CN106366849A - Preparation method of antibacterial, anti-radiation and anticorrosion paint - Google Patents
Preparation method of antibacterial, anti-radiation and anticorrosion paint Download PDFInfo
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- CN106366849A CN106366849A CN201610748934.2A CN201610748934A CN106366849A CN 106366849 A CN106366849 A CN 106366849A CN 201610748934 A CN201610748934 A CN 201610748934A CN 106366849 A CN106366849 A CN 106366849A
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
- C09D5/08—Anti-corrosive paints
-
- 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
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- 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
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a preparation method of antibacterial, anti-radiation and anticorrosion paint. The preparation method comprises the following steps of (1) preparing a resin solution; (2) performing ultrasonic stirring on 1/2 resin solution; dropping an antibacterial compound water solution; continuously performing the ultrasonic stirring; (3) performing ultrasonic stirring on 1/2 resin solution; adding nanometer bamboo charcoal and photochromic compounds; continuously performing the ultrasonic stirring; (4) adding amine resin, pigment, an antifoaming agent, sodium poly hydroxy acid salt, dibutyl phthalate, a flatting agent and mosquito repellent particles into a grinding machine to be ground; (5) mixing and stirring the substances prepared in the steps (2), (3) and (4); adding bentonite; performing stirring, grinding and filtering; then performing sealing and packaging. The preparation method has the advantages that through the synergistic effect among the additives, the paint has excellent antibacterial and photochromic effects, anti-radiation performance and air purification characteristics; the mosquito repellent effect is also achieved; the requirements of multifunctional paint are met; the application of the paint is further expanded.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of antibiotic radiation proof anticorrosive paint and its preparation side
Method.
Background technology
Existing coating function is more single, such as antibiotic paint, anti-static coatings or except methanal paint etc., often by
The coating of mixing several functions reaches multifunctional characteristics, but is relatively inaccessible to desired effect.
Content of the invention
The technical problem to be solved there is provided antibiotic radiation proof anticorrosive paint and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of antibiotic radiation proof anticorrosive paint, comprises the following steps:
(1) 40 ~ 50 parts of epoxy resin, 25 ~ 35 parts of polyphenylene sulfides are added in 30 ~ 45 parts of n-butyl alcohol, ultrasonic agitation is (super
Acoustical power 300 ~ 500w, mixing speed 300 ~ 500rpm) 60 ~ 90min, obtain resin solution；
(2) ultrasonic agitation (ultrasonic power 300 ~ 500w, mixing speed 300 ~ 500rpm) 1/2 resin solution, Deca 5 ~ 10ml is dense
Spend for 0.005 ~ 0.01mol/l antibiotic complex aqueous solution, continuation ultrasonic agitation 20 ~ 30min；
This antibiotic complex, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, 500 ~
800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters after bake
Dry；
(3) ultrasonic agitation (ultrasonic power 300 ~ 500w, mixing speed 300 ~ 500rpm) 1/2 resin solution, adds 0.5 ~ 5 part and receives
Rice bamboo charcoal, continues ultrasonic agitation 20 ~ 30min；Add 1 ~ 3 part of photochromic complex, continue ultrasonic agitation 20 ~ 30min；
Described bamboo charcoal nano and photochromic complex all carry out coupling agent pretreatment, and concrete steps and antibiotic complex are through even
Connection agent pretreatment is the same.
