CN106189717A - A kind of preparation method of photochromic anticorrosive paint - Google Patents

A kind of preparation method of photochromic anticorrosive paint Download PDF

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Publication number
CN106189717A
CN106189717A CN201610748933.8A CN201610748933A CN106189717A CN 106189717 A CN106189717 A CN 106189717A CN 201610748933 A CN201610748933 A CN 201610748933A CN 106189717 A CN106189717 A CN 106189717A
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quantum dot
photochromic
graphene quantum
ultrasonic agitation
preparation
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陆庚
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Gaoming District Of Foshan City Is Runying Technology Co Ltd
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Gaoming District Of Foshan City Is Runying Technology Co Ltd
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    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Abstract

The invention discloses the preparation method of a kind of photochromic anticorrosive paint, comprise the following steps: (1) prepares resin solution；(2) ultrasonic agitation 1/2 resin solution, drips antibiotic complex aqueous solution, continues ultrasonic agitation；(3) ultrasonic agitation 1/2 resin solution, adds kieselguhr/inorganic oxide and photochromic complex, continues ultrasonic agitation；(4) amino resins, pigment, defoamer, poly-hydroxy acid sodium salt, dibutyl phthalate, levelling agent and anophelifuge granule are added grinding machine for grinding；(5) stir after material mixing step (2), (3) and (4) prepared, add bentonite, stirring, grind, filter, then pack.The present invention is by the synergism between functional additive so that coating has excellent antibacterial, photochromic effect and deodoriging properties and anti-formaldehyde characteristic, also has mosquito repellent function, meets the demand of multifunctional coating, widens the application of coating further.

Description

A kind of preparation method of photochromic anticorrosive paint
Technical field
The present invention relates to technical field of coatings, particularly relate to a kind of photochromic anticorrosive paint and preparation side thereof 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.
Summary of the invention
The technical problem to be solved there is provided photochromic anticorrosive paint and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs:
The preparation method of a kind of photochromic anticorrosive paint, comprises the following steps:
(1) joining in 30 ~ 45 parts of n-butyl alcohol by 40 ~ 50 parts of epoxy resin, 25 ~ 35 parts of polyphenylene sulfides, 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, 5 ~ 10ml is dense in dropping Degree is 0.005 ~ 0.01mol/L antibiotic complex aqueous solution, continues ultrasonic agitation 20 ~ 30min；
This antibiotic complex, through coupling agent pretreatment, is specially and joins in dehydrated alcohol by antibiotic complex, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters after bake Dry；
(3) ultrasonic agitation (ultrasonic power 300 ~ 500W, mixing speed 300 ~ 500rpm) 1/2 resin solution, adds 0.5 ~ 3 part of silicon Diatomaceous earth/inorganic oxide, continues ultrasonic agitation 20 ~ 30min；Add 1 ~ 3 part of photochromic complex, continue ultrasonic agitation 20 ~30min；
Described kieselguhr/inorganic oxide and photochromic complex all carry out coupling agent pretreatment, and concrete steps are multiple with antibacterial Compound is the same through coupling agent pretreatment.
Wherein, described photochromic complex preparation method is as follows: under nitrogen environment, is 0.05 ~ 0.5mol/L by concentration Protonic acid solution and DBSA that concentration is 0.05 ~ 0.5mol/L mix with volume ratio 3:1 ~ 3, 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 dripping 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 final vacuum for several times is dried, 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 Adding tetraethyl orthosilicate after mixing uniformly, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged And clean acquisition precipitation with acetone and deionized water successively；This is deposited at 90 DEG C and is dried 3h, 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, the most 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.
Wherein, described kieselguhr/inorganic oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls Particle diameter is between 10 ~ 300nm；Being dispersed in the aqueous solution of 120ml by kieselguhr, add inorganic oxide, 100 ~ 200W is ultrasonic 100 ~ 300rpm stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/nothing Machine oxide；Wherein said kieselguhr is 1 ~ 2:3 ~ 5 with the weight ratio of inorganic oxide.
(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 material mixing step (2), (3) and step (4) prepared, add 0.5 ~ 1 part of swelling Continue stirring 60 ~ 90min after soil, then at grinding machine for grinding 90 ~ 120min, filter, obtain photochromic anticorrosive paint, then Seal, pack.
