CN106084921A - A kind of preparation method of waterborne antibacterial inorganic coating - Google Patents
A kind of preparation method of waterborne antibacterial inorganic coating Download PDFInfo
- Publication number
- CN106084921A CN106084921A CN201610748637.8A CN201610748637A CN106084921A CN 106084921 A CN106084921 A CN 106084921A CN 201610748637 A CN201610748637 A CN 201610748637A CN 106084921 A CN106084921 A CN 106084921A
- Authority
- CN
- China
- Prior art keywords
- solution
- quantum dot
- graphene quantum
- silver
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Abstract
The invention discloses the preparation method of a kind of waterborne antibacterial inorganic coating, it comprises the following steps: kieselguhr is scattered in aqueous solution by (1), ultrasonic agitation limit, limit dropping antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；(2) at room temperature, first by water, defoamer mix and blend, add pigment and filler, after being sufficiently stirred for, obtain solution A；(3) Ludox and polymer solution are mixed, be sufficiently stirred for；Add kieselguhr/antibiotic complex, stir to obtain solution B；(4) in step (3) gained solution B, add coalescents and thickening agent, be sufficiently stirred for obtaining solution C；(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter.The present invention is through reasonably collocation kieselguhr and antimicrobial composite material, the synergism between functional additive so that inorganic coating has excellent antibacterial and anti-formaldehyde characteristic, meets multi-functional demand, widens the application of inorganic coating further.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to the preparation method of a kind of waterborne antibacterial inorganic coating.
Background technology
Inorganic coating is primarily referred to as, using silicate and phosphate compound as binding agent, adding various face, filler, helping
The coating that agent, firming agent are formulated, wherein silicate macromolecular compound can be divided into again alkali silicate and Ludox.This
Coating kind using inorganic binder as film forming matter has that film-forming temperature is low, its film has excellent weatherability, in ultraviolet
Thermostability highly stable, good under light action, meet fire and do not fire, preferable stain resistance, be difficult to inhale ash, lucid and lively dress can be kept
Decorations effect, make with use during non-volatility Organic substance produces, does not pollutes the environment, raw material resources enriches, cost
The series of advantages such as cheap, thus be widely used.But existing aqueous inorganic paint function is more single, it is more difficult to full
The multi-functional feature of foot.
Summary of the invention
The technical problem to be solved there is provided the preparation method of a kind of waterborne antibacterial inorganic coating.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being scattered in aqueous solution by 2 ~ 5 parts of kieselguhr, (100 ~ 300W ultrasonic power, 100 ~ 300rpm stirs limit ultrasonic agitation
Speed) limit dropping 3 ~ 8mL concentration is the antibiotic complex aqueous dispersions of 0.01 ~ 0.1mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex.
(2) at room temperature, first by 25 ~ 35 parts of water, 0.5 ~ 1 part of defoamer mix and blend, add 5 ~ 10 parts of pigment and 20 ~
30 parts of filleies, after being sufficiently stirred for, are filtrated to get homogeneous solution A；
(3) by described 20 ~ 30 parts of Ludox and 5 ~ 12 parts of polymer solution mixing, it is sufficiently stirred for；Add 1 ~ 5 part of kieselguhr/anti-
Bacterium complex, stirs 30 ~ 60min, obtains homogeneous solution B；
(4) in the solution B of step (3) gained, add 1 ~ 3 part of coalescents and 0.05 ~ 0.3 part of thickening agent, be sufficiently stirred for, mistake
Filter obtains homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Preferably, described Ludox is the nano level silica dioxide granule (particle diameter about 10nm) dispersion liquid in water.
The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol.Described pigment is titanium dioxide or white carbon black.
Described filler is selected from Pulvis Talci, calcium carbonate, the combination of one or more in silicon calcium powder.
Described defoamer is selected from isooctanol, the combination of one or more in isopropanol.
Described coalescents one in ethylene glycol, 2-Butoxyethyl acetate, acetic acid, ethanol, the ethyl acetate or
Multiple combination.
Described thickening agent is PUR40 polyurethane thickener.
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, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the load silver/titanium dioxide that step (5) prepares
Graphene 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.