Wherein, described photochromic complex preparation method is as follows: under nitrogen environment, concentration is 0.05 ~ 0.5mol/l
Protonic acid solution and concentration be 0.05 ~ 0.5mol/l DBSA with volume ratio 3:1 ~ 3 mix, be simultaneously introduced light
Mutagens toner, adds aniline after magnetic agitation 60 ~ 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10；Continuously stirred
After 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；
Acetone, deionized water wash are vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；By 1 ~ 10g nanometer
Polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, stir
Mix and uniformly add tetraethyl orthosilicate afterwards, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged
And acquisition precipitation is cleaned successively with acetone and deionized water；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/light
Mutagens toner complex/sio2；By nano polyaniline/photochromic flour complexes/sio2Be placed under argon gas atmosphere carry out 800 ~
1000 DEG C of heat treatment 1 ~ 2h, remove polyaniline, photochromic powder/porous sio2, i.e. photochromic complex.Described photochromic
Powder is rare earth oxide, and described rare earth oxide is nd2o3、er2o3、pr2o3、ceo2、sm2o3、la2o3、y2o3、yb2o3In at least
A kind of.
(4) by 5 ~ 15 parts of amino resins, 1 ~ 10 part of pigment, 0.1 ~ 0.5 part of defoamer, 0.1 ~ 1 part of poly- hydroxy acid sodium salt, 0.1 ~
3 parts of dibutyl phthalates, 0.1 ~ 0.5 part of levelling agent and 0 ~ 3 part of anophelifuge granule add in grinder, are ground to fineness and are less than
30 microns.
(5) stir 60 ~ 90min after the material mixing that step (2), (3) and step (4) are obtained, add 0.5 ~ 1 part of swelling
Continue stirring 60 ~ 90min after soil, then in grinding machine for grinding 90 ~ 120min, filter, obtain antibiotic radiation proof anticorrosive paint,
Seal again, pack.
Described epoxy resin is selected from 665 commercially available organosilicon epoxy resins；Described amino resins are selected from commercially available 520
Lauxite；Described pigment is selected from one of titanium dioxide, zinc oxide, iron oxide red or phthalocyanine green；Described defoamer choosing
From tributyl phosphate, polyethers defoamer, silica-type defoamer or methyl-silicone oil；Described polyethers defoamer is selected from city
One of gp type defoamer, gpe type defoamer or gpes type defoamer of selling；Described poly- hydroxy acid sodium salt is poly- 2-
Hydroxy acid sodium-salt；Described levelling agent is selected from silicone oil, polydimethylsiloxane, polyether polyester azo polyether polyeste or alkane
One of base azo polyether polyeste.
Coupling agent is silane coupler, titanate coupling agent or its mixture.
In the present invention, a kind of preparation method of antimicrobial composite material comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule
Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is
Water；Ultrasonic agitation (500 ~ 1000w ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, Deca walks
Suddenly the half graphene quantum dot suspension that (1) is obtained, continues ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005 ~ 0.01g graphite oxide is added to 5 ~
In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g loads the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, and dries the graphene quantum dot of the load zinc oxide that must be surface-treated.
(4) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction temperature
Spend for 45 ~ 60 DEG C, Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000w ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c
Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 m sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to
100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis-
Titanium oxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~
In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(8) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.2
The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (the ultrasonic work(of 500 ~ 1000w
Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone loading zinc oxide that step (3) is obtained
Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that black alkene quantum dot and step (7) are obtained
10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, clearly
Wash, dry to obtain antimicrobial composite material.
The invention has the following beneficial effects:
The present invention first prepares the graphene quantum dot of load zinc oxide and the graphene quantum dot of load silver/titanium dioxide respectively,
Then it is surface-treated, is finally attached on porous graphene, can preferably load and fixing Nano silver grain and zinc oxide, prevent
Stop its reunion, significantly improve the stability of Nano silver grain and zinc oxide, make Nano silver grain and zinc oxide have more efficient
Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously
Agent has more preferable antibacterial effect, and antibacterial is lasting；
The bamboo charcoal nano that the present invention adopts contains the multiple beneficial element such as charcoal, hydrogen, oxygen, fine and closely woven porous, can block and absorb each
The erosion of the harm ray that kind of electrical equipment produces, makes human body thoroughly exempt the harm of harm ray, bamboo charcoal nano also can produce bear from
Son, adsorbs and decomposes various free harmful substances, automatically adjusts humidity, also can produce the far infrared being best suitable for human body；
The photochromic complex that the present invention adopts has photochromic effect, makes product more rich and varied, can be with photograph
The shades of colour penetrated the difference of light intensity and change, is a splendid legacy, full of magnificent carriage, increases sentiment and artistic effect to coating；
The present invention is through rational arrange in pairs or groups bamboo charcoal nano, photochromic complex, antimicrobial composite material and anophelifuge granule, function
Synergism between additive is so that coating has excellent antibacterial, photochromic effect and shielding property and purifies empty
Gas characteristic, also has mosquito repellent function, meets the demand of multifunctional coating, widens the application of coating further.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 50ml mass fraction is 98%
Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 30min simultaneously, swashs
Photoirradiation power is 2w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is
Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml zinc oxide fluid dispersion, Deca step (1) be obtained one
Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene of zinc oxide
Quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005g graphite oxide is added to the dispersion of 8ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to load the Graphene of zinc oxide
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing
It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200w, at 240 DEG C, react 60min；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processing.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another
Schungite alkene quantum dot suspension, Deca concentration is 0.005mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense
Spend for 0.08mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.1g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(6) 0.3mol/l titanium source (titanium source is potassium fluotitanate) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005g graphite oxide is added to dividing of 10ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.3g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 200w, at 240 DEG C react 60min；Cooling, filters, dries
The load silver/titanium dioxide graphene quantum dot of surface treatment.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the graphene quantum dot loading zinc oxide that step (3) is obtained
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min being obtained with step (7), Ran Houyi
To the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.7g c60 powder, measure the dense sulfur that 80ml mass fraction is 98%
Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 45min simultaneously, swashs
Photoirradiation power is 1.5w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, Deca step (1) is obtained
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.008g graphite oxide is added to dividing of 10ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to load the graphite of zinc oxide
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face is processed.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another
Schungite alkene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense
Spend for 0.05mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(6) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) is obtained, then moves to
In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g c60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 5h；Rapidly join 100ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 60min simultaneously, swashs
Photoirradiation power is 1w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 1mg/ml, solvent is water；
Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, the half that Deca step (1) is obtained
Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene amount of zinc oxide
Sub- point.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.01g graphite oxide is added to the dispersion of 5ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.3g to load the Graphene of zinc oxide
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing
It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processing.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another
Schungite alkene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense
Spend for 0.01mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(6) 0.1mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added to
In 1 mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to
110 DEG C, after reaction 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide
Graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.01g graphite oxide is added to the dispersion of 5ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to carry silver/titanium dioxide Graphene
Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing
It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface
The load silver/titanium dioxide graphene quantum dot processing.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min that step (7) is obtained, then moves to
In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Comparative example 1
A kind of preparation method of antimicrobial composite material, comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.01mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of antimicrobial composite material, comprises the following steps: weigh porous graphene (2 ~ 5 layers, hole size about 3 ~
6nm, layer size 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan
Base sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, Deca concentration is
0.003mol/l silver nitrate solution, controlling reaction temperature is 50 DEG C, and Deca concentration is 0.04mol/l two citric acid monohydrate trisodiums,
Continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene antibiosis material that must load silver.
The detailed process that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated and step are as follows:
The antibacterial of test is respectively staphylococcus aureuses and escherichia coli；With reference to minimal inhibitory concentration (minimal
Inhibitory concentration, mic) method of testing (xiang cai, shaozao tan, aili yu,
jinglin zhang, jiahao liu, wenjie mai, zhenyou jiang. sodium1-
naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver
nanoparticles with lower cytotoxicity and long-term antibacterial
Activity.chemistry-an asian journal. 2012,7 (7): 1664-1670.), first weighed with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with mh meat soup to serial dilute again
Release variable concentrations, be added separately in the mh culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/ml,
Then shaken cultivation 24h at 37 DEG C, observes as a result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, no
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (mic) for this antibacterial with the antibacterial of not long tube.
Table 1: the anti-microbial property of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, add prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200ml saline (0.9mass%), and soak 6 respectively in water, 24, sample after 72h, measure it
Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Embodiment 4
A kind of preparation method of antibiotic radiation proof anticorrosive paint, it comprises the following steps:
(1) 45 part of 665 organosilicon epoxy resin, 30 parts of polyphenylene sulfides are added in 40 parts of n-butyl alcohol, ultrasonic agitation is (super
Acoustical power 400w, mixing speed 400rpm) 90min, obtain resin solution；
(2) ultrasonic agitation (ultrasonic power 500w, mixing speed 500rpm) 1/2 resin solution, Deca 8ml concentration is
0.005mol/l embodiment 2 antibiotic complex aqueous solution, continues ultrasonic agitation 30min；This antibiotic complex is pre- through coupling agent
Process, specially antibiotic complex is added in dehydrated alcohol, 800rpm stirs 2h；Dropwise Deca accounts for antibiotic complex matter
The silane coupler of amount fraction 2%, continues stirring 1h, filters post-drying；
(3) ultrasonic agitation (ultrasonic power 500w, mixing speed 500rpm) 1/2 resin solution, adds 5 parts of bamboo charcoal nano (particle diameters
Between 100 ~ 500nm), continue ultrasonic agitation 30min；Add 1 part of photochromic complex, continue ultrasonic agitation 30min；
Described bamboo charcoal nano and photochromic complex carry out coupling agent pretreatment respectively, particularly as follows: bamboo charcoal nano or light-induced variable
Color complex is added in dehydrated alcohol, and 800rpm stirs 2h；Dropwise Deca accounts for bamboo charcoal nano or photochromic compound substance
The silane coupler of amount fraction 2%, continues stirring 2h, filters post-drying.
Described photochromic complex is obtained by the following method: under nitrogen environment, by the proton for 0.4mol/l for the concentration
Acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder
(nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min
Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is
1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain
Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with
Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder
Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove
Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
(4) by 10 part of 520 Lauxite, 5 parts of pigment, 0.2 part of silica-type defoamer, 0.5 part of poly- 2- hydroxy
Acid sodium-salt, 0.1 part of dibutyl phthalate, 0.3 part of polydimethylsiloxane and 3 parts of anophelifuge granules add in grinder, grind
It is milled to fineness and be less than 30 microns.
(5) stir 90min after the material mixing that step (2), (3) and step (4) are obtained, after adding 0.8 part of bentonite
Continue stirring 90min, then in grinding machine for grinding 120min, filter, obtain antibiotic radiation proof anticorrosive paint, then seal, wrap
Dress.
Embodiment 5
A kind of preparation method of antibiotic radiation proof anticorrosive paint, it comprises the following steps:
(1) 45 part of 665 organosilicon epoxy resin, 30 parts of polyphenylene sulfides are added in 40 parts of n-butyl alcohol, ultrasonic agitation is (super
Acoustical power 400w, mixing speed 400rpm) 90min, obtain resin solution；
(2) ultrasonic agitation (ultrasonic power 500w, mixing speed 500rpm) 1/2 resin solution, Deca 8ml concentration is
0.008mol/l embodiment 2 antibiotic complex aqueous solution, continues ultrasonic agitation 30min；This antibiotic complex is pre- through coupling agent
Process, specially antibiotic complex is added in dehydrated alcohol, 800rpm stirs 2h；Dropwise Deca accounts for antibiotic complex matter
The silane coupler of amount fraction 2%, continues stirring 1h, filters post-drying；
(3) ultrasonic agitation (ultrasonic power 500w, mixing speed 500rpm) 1/2 resin solution, adds 3 parts of bamboo charcoal nano (particle diameters
Between 100 ~ 500nm), continue ultrasonic agitation 30min；Add 2 parts of photochromic complex, continue ultrasonic agitation 30min；
Described bamboo charcoal nano and photochromic complex carry out coupling agent pretreatment respectively, particularly as follows: bamboo charcoal nano or light-induced variable
Color complex is added in dehydrated alcohol, and 800rpm stirs 2h；Dropwise Deca accounts for bamboo charcoal nano or photochromic compound substance
The silane coupler of amount fraction 2%, continues stirring 2h, filters post-drying.
Described photochromic complex is obtained by the following method: under nitrogen environment, by the proton for 0.4mol/l for the concentration
Acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder
(nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min
Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is
1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain
Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with
Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder
Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove
Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
(4) by 10 part of 520 Lauxite, 5 parts of pigment, 0.2 part of silica-type defoamer, 0.5 part of poly- 2- hydroxy
Acid sodium-salt, 0.1 part of dibutyl phthalate, 0.3 part of polydimethylsiloxane and 3 parts of anophelifuge granules add in grinder, grind
It is milled to fineness and be less than 30 microns.
(5) stir 90min after the material mixing that step (2), (3) and step (4) are obtained, after adding 0.8 part of bentonite
Continue stirring 90min, then in grinding machine for grinding 120min, filter, obtain antibiotic radiation proof anticorrosive paint, then seal, wrap
Dress.
Embodiment 6
A kind of preparation method of antibiotic radiation proof anticorrosive paint, it comprises the following steps:
(1) 45 part of 665 organosilicon epoxy resin, 30 parts of polyphenylene sulfides are added in 40 parts of n-butyl alcohol, ultrasonic agitation is (super
Acoustical power 400w, mixing speed 400rpm) 90min, obtain resin solution；
(2) ultrasonic agitation (ultrasonic power 500w, mixing speed 500rpm) 1/2 resin solution, Deca 8ml concentration is 0.01mol/
L embodiment 2 antibiotic complex aqueous solution, continues ultrasonic agitation 30min；This antibiotic complex through coupling agent pretreatment, specifically
It is that antibiotic complex is added in dehydrated alcohol, 800rpm stirs 2h；Dropwise Deca accounts for antibiotic complex mass fraction 2%
Silane coupler, continues stirring 1h, filters post-drying；
(3) ultrasonic agitation (ultrasonic power 500w, mixing speed 500rpm) 1/2 resin solution, adds 0.5 part of bamboo charcoal nano (grain
Footpath is between 100 ~ 500nm), continue ultrasonic agitation 30min；Add 3 parts of photochromic complex, continue ultrasonic agitation 30min；
Described bamboo charcoal nano and photochromic complex carry out coupling agent pretreatment respectively, particularly as follows: bamboo charcoal nano or light-induced variable
Color complex is added in dehydrated alcohol, and 800rpm stirs 2h；Dropwise Deca accounts for bamboo charcoal nano or photochromic compound substance
The silane coupler of amount fraction 2%, continues stirring 2h, filters post-drying.
Described photochromic complex is obtained by the following method: under nitrogen environment, by the proton for 0.4mol/l for the concentration
Acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder
(nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min
Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is
1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain
Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with
Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder
Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove
Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
(4) by 10 part of 520 Lauxite, 5 parts of pigment, 0.2 part of silica-type defoamer, 0.5 part of poly- 2- hydroxy
Acid sodium-salt, 0.1 part of dibutyl phthalate, 0.3 part of polydimethylsiloxane and 3 parts of anophelifuge granules add in grinder, grind
It is milled to fineness and be less than 30 microns.
(5) stir 90min after the material mixing that step (2), (3) and step (4) are obtained, after adding 0.8 part of bentonite
Continue stirring 90min, then in grinding machine for grinding 120min, filter, obtain antibiotic radiation proof anticorrosive paint, then seal, wrap
Dress.
Comparative example 3
Based on the preparation method of embodiment 6, difference is: described photochromic complex is nd2o3、pr2o3、la2o3With
yb2o3It is obtained by mixing by weight 1:2:1:3.
Comparative example 4
Based on the preparation method of embodiment 6, difference is: is not added with described bamboo charcoal nano.
Performance test to embodiment 4～6 and the antibiotic radiation proof anticorrosive paint of comparative example 3 ~ 4 gained is entered according to GB
OK, test result see table:
Antibacterial Evaluation for Uniformity: coating is coated uniformly on glass or ceramic wafer, chooses 100 regions and carry out sterilizing test,
Uniformity Analysis are carried out to the data recording, by the uniformity=100* (1- standard deviation/meansigma methodss).When the uniformity is more than
97%, then be labeled as ▲；When the uniformity is more than 90% and is less than 97%, then it is labeled as ☆；When the uniformity is less than 90%, then it is labeled as
╳.
Air purification effect test is as follows: contrast uses concentration of formaldehyde indoor in front and back and electromagnetic radiation etc., to characterize it
Absorbability.In 10 square metres of vacant room between, place following article: 1. make 10, the clamping plate of furniture, surface is no
Packaging；2. 5 barrels are painted, bung is opened；3. television set 1, opening；4. electric fan 1, opening.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (10)
1. a kind of preparation method of antibiotic radiation proof anticorrosive paint, comprises the following steps:
(1) 40 ~ 50 parts of epoxy resin, 25 ~ 35 parts of polyphenylene sulfides are added in 30 ~ 45 parts of n-butyl alcohol, ultrasonic agitation 60 ~
90min, obtains resin solution；
(2) ultrasonic agitation 1/2 resin solution, Deca 5 ~ 10ml concentration is 0.005 ~ 0.01mol/l antibiotic complex aqueous solution, continues
Continuous ultrasonic agitation 20 ~ 30min；
(3) ultrasonic agitation 1/2 resin solution, adds 0.5 ~ 5 part of bamboo charcoal nano, continues ultrasonic agitation 20 ~ 30min；Add 1 ~ 3
The photochromic complex of part, continues ultrasonic agitation 20 ~ 30min；
(4) by 5 ~ 15 parts of amino resins, 1 ~ 10 part of pigment, 0.1 ~ 0.5 part of defoamer, 0.1 ~ 1 part of poly- hydroxy acid sodium salt, 0.1 ~ 3 part
Dibutyl phthalate, 0.1 ~ 0.5 part of levelling agent and 0 ~ 3 part of anophelifuge granule add in grinder, are ground to fineness and are less than 30
Micron；
(5) stir 60 ~ 90min after the material mixing that step (2), (3) and step (4) are obtained, after adding 0.5 ~ 1 part of bentonite
Continue stirring 60 ~ 90min, then in grinding machine for grinding 90 ~ 120min, filter, obtain antibiotic radiation proof anticorrosive paint, closeer
Envelope, packaging.
2. the preparation method of antibiotic radiation proof anticorrosive paint according to claim 1 is it is characterised in that described antibacterial is combined
Thing, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, and 500 ~ 800rpm stirs 1 ~ 2h；By
Drip the coupling agent that Deca accounts for antibiotic complex mass fraction 2%, continue stirring 1 ~ 2h, filter post-drying.
3. the preparation method of antibiotic radiation proof anticorrosive paint according to claim 1 is it is characterised in that described photochromic
Complex preparation method is as follows: under nitrogen environment, concentration is the protonic acid solution of 0.05 ~ 0.5mol/l and concentration be 0.05 ~
The DBSA of 0.5mol/l is mixed with volume ratio 3:1 ~ 3, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~
Aniline is added, the color-change powder of light and aniline mass ratio are 1:5 ~ 10 after 120min；After continuously stirred 60 ~ 90min, dropwise Deca mistake
Ammonium sulfate, aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are for several times
After be vacuum dried, nano polyaniline/photochromic flour complexes of milling to obtain；1 ~ 10g nano polyaniline/photochromic powder is combined
Thing ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into positive silicic acid second
Ester, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Carry out centrifugation and use acetone and deionization successively
Water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/photochromic flour complexes/sio2；
By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove
Polyaniline, photochromic powder/porous sio2, i.e. photochromic complex.
4. the preparation method of antibiotic radiation proof anticorrosive paint according to claim 3 is it is characterised in that described bamboo charcoal nano
For particle diameter between 100 ~ 500nm bamboo charcoal nano.
5. the preparation method of the antibiotic radiation proof anticorrosive paint according to claim 1 or 4 is it is characterised in that described antibacterial
Complex is obtained by the following method:
(1) prepare graphene quantum dot suspension: 100rpm speed stirring graphene quantum dot suspension, laser irradiation 30 simultaneously
~ 60min, laser irradiation power is 1 ~ 2w；
(2) weigh Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that Deca step (1) is obtained, continue ultrasonic agitation 30 ~
60min；Centrifugation, cleaning, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface treatment of the graphene quantum dot of load zinc oxide；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, Deca silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, Deca two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry the graphene quantum dot that must load silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried to obtain sio2The stone of the load silver of cladding
Black alkene quantum dot；
(6) 0.1 ~ 0.3mol/l titanium source is added in 1mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2
Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, is aged, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~
100ml graphene dispersion solution, the graphene quantum dot of load zinc oxide that addition step (3) is obtained and step (7) are obtained
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
It is incubated 15 ~ 30min at 120 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
6. the preparation method of antibiotic radiation proof anticorrosive paint according to claim 5 is it is characterised in that described Graphene amount
Son point suspension preparation method as follows: weigh 0.5 ~ 0.8g c60 powder, measure 50 ~ 100ml mass fraction be 98% dense
Sulphuric acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 300 ~ 500rpm simultaneously
Mix, obtain mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water into
Bath, keeps 30 ~ 40 DEG C of bath temperature, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with molecular cut off be
1000 bag filter is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, with
Shi Jiguang irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2w.
7. the preparation method of antibiotic radiation proof anticorrosive paint according to claim 5 is it is characterised in that black alkene is 2 ~ 5 layers,
Hole size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
8. antibiotic radiation proof anticorrosive paint according to claim 5 preparation method it is characterised in that described load silver-colored/bis-
The surface treatment of titanium oxide graphene quantum dot particularly as follows: be added to the dispersant of 5 ~ 10ml by 0.005 ~ 0.01g graphite oxide
In, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to carry silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to
Liner is in the microwave hydrothermal reaction kettle of politef, is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is after sealing
200 ~ 400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, dries the load silver/titanium dioxide graphite that must be surface-treated
Alkene quantum dot.
9. the preparation method of antibiotic radiation proof anticorrosive paint according to claim 5 is it is characterised in that described load aoxidizes
The surface treatment of the graphene quantum dot of zinc particularly as follows: 0.005 ~ 0.01g graphite oxide is added in the dispersant of 5 ~ 10ml,
Ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to load the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to liner
For, in the microwave hydrothermal reaction kettle of politef, being placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power be 200 ~
400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, and dries the Graphene quantum of the load zinc oxide that must be surface-treated
Point.
10. a kind of antibiotic radiation proof anticorrosive paint is it is characterised in that press the arbitrary described preparation method system of claim 1 to 9
?.
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| CN110511636A (en) * | 2019-09-09 | 2019-11-29 | 天津孚信阳光科技有限公司 | A kind of photochromic mosquito repellent water paint and preparation method thereof |
| CN112568238A (en) * | 2020-12-22 | 2021-03-30 | 常州山由帝杉防护材料制造有限公司 | Industrial antibacterial liquid, preparation method thereof and special preparation device |
| CN115339172A (en) * | 2022-10-17 | 2022-11-15 | 宁波时代铝箔科技股份有限公司 | Preparation method of antibacterial aluminum foil material, antibacterial aluminum foil and aluminum foil lunch box |
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Application publication date: 20170201 |