Described epoxy resin is selected from 665 commercially available organosilicon epoxy resins；Described amino resins is selected from commercially available 520 Lauxite；Described pigment one in 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 in GP type defoamer, GPE type defoamer or the GPES type defoamer sold；Described poly-hydroxy acid sodium salt is poly-2- Hydroxy acid sodium-salt；Described levelling agent is selected from silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane or alkane One in base modified organic silicon oxygen alkane.
Coupling agent is silane coupler, titanate coupling agent or its mixture.
In the present invention, the preparation method of a kind of antimicrobial composite material comprises the following steps:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is Water；Ultrasonic agitation (500 ~ 1000W ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, dropping step Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~ In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min； Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~ 500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon (being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25 DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added Enter in 1 M sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis- Titanium oxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~ In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ 0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(8) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.2 The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (the ultrasonic merit of 500 ~ 1000W Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone of the load zinc oxide that step (3) prepares Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that ink alkene quantum dot and step (7) prepare 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal, clearly Wash, dry to obtain antimicrobial composite material.
There is advantages that
The present invention the most first prepares graphene quantum dot and the graphene quantum dot of load silver/titanium dioxide of load zinc oxide, Then surface processes, and is finally attached on porous graphene, can preferably load and fix Nano silver grain and zinc oxide, anti- Only it is reunited, and significantly improves the stability of Nano silver grain and zinc oxide, makes Nano silver grain and zinc oxide have more efficient Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously Agent has a more preferable antibacterial effect, antibacterial persistently；
The inorganic oxide main component that the present invention uses has more than the 10 kind of trace element favourable to human body such as magnesium, aluminum, ferrum, by Being the special polarity crystalline solid of a kind of structure in it, self can produce electron ion for a long time, and forever discharge negative aeroion, reach Deodorization purifies the effect of air.After being ground by inorganic oxide and be immersed in inside kieselguhr, can effectively improve it stable Property, kieselguhr can also adsorb harmful gas particularly formaldehyde in air simultaneously, improves the effect purifying air further；
The photochromic complex that the present invention uses has photochromic effect, makes product more rich and varied, can be along with photograph The shades of colour penetrating 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 kieselguhr/inorganic oxide of reasonably arranging in pairs or groups, photochromic complex, antimicrobial composite material and anophelifuge Granule, the synergism between functional additive so that coating have excellent antibacterial, photochromic effect and deodoriging properties and Anti-formaldehyde characteristic, also has mosquito repellent function, meets the demand of multifunctional coating, widens the application of 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 preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 50ml mass fraction is 98% Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash Photoirradiation power is 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml zinc oxide fluid dispersion, dropping step (1) prepare one Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene of zinc oxide Quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005g graphite oxide joins the dispersion of 8mL In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.2g load zinc oxide Graphene Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another Schungite alkene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense Degree is 0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.1g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding Carry the graphene quantum dot of silver.
(6) 0.3mol/L titanium source (titanium source is potassium fluotitanate) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts pH with concentrated ammonia solution Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005g graphite oxide joins dividing of 10mL In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.3g load silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries The load silver/titanium dioxide graphene quantum dot that surface processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, add the graphene quantum dot of the load zinc oxide that step (3) prepares Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min prepared with step (7), then moves To the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.7g C60 powder, measure the dense sulfur that 80ml mass fraction is 98% Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash Photoirradiation power is 1.5W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, dropping step (1) prepares Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.3g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table The load silver/titanium dioxide graphene quantum dot that face processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) prepares, then moves to In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g C60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 5h；Rapidly join 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 60min, swash Photoirradiation power is 1W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 1mg/ml, solvent is water； Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, the half that dropping step (1) prepares Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene amount of zinc oxide Sub-point.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.01g graphite oxide joins the dispersion of 5mL In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.3g load zinc oxide Graphene Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another Schungite alkene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense Degree is 0.01mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding Carry the graphene quantum dot of silver.