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；
Kieselguhr has harmful gas effect particularly formaldehyde in absorption air, has the effect purifying air；
The present invention is through reasonably collocation kieselguhr and antimicrobial composite material, the synergism between functional additive so that nothing
Machine coating has excellent antibacterial and anti-formaldehyde characteristic, meets multi-functional demand, widens the application of inorganic coating 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 about 100 ~ 500nm, layer size 100 ~
500nm) being configured to the graphene dispersion solution that concentration is 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation
(1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, adds load silver/dioxy that step (5) prepares
Change titanium graphene quantum dot, ultrasonic agitation 30min, then move in the reactor of politef, be incubated at 100 DEG C
30min；Cooling, centrifugal, clean, 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 about 100 ~ 500nm, layer size 100 ~
500nm) being configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation
(1000W ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, adds load silver/titanium dioxide that step (5) prepares
Titanium graphene quantum dot, ultrasonic agitation 30min, then move in the reactor of politef, at 100 DEG C, be incubated 30min；
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 about 100 ~ 500nm, layer size 100 ~
500nm) being configured to the graphene dispersion solution that concentration is 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation
(1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, adds load silver/dioxy that step (5) prepares
Change titanium graphene quantum dot, ultrasonic agitation 30min, then move in the reactor of politef, be incubated at 100 DEG C
30min；Cooling, centrifugal, clean, 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
Graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm, layer size 100 ~ 500nm) is configured to concentration and is
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, dropping concentration is 0.001mol/L silver nitrate solution, controls reaction temperature
Being 50 DEG C, dropping concentration is 0.01mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, dries
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) porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm, layer size 100 ~ 500nm) is weighed
Being configured to the graphene dispersion solution that concentration is 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W
Ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, add the Ag/SiO that step (3) prepares2/ titanium dioxide
Titanium, 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.
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 waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 2 parts of kieselguhr, (200W ultrasonic power, 100rpm stirs speed to limit ultrasonic agitation
Degree) limit dropping 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.08mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex.
(2) at room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of calcium carbonate, fill
After dividing stirring, it is filtrated to get homogeneous solution A；
(3) by described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；Add 3 parts of kieselguhr/antibacterial compound
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is that nano level silica dioxide granule (particle diameter about 10nm) is in water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
(4) in the solution B of step (3) gained, add 2 parts of coalescents and 0.1 part of PUR40 polyurethane thickener, fully stir
Mix, be filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Embodiment 5
A kind of preparation method of waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 3 parts of kieselguhr, (200W ultrasonic power, 100rpm stirs speed to limit ultrasonic agitation
Degree) limit dropping 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.05mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex.
(2) at room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of calcium carbonate, fill
After dividing stirring, it is filtrated to get homogeneous solution A；
(3) by described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；Add 3 parts of kieselguhr/antibacterial compound
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is that nano level silica dioxide granule (particle diameter about 10nm) is in water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
(4) in the solution B of step (3) gained, add 2 parts of coalescents and 0.1 part of PUR40 polyurethane thickener, fully stir
Mix, be filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Embodiment 6
A kind of preparation method of waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 5 parts of kieselguhr, (200W ultrasonic power, 100rpm stirs speed to limit ultrasonic agitation
Degree) limit dropping 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.01mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex.
(2) at room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of calcium carbonate, fill
After dividing stirring, it is filtrated to get homogeneous solution A；
(3) by described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；Add 3 parts of kieselguhr/antibacterial compound
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is that nano level silica dioxide granule (particle diameter about 10nm) is in water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
(4) in the solution B of step (3) gained, add 2 parts of coalescents and 0.1 part of PUR40 polyurethane thickener, fully stir
Mix, be filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Comparative example 3
Preparation method based on embodiment 6, difference is: remove step (1), and kieselguhr/antibiotic complex changes into antibacterial
Complex.
Comparative example 4
Preparation method based on embodiment 6, difference is: remove antibiotic complex.
The main performance index of aqueous inorganic paint such as following table:
Antibacterial Evaluation for Uniformity: be coated uniformly on by coating on glass or ceramic wafer, chooses 100 regions and carries out sterilizing test,
The data recorded are carried out Uniformity Analysis, by the uniformity=100* (1-standard deviation/meansigma methods).When the uniformity is more than
97%, then be labeled as ▲；When the uniformity is more than 90% and less than 97%, then it is labeled as ☆；When the uniformity is less than 90%, then it is labeled as
╳。
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained
Art scheme, all should fall within the scope and spirit of the invention.
