~ 2:3 ~ 5 with the weight ratio of inorganic oxide.
(4) mixture that master batch mixing prepared for step (2) (3) is mixed thoroughly acquisition pours the hopper of double screw extruder into
In, it is extruded into wire through double screw extruder, after the bosh of 0 ~ 5 DEG C cools down, hair-dryer air-dries, described hair-dryer
Air outlet temperature is maintained at 10 ~ 20 DEG C, and it is antibacterial except formaldehyde master batch that last pelletize obtains described polylactic acid.
Coupling agent is silane coupler, titanate coupling agent or its mixture.
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；
The inorganic oxide main component that the present invention uses has more than the 10 kind of trace element favourable to human body such as magnesium, aluminum, ferrum, by
Being the special polarity crystalline solid of a kind of structure in it, self can produce electron ion for a long time, and forever discharge negative aeroion, reach
Deodorization purifies the effect of air.After being ground by inorganic oxide and be immersed in inside kieselguhr, can effectively improve it stable
Property, kieselguhr can also adsorb harmful gas particularly formaldehyde in air simultaneously, improves the effect purifying air further；
The present invention is through kieselguhr/inorganic oxide and the antimicrobial composite material of reasonably arranging in pairs or groups, working in coordination with between functional additive
Effect so that polylactic acid master batch has excellent antibacterial and deodoriging properties and anti-formaldehyde characteristic, meets multi-functional polylactic acid master batch
Demand, widen the application of polylactic acid master batch 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 polylactic acid is antibacterial except the preparation method of formaldehyde master batch, and 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,
Ultrasonic limit, limit microwave exposure 30min；Washing, discharging, it is dried, obtains 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), dropping 3mL concentration is that the embodiment 2 of 0.1mol/L is antibacterial
Complex aqueous dispersions, ultrasonic agitation (300W ultrasonic power, 300rpm mixing speed) 60min, obtain antibacterial polylactic acid mixing
Liquid；Then pass to spray dryer stocks in groove, with the speed of 300ml/min, antibacterial polylactic acid mixed liquor is ejected into spraying
In exsiccator, it is dried to obtain antibacterial matrices；This antibiotic complex, through coupling agent pretreatment, is specially and is joined by antibiotic complex
In dehydrated alcohol, 800rpm stirs 2h；Dropwise dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1h, mistake
Filter post-drying；
(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), dropping 3mL concentration is the kieselguhr/inorganic oxide of 2g/L
Thing aqueous dispersions, ultrasonic agitation (300W ultrasonic power, 300rpm mixing speed) 60min, must remove formaldehyde polylactic acid mixed liquor；
Then pass to spray dryer stocks in groove, will be ejected into spraying except formaldehyde polylactic acid mixed liquor with the speed of 300ml/min
In exsiccator, it is dried except formaldehyde master batch；Described kieselguhr/inorganic oxide carries out coupling agent pretreatment, particularly as follows: diatom
Soil/inorganic oxide joins in dehydrated alcohol, and 800rpm stirs 2h；Dropwise dropping accounts for kieselguhr/inorganic oxide quality and divides
The coupling agent of several 2%, continues stirring 1h, filters post-drying.Described kieselguhr/inorganic oxide preparation method is as follows: below mixing
The raw material of percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%,
Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, the big flow circulation putting into the exploitation of PUHLER company is sleeping
Formula sand mill is ground, controls particle diameter between 10 ~ 300nm；Kieselguhr is dispersed in the aqueous solution of 120ml, adds
Inorganic oxide, the ultrasonic 300rpm of 200W stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans,
It is dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr is 1:4 with the weight ratio of inorganic oxide.
(4) mixture that master batch mixing prepared for step (2) (3) is mixed thoroughly acquisition pours the hopper of double screw extruder into
In, it is extruded into wire through double screw extruder, after the bosh of 0 ~ 5 DEG C cools down, hair-dryer air-dries, described hair-dryer
Air outlet temperature is maintained at 10 ~ 20 DEG C, and it is antibacterial except formaldehyde master batch that last pelletize obtains described polylactic acid.
Embodiment 5
A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch, and 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,
Ultrasonic limit, limit microwave exposure 30min；Washing, discharging, it is dried, obtains 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), dropping 3mL concentration is that the embodiment 2 of 0.3mol/L is antibacterial
Complex aqueous dispersions, ultrasonic agitation (300W ultrasonic power, 300rpm mixing speed) 60min, obtain antibacterial polylactic acid mixing
Liquid；Then pass to spray dryer stocks in groove, with the speed of 300ml/min, antibacterial polylactic acid mixed liquor is ejected into spraying
In exsiccator, it is dried to obtain antibacterial matrices；This antibiotic complex, through coupling agent pretreatment, is specially and is joined by antibiotic complex
In dehydrated alcohol, 800rpm stirs 2h；Dropwise dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1h, mistake
Filter post-drying；
(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), dropping 3mL concentration is the kieselguhr/inorganic oxygen of 1.5g/L
Compound aqueous dispersions, ultrasonic agitation (300W ultrasonic power, 300rpm mixing speed) 60min, must mix except formaldehyde polylactic acid
Liquid；Then pass to spray dryer stocks in groove, will be ejected into spray except formaldehyde polylactic acid mixed liquor with the speed of 300ml/min
In mist exsiccator, it is dried except formaldehyde master batch；Described kieselguhr/inorganic oxide carries out coupling agent pretreatment, particularly as follows: diatom
Soil/inorganic oxide joins in dehydrated alcohol, and 800rpm stirs 2h；Dropwise dropping accounts for kieselguhr/inorganic oxide quality and divides
The coupling agent of several 2%, continues stirring 1h, filters post-drying.Described kieselguhr/inorganic oxide preparation method is as follows: below mixing
The raw material of percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%,
Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, the big flow circulation putting into the exploitation of PUHLER company is sleeping
Formula sand mill is ground, controls particle diameter between 10 ~ 300nm；Kieselguhr is dispersed in the aqueous solution of 120ml, adds
Inorganic oxide, the ultrasonic 300rpm of 200W stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans,
It is dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr is 1:4 with the weight ratio of inorganic oxide.
(4) mixture that master batch mixing prepared for step (2) (3) is mixed thoroughly acquisition pours the hopper of double screw extruder into
In, it is extruded into wire through double screw extruder, after the bosh of 0 ~ 5 DEG C cools down, hair-dryer air-dries, described hair-dryer
Air outlet temperature is maintained at 10 ~ 20 DEG C, and it is antibacterial except formaldehyde master batch that last pelletize obtains described polylactic acid.
Embodiment 6
A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch, and 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,
Ultrasonic limit, limit microwave exposure 30min；Washing, discharging, it is dried, obtains 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), dropping 3mL concentration is that the embodiment 2 of 0.5mol/L is antibacterial
Complex aqueous dispersions, ultrasonic agitation (300W ultrasonic power, 300rpm mixing speed) 60min, obtain antibacterial polylactic acid mixing
Liquid；Then pass to spray dryer stocks in groove, with the speed of 300ml/min, antibacterial polylactic acid mixed liquor is ejected into spraying
In exsiccator, it is dried to obtain antibacterial matrices；This antibiotic complex, through coupling agent pretreatment, is specially and is joined by antibiotic complex
In dehydrated alcohol, 800rpm stirs 2h；Dropwise dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1h, mistake
Filter post-drying；
(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), dropping 3mL concentration is the kieselguhr/inorganic oxide of 1g/L
Thing aqueous dispersions, ultrasonic agitation (300W ultrasonic power, 300rpm mixing speed) 60min, must remove formaldehyde polylactic acid mixed liquor；
Then pass to spray dryer stocks in groove, will be ejected into spraying except formaldehyde polylactic acid mixed liquor with the speed of 300ml/min
In exsiccator, it is dried except formaldehyde master batch；Described kieselguhr/inorganic oxide carries out coupling agent pretreatment, particularly as follows: diatom
Soil/inorganic oxide joins in dehydrated alcohol, and 800rpm stirs 2h；Dropwise dropping accounts for kieselguhr/inorganic oxide quality and divides
The coupling agent of several 2%, continues stirring 1h, filters post-drying.Described kieselguhr/inorganic oxide preparation method is as follows: below mixing
The raw material of percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%,
Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, the big flow circulation putting into the exploitation of PUHLER company is sleeping
Formula sand mill is ground, controls particle diameter between 10 ~ 300nm；Kieselguhr is dispersed in the aqueous solution of 120ml, adds
Inorganic oxide, the ultrasonic 300rpm of 200W stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans,
It is dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr is 1:4 with the weight ratio of inorganic oxide.
(4) mixture that master batch mixing prepared for step (2) (3) is mixed thoroughly acquisition pours the hopper of double screw extruder into
In, it is extruded into wire through double screw extruder, after the bosh of 0 ~ 5 DEG C cools down, hair-dryer air-dries, described hair-dryer
Air outlet temperature is maintained at 10 ~ 20 DEG C, and it is antibacterial except formaldehyde master batch that last pelletize obtains described polylactic acid.
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 kieselguhr/inorganic oxide.
Embodiment 4 ~ 6 and the antibacterial and deodouring of comparative example 3,4 poly-lactic acid material and purifying formaldehyde performance are tested, result
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 (9)
1. polylactic acid is antibacterial except a preparation method for formaldehyde master batch, and 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,
Ultrasonic limit, limit microwave exposure 30min；Washing, discharging, it is dried, obtains pretreatment polylactic acid；
(2) at the heating temperature, half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution；Ultrasonic
Under stirring, dropping concentration is the antibiotic complex aqueous dispersions of 0.1 ~ 0.5mol/L, and ultrasonic agitation 30 ~ 60min obtains antibacterial poly-breast
Acid mixed liquor；Then pass to spray dryer stocks in groove, and antibacterial polylactic acid is mixed by the speed with 200～300ml/min
Liquid is ejected in spray dryer, is dried to obtain antibacterial matrices；
(3) at the heating temperature, half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution；Ultrasonic
Under stirring, dropping concentration is the kieselguhr/inorganic oxide aqueous dispersions of 1 ~ 2g/L, and ultrasonic agitation 30 ~ 60min must remove formaldehyde
Polylactic acid mixed liquor；Then pass to spray dryer stocks in groove, and the speed with 200～300ml/min will be except the poly-breast of formaldehyde
Acid mixed liquor is ejected in spray dryer, is dried except formaldehyde master batch；
(4) master batch mixing step (2) (3) prepared is mixed thoroughly in the hopper that the mixture of acquisition pours double screw extruder into, warp
Double screw extruder is extruded into wire, and after the bosh of 0 ~ 5 DEG C cools down, hair-dryer air-dries, described hair-dryer air outlet
Temperature is maintained at 10 ~ 20 DEG C, and it is antibacterial except formaldehyde master batch that last pelletize obtains described polylactic acid.
Polylactic acid the most according to claim 1 is antibacterial except the preparation method of formaldehyde master batch, 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.
Polylactic acid the most according to claim 1 is antibacterial except the preparation method of formaldehyde master batch, it is characterised in that described diatom
Soil/inorganic oxide carries out coupling agent pretreatment, particularly as follows: kieselguhr/inorganic oxide joins in dehydrated alcohol, 500 ~
800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the coupling agent of kieselguhr/inorganic oxide mass fraction 2%, continues stirring 1 ~ 2h, mistake
Filter post-drying.
4. antibacterial except the preparation method of formaldehyde master batch according to the polylactic acid described in claim 1 or 3, it is characterised in that described silicon
Diatomaceous earth/inorganic oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2
16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2
7%, put into PUHLER company exploitation big flow circulation horizontal sand mill in be ground, control particle diameter 10 ~ 300nm it
Between；Being dispersed in the aqueous solution of 120ml by kieselguhr, add inorganic oxide, the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 2h,
Allowing nano material well in kieselguhr hole, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein said
Kieselguhr is 1 ~ 2:3 ~ 5 with the weight ratio of inorganic oxide.
Polylactic acid the most according to claim 1 is antibacterial except the preparation method of formaldehyde master batch, it is characterised in that described antibacterial multiple
Compound prepares by the following method:
(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.
Polylactic acid the most according to claim 5 is antibacterial except the preparation method of formaldehyde master batch, 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.
Polylactic acid the most according to claim 5 is antibacterial except the preparation method of formaldehyde master batch, it is characterised in that described porous stone
Ink alkene is 2 ~ 5 layers, the porous graphene of hole size about 3 ~ 6nm.
Polylactic acid the most according to claim 5 is antibacterial except the preparation method of formaldehyde master batch, it is characterised in that and 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.
Polylactic acid the most according to claim 5 is antibacterial except the preparation method of formaldehyde master batch, it is characterised in that described titanium source is
Potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
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