(6) 0.1mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined In 1 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 110 DEG C, after reaction 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide Graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.01g graphite oxide joins the dispersion of 5mL In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.1g load silver/titanium dioxide Graphene Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface The load silver/titanium dioxide graphene quantum dot processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min that step (7) prepares, then moves to In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 1
The preparation method of a kind of antimicrobial composite material, comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000 My god, obtain graphene quantum dot suspension.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml Graphene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration For 0.01mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding Carry the graphene quantum dot of silver.
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, add the SiO that step (3) prepares2Cladding carries silver graphene quantum dot, Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean, Dry to obtain antimicrobial composite material.
Comparative example 2
The preparation method of a kind of antimicrobial composite material, comprises the following steps: weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan Base sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, dropping concentration is 0.003mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and dropping concentration is 0.04mol/L bis-citric acid monohydrate trisodium, Continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene antibiosis material of silver.
Detailed process and step that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated are as follows:
The antibacterial of test is respectively staphylococcus aureus and escherichia coli；With reference to minimal inhibitory concentration (minimal Inhibitory concentration, MIC) method of testing (Xiang Cai, Shaozao Tan, Aili Yu, Jinglin Zhang, Jiahao Liu, Wenjie Mai, Zhenyou Jiang. Sodium1- naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver nanoparticles with lower cytotoxicity and long-term antibacterial Activity.Chemistry-An Asian Journal. 2012,7 (7): 1664-1670.), first weigh with electronic balance Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material MH meat soup to the most serial dilute Release variable concentrations, be added separately in the MH culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/mL, Then shaken cultivation 24h at 37 DEG C, observes its result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, nothing The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of the longest tube.
Table 1: embodiment 1 ~ 3 and the anti-microbial property of comparative example 1,2 antimicrobial composite material
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, adds prepared by each embodiment of 1g and comparative example in bottle Antimicrobial composite material sample and 200mL saline (0.9mass%), and in water, soak 6 respectively, 24, sample after 72h, measure it Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite material
Embodiment 4
A kind of preparation method of photochromic anticorrosive paint, it comprises the following steps:
(1) joining in 40 parts of n-butyl alcohol by 45 part of 665 organosilicon epoxy resin, 30 parts of polyphenylene sulfides, 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, dropping 8ml concentration is 0.005mol/L embodiment 2 antibiotic complex aqueous solution, continues ultrasonic agitation 30min；This antibiotic complex is pre-through coupling agent Processing, be specially and join in dehydrated alcohol by antibiotic complex, 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex matter The silane coupler of amount mark 2%, continues stirring 1h, filters post-drying；
(3) ultrasonic agitation (ultrasonic power 500W, mixing speed 500rpm) 1/2 resin solution, adds 3 parts of kieselguhr/inorganic oxygen Compound, continues ultrasonic agitation 30min；Add 1 part of photochromic complex, continue ultrasonic agitation 30min；
Described kieselguhr/inorganic oxide and photochromic complex carry out coupling agent pretreatment respectively, particularly as follows: kieselguhr/ Inorganic oxide or photochromic complex join in dehydrated alcohol, and 800rpm stirs 2h；Dropwise dropping accounts for kieselguhr/nothing Machine oxide or the silane coupler of photochromic complex mass fraction 2%, continue stirring 2h, filter post-drying.
Described photochromic complex prepares by the following method: under nitrogen environment, is the proton of 0.4mol/L by concentration Acid solution and the DBSA that concentration is 0.3mol/L mix 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 dripping 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 final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain 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, the most photochromic complex.
Described kieselguhr/inorganic oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls particle diameter Between 10 ~ 300nm；Being dispersed in the aqueous solution of 120ml by kieselguhr, add inorganic oxide, the ultrasonic 150rpm of 120W stirs Mixing 2h, allow nano material well in kieselguhr hole, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein Described kieselguhr is 1:3 with the weight ratio of inorganic oxide.
(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 less than 30 microns.
(5) 90min is stirred, after adding 0.8 part of bentonite after material mixing step (2), (3) and step (4) prepared Continue stirring 90min, then in grinding machine for grinding 120min, filter, obtain photochromic anticorrosive paint, then seal, pack.
Embodiment 5
A kind of preparation method of photochromic anticorrosive paint, it comprises the following steps:
(1) joining in 40 parts of n-butyl alcohol by 45 part of 665 organosilicon epoxy resin, 30 parts of polyphenylene sulfides, 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, dropping 8ml concentration is 0.008mol/L embodiment 2 antibiotic complex aqueous solution, continues ultrasonic agitation 30min；This antibiotic complex is pre-through coupling agent Processing, be specially and join in dehydrated alcohol by antibiotic complex, 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex matter The silane coupler of amount mark 2%, continues stirring 1h, filters post-drying；
(3) ultrasonic agitation (ultrasonic power 500W, mixing speed 500rpm) 1/2 resin solution, adds 1.5 parts of kieselguhr/inorganic Oxide, continues ultrasonic agitation 30min；Add 2 parts of photochromic complex, continue ultrasonic agitation 30min；
Described kieselguhr/inorganic oxide and photochromic complex carry out coupling agent pretreatment respectively, particularly as follows: kieselguhr/ Inorganic oxide or photochromic complex join in dehydrated alcohol, and 800rpm stirs 2h；Dropwise dropping accounts for kieselguhr/nothing Machine oxide or the silane coupler of photochromic complex mass fraction 2%, continue stirring 2h, filter post-drying.
Described photochromic complex prepares by the following method: under nitrogen environment, is the proton of 0.4mol/L by concentration Acid solution and the DBSA that concentration is 0.3mol/L mix 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 dripping 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 final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain 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, the most photochromic complex.Described kieselguhr/inorganic oxide preparation method is such as Under: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, put into the big of PUHLER company exploitation Flow circulation horizontal sand mill is ground, controls particle diameter between 10 ~ 300nm；Kieselguhr is dispersed in the water-soluble of 120ml In liquid, adding inorganic oxide, the ultrasonic 150rpm of 120W stirs 2h, allow nano material well in kieselguhr hole, repeatedly Sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr is 1:4 with the weight ratio of inorganic oxide.
(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 less than 30 microns.
(5) 90min is stirred, after adding 0.8 part of bentonite after material mixing step (2), (3) and step (4) prepared Continue stirring 90min, then in grinding machine for grinding 120min, filter, obtain photochromic anticorrosive paint, then seal, pack.
Embodiment 6
A kind of preparation method of photochromic anticorrosive paint, it comprises the following steps:
(1) joining in 40 parts of n-butyl alcohol by 45 part of 665 organosilicon epoxy resin, 30 parts of polyphenylene sulfides, 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, dropping 8ml concentration is 0.01mol/ L embodiment 2 antibiotic complex aqueous solution, continues ultrasonic agitation 30min；This antibiotic complex is through coupling agent pretreatment, specifically For joining in dehydrated alcohol by antibiotic complex, 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex mass fraction 2% 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 kieselguhr/inorganic Oxide, continues ultrasonic agitation 30min；Add 3 parts of photochromic complex, continue ultrasonic agitation 30min；
Described kieselguhr/inorganic oxide and photochromic complex carry out coupling agent pretreatment respectively, particularly as follows: kieselguhr/ Inorganic oxide or photochromic complex join in dehydrated alcohol, and 800rpm stirs 2h；Dropwise dropping accounts for kieselguhr/nothing Machine oxide or the silane coupler of photochromic complex mass fraction 2%, continue stirring 2h, filter post-drying.
Described photochromic complex prepares by the following method: under nitrogen environment, is the proton of 0.4mol/L by concentration Acid solution and the DBSA that concentration is 0.3mol/L mix 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 dripping 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 final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain 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, the most photochromic complex.Described kieselguhr/inorganic oxide preparation method is such as Under: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, put into the big of PUHLER company exploitation Flow circulation horizontal sand mill is ground, controls particle diameter between 10 ~ 300nm；Kieselguhr is dispersed in the water-soluble of 120ml In liquid, adding inorganic oxide, the ultrasonic 150rpm of 120W stirs 2h, allow nano material well in kieselguhr hole, repeatedly Sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr is 1:5 with the weight ratio of inorganic oxide.
(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 less than 30 microns.
(5) 90min is stirred, after adding 0.8 part of bentonite after material mixing step (2), (3) and step (4) prepared Continue stirring 90min, then in grinding machine for grinding 120min, filter, obtain photochromic anticorrosive paint, then seal, pack.
Comparative example 3
Preparation method based on 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
Preparation method based on embodiment 6, difference is: be not added with described inorganic oxide.
Comparative example 5
Preparation method based on embodiment 6, difference is: be not added with described kieselguhr.
To embodiment 4～6 and the performance test of photochromic anticorrosive paint of comparative example 3 ~ 5 gained carry out according to GB, Test result see table:
Antibacterial Evaluation for Uniformity: be coated in by coating on glass or ceramic wafer, chooses 100 regions and carries out sterilizing test, to survey The data obtained carry 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.
Air purification effect test is as follows: indoor concentration of formaldehyde and electromagnetic radiation etc. before and after contrast use, to characterize it Absorbability.Between one in the vacant room of 10 square metres, place following article: 1. make 10, the clamping plate of furniture, surface without Packaging；2. paint 5 barrels, 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 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 (10)

1. a preparation method for photochromic anticorrosive paint, comprises the following steps:
(1) 40 ~ 50 parts of epoxy resin, 25 ~ 35 parts of polyphenylene sulfides are joined in 30 ~ 45 parts of n-butyl alcohol, ultrasonic agitation 60 ~ 90min, obtains resin solution；
(2) ultrasonic agitation 1/2 resin solution, dropping 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 ~ 3 part of kieselguhr/inorganic oxide, continues ultrasonic agitation 20 ~ 30min； Add 1 ~ 3 part of photochromic complex, continue 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 less than 30 Micron；
(5) 60 ~ 90min is stirred, after adding 0.5 ~ 1 part of bentonite after material mixing step (2), (3) and step (4) prepared Continue stirring 60 ~ 90min, then at grinding machine for grinding 90 ~ 120min, filter, obtain photochromic anticorrosive paint, closeer Envelope, packaging.
The preparation method of photochromic anticorrosive paint the most according to claim 1, it is characterised in that described antibiotic complex Through coupling agent pretreatment, being specially and join in dehydrated alcohol by antibiotic complex, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters post-drying.
The preparation method of photochromic anticorrosive paint the most according to claim 1, it is characterised in that described photochromic multiple Compound preparation method is as follows: under nitrogen environment, by protonic acid solution that concentration is 0.05 ~ 0.5mol/L and concentration be 0.05 ~ The DBSA of 0.5mol/L mixes with volume ratio 3:1 ~ 3, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~ Adding aniline after 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10；After continuously stirred 60 ~ 90min, dropwise dripped 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 Final vacuum is 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, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged and successively with acetone and deionization Water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, 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, the most photochromic complex.
The preparation method of photochromic anticorrosive paint the most according to claim 3, it is characterised in that described kieselguhr/nothing Machine oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, put into The big flow circulation horizontal sand mill of PUHLER company exploitation is ground, controls particle diameter between 10 ~ 300nm；By diatom Soil is dispersed in the aqueous solution of 120ml, adds inorganic oxide, and the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 2h, allows nanometer material Expect that repeatedly sucking filtration cleans well in kieselguhr hole, be dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr with The weight ratio of inorganic oxide is 1 ~ 2:3 ~ 5.
5. according to the preparation method of the photochromic anticorrosive paint described in claim 1 or 4, it is characterised in that described antibacterial multiple Compound prepares by the following method:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~ 100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that dropping step (1) prepares, continue ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly Wash, dry to load the graphene quantum dot of silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3 Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2 Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, the graphene quantum dot of the load zinc oxide that addition step (3) prepares and step (7) prepare Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~ 15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of photochromic anticorrosive paint the most according to claim 5, 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 photochromic anticorrosive paint the most according to claim 5, it is characterised in that ink alkene is 2 ~ 5 layers, hole Size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
The preparation method of photochromic anticorrosive paint the most according to claim 5, 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 photochromic anticorrosive paint the most according to claim 5, it is characterised in that described load zinc oxide The surface of graphene quantum dot process particularly as follows: 0.005 ~ 0.01g graphite oxide is joined in the dispersant of 5 ~ 10mL, super Sound stirs and adds the graphene quantum dot of 0.1 ~ 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, and moving to liner is 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 zinc oxide Graphene quantum Point.
10. a photochromic anticorrosive paint, it is characterised in that prepare by the arbitrary described preparation method of claim 1 to 9.
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Application publication date: 20161207