Claims (6)
1. a preparation method for waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being scattered in aqueous solution by 2 ~ 5 parts of kieselguhr, ultrasonic agitation limit, limit dropping 3 ~ 8mL concentration is 0.01 ~ 0.1mol/L's
Antibiotic complex aqueous dispersions；Standing 90min, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；
(2) at room temperature, first by 25 ~ 35 parts of water, 0.5 ~ 1 part of defoamer mix and blend, 5 ~ 10 parts of pigment and 20 ~ 30 parts are added
Filler, after being sufficiently stirred for, is filtrated to get homogeneous solution A；
(3) by described 20 ~ 30 parts of Ludox and 5 ~ 12 parts of polymer solution mixing, it is sufficiently stirred for；Add 1 ~ 5 part of kieselguhr/anti-
Bacterium complex, stirs 30 ~ 60min, obtains homogeneous solution B；
(4) in the solution B of step (3) gained, add 1 ~ 3 part of coalescents and 0.05 ~ 0.3 part of thickening agent, be sufficiently stirred for, mistake
Filter obtains homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
The preparation method of waterborne antibacterial inorganic coating the most according to claim 1, it is characterised in that described antibiotic complex
Prepare 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.
The preparation method of waterborne antibacterial inorganic coating the most according to claim 2, it is characterised in that described Graphene quantum
The preparation method of some suspension is as follows: weighs 0.5 ~ 0.8g C60 powder, measures the dense sulfur that 50 ~ 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 300 ~ 500rpm simultaneously,
Obtain mixed liquor；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, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with molecular cut off be
The bag filter of 1000 is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, with
Shi Jiguang irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
The preparation method of waterborne antibacterial inorganic coating the most according to claim 2, it is characterised in that described porous graphene
It is 2 ~ 5 layers, hole size about 3 ~ 6nm, the porous graphene of layer size about 100 ~ 500nm.
The preparation method of waterborne antibacterial inorganic coating the most according to claim 2, it is characterised in that described load silver/dioxy
The surface changing titanium graphene quantum dot processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL,
Ultrasonic agitation also adds 0.1 ~ 0.3g load silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to liner
For in the microwave hydrothermal reaction kettle of 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 silver/titanium dioxide Graphene amount
Sub-point.
The preparation method of waterborne antibacterial inorganic coating the most according to claim 2, it is characterised in that described titanium source is fluorine titanium
Acid potassium, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748637.8A CN106084921A (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of waterborne antibacterial inorganic coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748637.8A CN106084921A (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of waterborne antibacterial inorganic coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106084921A true CN106084921A (en) | 2016-11-09 |
Family
ID=57223845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610748637.8A Pending CN106084921A (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of waterborne antibacterial inorganic coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106084921A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110294865A (en) * | 2019-04-16 | 2019-10-01 | 山西大医院（山西医学科学院） | One kind having hydrophobic bio-medical antibacterial agent |
| CN115521685A (en) * | 2022-10-08 | 2022-12-27 | 北京星驰恒动科技发展有限公司 | Coating, preparation method of coating and space cabin |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872889A (en) * | 2012-10-10 | 2013-01-16 | 江苏大学 | Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same |
| CN103081946A (en) * | 2013-01-18 | 2013-05-08 | 湖南元素密码石墨烯研究院（有限合伙） | Porous graphene loaded cerium nano composite antibacterial agent and preparation method thereof |
| CN103143338A (en) * | 2013-03-21 | 2013-06-12 | 四川农业大学 | Porous titanium dioxide/graphene composite material and preparation method thereof |
| CN103483884A (en) * | 2013-09-25 | 2014-01-01 | 上海新安纳电子科技有限公司 | High-performance waterborne inorganic paint and preparation method thereof |
| CN104211050A (en) * | 2014-07-15 | 2014-12-17 | 中国科学技术大学 | Preparation method of suspension liquid and powder of graphene quantum dot |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| WO2016011180A1 (en) * | 2014-07-17 | 2016-01-21 | Santhanam Kalathur S V | Electrochemical process for producing graphene, graphene oxide, metal composites and coated substrates |
| CN105348890A (en) * | 2015-12-18 | 2016-02-24 | 陈荣芳 | Preparation method of light-emitting composite paint |
| CN106465711A (en) * | 2016-08-29 | 2017-03-01 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of multifunctional aqueous inorganic coating |
-
2016
- 2016-08-29 CN CN201610748637.8A patent/CN106084921A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872889A (en) * | 2012-10-10 | 2013-01-16 | 江苏大学 | Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same |
| CN103081946A (en) * | 2013-01-18 | 2013-05-08 | 湖南元素密码石墨烯研究院（有限合伙） | Porous graphene loaded cerium nano composite antibacterial agent and preparation method thereof |
| CN103143338A (en) * | 2013-03-21 | 2013-06-12 | 四川农业大学 | Porous titanium dioxide/graphene composite material and preparation method thereof |
| CN103483884A (en) * | 2013-09-25 | 2014-01-01 | 上海新安纳电子科技有限公司 | High-performance waterborne inorganic paint and preparation method thereof |
| CN104211050A (en) * | 2014-07-15 | 2014-12-17 | 中国科学技术大学 | Preparation method of suspension liquid and powder of graphene quantum dot |
| WO2016011180A1 (en) * | 2014-07-17 | 2016-01-21 | Santhanam Kalathur S V | Electrochemical process for producing graphene, graphene oxide, metal composites and coated substrates |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| CN105348890A (en) * | 2015-12-18 | 2016-02-24 | 陈荣芳 | Preparation method of light-emitting composite paint |
| CN106465711A (en) * | 2016-08-29 | 2017-03-01 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of multifunctional aqueous inorganic coating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110294865A (en) * | 2019-04-16 | 2019-10-01 | 山西大医院（山西医学科学院） | One kind having hydrophobic bio-medical antibacterial agent |
| CN115521685A (en) * | 2022-10-08 | 2022-12-27 | 北京星驰恒动科技发展有限公司 | Coating, preparation method of coating and space cabin |
| CN115521685B (en) * | 2022-10-08 | 2023-10-27 | 北京星驰恒动科技发展有限公司 | Paint, preparation method of paint and space capsule |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106221316A (en) | A kind of preparation method of waterborne antibacterial deodorization inorganic coating | |
| CN106085139A (en) | A kind of preparation method of anticorrosive paint | |
| CN106317386A (en) | Preparing method of antibacterial polylactic acid material | |
| CN106085156A (en) | A kind of wash resistant anti static antibacterial coating and preparation method thereof | |
| CN106366848A (en) | Preparation method of anti-corrosion, antibacterial and formaldehyde-scavenging paint | |
| CN106349874A (en) | Anticorrosion coating preparing method | |
| CN106366767A (en) | Multifunctional water-based ink and preparing method thereof | |
| CN106118227A (en) | A kind of conduction water color ink and preparation method thereof | |
| CN106283858A (en) | A kind of preparation method of photochromic corrugated board | |
| CN106283878A (en) | A kind of preparation method of antibiotic antistatic corrugated board | |
| CN106084981A (en) | A kind of antibacterial and deodouring gravure water color ink and preparation method thereof | |
| CN106221542A (en) | A kind of wear-resisting anti static antibacterial coating and preparation method thereof | |
| CN106220831A (en) | A kind of preparation method of poly-lactic acid material | |
| CN106084921A (en) | A kind of preparation method of waterborne antibacterial inorganic coating | |
| CN106221150A (en) | A kind of preparation method of PET/PTT alloy capable of purifying air | |
| CN106221556A (en) | A kind of deodorization ultraviolet-curing paint and preparation method thereof | |
| CN106084923A (en) | A kind of preparation method of aqueous deodorization inorganic coating | |
| CN106189717A (en) | A kind of preparation method of photochromic anticorrosive paint | |
| CN106366757A (en) | Preparation method of water-soluble photochromic ink | |
| CN106189146A (en) | A kind of preparation method of polylactic acid antibacterial matrices | |
| CN106366849A (en) | Preparation method of antibacterial, anti-radiation and anticorrosion paint | |
| CN106243936A (en) | A kind of wash resistant coating and preparation method thereof | |
| CN106084704A (en) | A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch | |
| CN106189400A (en) | A kind of preparation method of the photochromic inorganic coating of aqueous | |
| CN106084982A (en) | A kind of preparation method of water-based ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |