CN106366885A - Wear-proof, antibacterial and radiation protective paint and preparation method thereof - Google Patents
Wear-proof, antibacterial and radiation protective paint and preparation method thereof Download PDFInfo
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- CN106366885A CN106366885A CN201610748908.XA CN201610748908A CN106366885A CN 106366885 A CN106366885 A CN 106366885A CN 201610748908 A CN201610748908 A CN 201610748908A CN 106366885 A CN106366885 A CN 106366885A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D5/14—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a wear-proof, antibacterial and radiation protective paint and a preparation method thereof. The preparation method comprises the steps that 1, a film former is dissolved in a solvent for mixing evenly, and then a film former solution is obtained; 2, 10-20 parts of an antibacterial/nanometer bamboo charcoal mixed material are added in one third of film former solution for high-speed distribution which is conducted for 60-90 minutes, and then an antibacterial/nanometer distribution liquid is obtained; 3, 10-20 parts of photochromic composite are added in another one third of film former solution for high-speed distribution which is conducted for 60-90 minutes, and then a photochromic distribution liquid is obtained; 4, the antibacterial/nanometer distribution liquid and the photochromic distribution liquid are placed in the rest one third film former solution for high-speed distribution which is conducted for 60-90 minutes, and then 3-5 parts of dispersing agent, 1-5 parts of flatting agent, 1-3 parts of defoaming agent and 1-5 parts of anti-settling agent are sequentially added, and the wear-proof, antibacterial and radiation protective paint is prepared after high-speed distribution to be uniform. The paint has excellent antibacterial, air-purifying and radiation-proof properties, and further has a photochromic property.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of wear-resistant antibacterial radiation shielding coating and its preparation side
Method.
Background technology
For the metal surface shell of electronic and electrical equipment, or the surface metal shell of all kinds of radiator, due to sudden and violent for a long time
It is exposed in the air it is easy to be corroded by the air oxygen and moisture content, and occur corruption to get rusty, the shadow that gets rusty of metal surface shell
Ring these electronic and electrical equipments, or the normal work of all kinds of radiator etc. and appearance looks elegant.It is thus desirable to its metal shell
Carry out the cladding protection of coating.However, the common coating of tradition is typically the higher insulator coating of resistivity so that this electronics is electric
Device equipment or spreader surface housing can slowly add up electrostatic during routine use, contacting side with surface metal shell
Coating on electrostatic energy be transmitted to quickly on surface metal shell, then underground is transferred to by ground connection, and with air contact one
The coating of side, then due to the insulating properties of coating, be difficult to conduct electrostatic and dissipate, can only accumulate gradually, more long-pending the more, finally very
To electric discharge phenomena occur, so can affect the normal safety using with user of electronic and electrical equipment.
The common traditional coating in market is natural resin or synthetic resin is base material, add various pigment, various filler,
Auxiliary agent solvent is machined to be fabricated by.Some resins wear no resistance and there is friction in use environment in some, use
Often result in paint film abrasion, and lose function；Again because the enzyme flora that environment hygrothermal environment etc. can cause paint film is given birth to.
Content of the invention
The technical problem to be solved there is provided a kind of wear-resistant antibacterial radiation shielding coating and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of wear-resistant antibacterial radiation shielding coating, it comprises the following steps:
(1) film forming matter is dissolved in solvent, film forming matter solution after mix homogeneously, is obtained；Described film forming matter is saturated polyester resin
Or polyurethane resin；
(2) 10 ~ 20 parts of antibacterials/bamboo charcoal nano compound is taken to add in 1/3 film forming matter solution, dispersion 60 ~ 90min, obtains at a high speed
Antibacterial/radioprotective dispersion liquid；Described antibacterial/bamboo charcoal nano compound is by antimicrobial composite material and bamboo charcoal nano by weight 1 ~ 3:
1 ~ 2 is obtained by mixing；
(3) 10 ~ 20 parts of photochromic complex are taken to add in 1/3 film forming matter solution, dispersion 60 ~ 90min, obtains light-induced variable at a high speed
Color dispersion liquid；
(4) antibacterial/radioprotective dispersion liquid, photochromic dispersion liquid are added in 1/3 film forming matter solution, at a high speed dispersion 60 ~
90min, sequentially adds 3 ~ 5 parts of dispersants, 1 ~ 5 part of levelling agent, 1 ~ 3 part of defoamer and 1 ~ 5 portion of anti-settling agent, is uniformly dispersed at a high speed
Wear-resistant antibacterial radiation shielding coating is obtained afterwards.
In the present invention, described defoamer is organic siliconresin class defoamer, modified organic silicone resin class defoamer and two
Silicon oxide and at least two of the mixing species defoamer of organic siliconresin；Described anti-settling agent is wax class anti-settling agent, silicon dioxide
Class anti-settling agent and at least one of polyureas anti-settling agent；Described levelling agent is solvent levelling agent, acrylic compounds levelling agent and has
At least one of machine silicon class levelling agent.Described dispersant is natural polymer subclass dispersant, synthesis high score subclass dispersant, multivalence
At least one of carboxylic acidss dispersant, block macromolecular copolymer analog dispersant and special ethylenic polymer species dispersant；Institute
State the mixture that solvent is esters solvent and ketones solvent, described esters solvent is ethyl acetate or butyl acetate, described ketone
Solvent is cyclohexanone, n- methyl pyrrolidone, butanone or methyl iso-butyl ketone (MIBK).
In the present invention, described photochromic complex preparation method is as follows: under nitrogen environment, by concentration be 0.05 ~
The protonic acid solution of 0.5mol/l and the DBSA that concentration is 0.05 ~ 0.5mol/l are mixed with volume ratio 3:1 ~ 3, with
When add photochromic powder, add aniline after magnetic agitation 60 ~ 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10；
After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；Anti- at 20 DEG C～30 DEG C
Answer 12 ~ 36h；Acetone, deionized water wash are vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；Will
1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add the water of volume ratio 4:1 afterwards
And ammonia, it is stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 60 ~
90min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited at 90 DEG C 3h is dried, with
To nano polyaniline/photochromic flour complexes/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed in argon
Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under atmosphere, remove polyaniline, photochromic powder/porous sio2, that is, photochromic compound
Thing.Described photochromic powder is rare earth oxide, and described rare earth oxide is nd2o3、er2o3、pr2o3、ceo2、sm2o3、la2o3、
y2o3、yb2o3At least one of.
In the present invention, described bamboo charcoal nano is the bamboo charcoal nano between 100 ~ 500nm for the particle diameter.
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) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and be configured to the graphite that concentration is 0.2 ~ 0.8mg/ml
Alkene dispersion soln, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w ultrasonic power, 600 ~ 800rpm stirs ultrasonic agitation
Mix speed) 80 ~ 100ml graphene dispersion solution, add the graphene quantum dot and the step that load zinc oxide that step (3) is obtained
(7) load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1 ~ 3) the ultrasonic agitation 10 ~ 30min, Ran Houyi being obtained
To the reactor of politef, it is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, cleaning, dry antibacterial be combined
Material.
The invention has the following beneficial effects:
The present invention is through scientific and reasonable collocation antimicrobial composite material, bamboo charcoal nano and photochromic complex so that coating has
There are excellent antibacterial, purify air and shielding property, also there is photochromic characteristic, present different under different illumination
Color, widens the range of application of coating further.Antimicrobial composite material of the present invention is compounded with silver particles and the antibacterial of titanium dioxide
Performance, has more preferable antibacterial effect compared to single silver nano antibacterial agent, and antibacterial persistently, and improves antibacterial uniformity.
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) be configured to concentration be 0.8mg/ml Graphene divide
Scattered solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml
Graphene dispersion solution, the graphene quantum dot of load zinc oxide that addition step (3) is obtained and the load silver that step (7) is obtained/
Titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min, then moves to the reactor of politef
In, 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) be configured to concentration be 0.5mg/ml Graphene divide
Scattered solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml stone
Black alkene dispersion soln, adds load silver/bis- that the prepared graphene quantum dot of load zinc oxide of step (3) and step (7) are obtained
Titanium oxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min, then moves to the reactor of politef
In, 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) be configured to concentration be 0.2mg/ml Graphene divide
Scattered solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml stone
Black alkene dispersion soln, adds load silver/bis- that the prepared graphene quantum dot of load zinc oxide of step (3) and step (7) are obtained
Titanium oxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min, then moves to the reactor of politef
In, 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) be configured to concentration be 0.2mg/ml Graphene divide
Scattered solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml
Graphene dispersion solution, adds the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, ultrasonic agitation 30min, Ran Houyi
To the reactor of politef, it 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) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation
(1000w ultrasonic power, 800rpm mixing speed) 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, continues 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 wear-resistant antibacterial radiation shielding coating, it comprises the following steps:
(1) 40 parts of polyurethane resins are dissolved in 25 parts of ethyl acetates and the mixed solvent of cyclohexanone, are obtained after mix homogeneously
Film forming matter solution；
(2) 10 parts of antibacterials/bamboo charcoal nano compound are taken to add in 1/3 film forming matter solution, dispersion 90min at a high speed, obtain antibacterial/anti-
Radiological dispersal liquid；Antimicrobial composite material and bamboo charcoal nano (particle diameter that described antibacterial/bamboo charcoal nano compound is obtained by embodiment 2
Between 100 ~ 500nm) it is obtained by mixing by weight 3:1；
(3) 20 parts of photochromic complex are taken to add in 1/3 film forming matter solution, dispersion 90min, obtains photochromic dispersion at a high speed
Liquid；
(4) antibacterial/radioprotective dispersion liquid, photochromic dispersion liquid are added in 1/3 film forming matter solution, dispersion 90min at a high speed, then
Sequentially add 4 parts of natural polymer subclass dispersants, 2 parts of silicone levelling agents, 2 parts of organic siliconresin class defoamer and 3 parts of waxes
Class anti-settling agent, is obtained wear-resistant antibacterial radiation shielding coating after being uniformly dispersed at a high speed.
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by concentration for 0.4mol/l's
Protonic 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.
Embodiment 5
A kind of preparation method of wear-resistant antibacterial radiation shielding coating, it comprises the following steps:
(1) 45 parts of polyurethane resins are dissolved in 20 parts of ethyl acetates and the mixed solvent of cyclohexanone, are obtained after mix homogeneously
Film forming matter solution；
(2) 15 parts of antibacterials/bamboo charcoal nano compound are taken to add in 1/3 film forming matter solution, dispersion 90min at a high speed, obtain antibacterial/anti-
Radiological dispersal liquid；Antimicrobial composite material and bamboo charcoal nano (particle diameter that described antibacterial/bamboo charcoal nano compound is obtained by embodiment 2
Between 100 ~ 500nm) it is obtained by mixing by weight 3:1；
(3) 15 parts of photochromic complex are taken to add in 1/3 film forming matter solution, dispersion 90min, obtains photochromic dispersion at a high speed
Liquid；
(4) antibacterial/radioprotective dispersion liquid, photochromic dispersion liquid are added in 1/3 film forming matter solution, dispersion 90min at a high speed, then
Sequentially add 4 parts of natural polymer subclass dispersants, 2 parts of silicone levelling agents, 2 parts of organic siliconresin class defoamer and 3 parts of waxes
Class anti-settling agent, is obtained wear-resistant antibacterial radiation shielding coating after being uniformly dispersed at a high speed.
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by concentration for 0.4mol/l's
Protonic 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.
Embodiment 6
A kind of preparation method of wear-resistant antibacterial radiation shielding coating, it comprises the following steps:
(1) 50 parts of polyurethane resins are dissolved in 30 parts of ethyl acetates and the mixed solvent of cyclohexanone, are obtained after mix homogeneously
Film forming matter solution；
(2) 20 parts of antibacterials/bamboo charcoal nano compound are taken to add in 1/3 film forming matter solution, dispersion 90min at a high speed, obtain antibacterial/anti-
Radiological dispersal liquid；Antimicrobial composite material and bamboo charcoal nano (particle diameter that described antibacterial/bamboo charcoal nano compound is obtained by embodiment 2
Between 100 ~ 500nm) it is obtained by mixing by weight 3:1；
(3) 10 parts of photochromic complex are taken to add in 1/3 film forming matter solution, dispersion 90min, obtains photochromic dispersion at a high speed
Liquid；
(4) antibacterial/radioprotective dispersion liquid, photochromic dispersion liquid are added in 1/3 film forming matter solution, dispersion 90min at a high speed, then
Sequentially add 4 parts of natural polymer subclass dispersants, 2 parts of silicone levelling agents, 2 parts of organic siliconresin class defoamer and 3 parts of waxes
Class anti-settling agent, is obtained wear-resistant antibacterial radiation shielding coating after being uniformly dispersed at a high speed.
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by concentration for 0.4mol/l's
Protonic 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.
Comparative example 3
A kind of preparation method of wear-resistant antibacterial radiation shielding coating, it comprises the following steps:
(1) 50 parts of polyurethane resins are dissolved in 30 parts of ethyl acetates and the mixed solvent of cyclohexanone, are obtained after mix homogeneously
Film forming matter solution；
(2) 10 parts of nano silver antimicrobials and 10 parts of nano bamboo powdered carbons are taken to add in 1/3 film forming matter solution, dispersion 90min, obtains at a high speed
To antibacterial/radioprotective dispersion liquid；
(3) 10 parts of photochromic powder are taken to add in 1/3 film forming matter solution, dispersion 90min, obtains photochromic dispersion liquid at a high speed；
(4) antibacterial/radioprotective dispersion liquid, photochromic dispersion liquid are added in 1/3 film forming matter solution, dispersion 90min at a high speed, then
Sequentially add 4 parts of natural polymer subclass dispersants, 2 parts of silicone levelling agents, 2 parts of organic siliconresin class defoamer and 3 parts of waxes
Class anti-settling agent, is obtained wear-resistant antibacterial radiation shielding coating after being uniformly dispersed at a high speed.
Wherein, described photochromic powder is nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3.
Comparative example 4
A kind of preparation method of wear-resistant antibacterial radiation shielding coating, it comprises the following steps:
(1) 50 parts of polyurethane resins are dissolved in 30 parts of ethyl acetates and the mixed solvent of cyclohexanone, are obtained after mix homogeneously
Film forming matter solution；
(2) 10 parts of photochromic powder are taken to add in film forming matter solution, dispersion 90min, obtains photochromic dispersion liquid at a high speed；Its
In, described photochromic powder is nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3；
(3) 4 parts of natural polymer subclass dispersants, 2 parts of silicone levelling agents, 2 parts of organic siliconresin class froth breakings are sequentially added
Agent and 3 portions of wax class anti-settling agents, are obtained wear-resistant antibacterial radiation shielding coating after being uniformly dispersed at a high speed.
The antibiotic antistatic coating of embodiment 4 ~ 6 and comparative example 3,4 is tested, result is as follows:
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 wear-resistant antibacterial radiation shielding coating, it comprises the following steps:
(1) 40 ~ 50 parts of film forming matters are dissolved in 20 ~ 30 parts of solvents, film forming matter solution after mix homogeneously, is obtained；
(2) 10 ~ 20 parts of antibacterials/bamboo charcoal nano compound is taken to add in 1/3 film forming matter solution, dispersion 60 ~ 90min, obtains at a high speed
Antibacterial/radioprotective dispersion liquid；Described antibacterial/bamboo charcoal nano compound is by antimicrobial composite material and bamboo charcoal nano by weight 1 ~ 3:
1 ~ 2 is obtained by mixing；
(3) 10 ~ 20 parts of photochromic complex are taken to add in 1/3 film forming matter solution, dispersion 60 ~ 90min, obtains light-induced variable at a high speed
Color dispersion liquid；
(4) antibacterial/radioprotective dispersion liquid, photochromic dispersion liquid are added in 1/3 film forming matter solution, at a high speed dispersion 60 ~
90min, sequentially adds 3 ~ 5 parts of dispersants, 1 ~ 5 part of levelling agent, 1 ~ 3 part of defoamer and 1 ~ 5 portion of anti-settling agent, is uniformly dispersed at a high speed
Wear-resistant antibacterial radiation shielding coating is obtained afterwards.
2. the preparation method of wear-resistant antibacterial radiation shielding coating according to claim 1 is it is characterised in that described film forming matter is
Saturated polyester resin or polyurethane resin.
3. the preparation method of wear-resistant antibacterial radiation shielding coating 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 wear-resistant antibacterial radiation shielding coating according to claim 1 is it is characterised in that described bamboo charcoal nano
For particle diameter between 100 ~ 500nm bamboo charcoal nano.
5. the preparation method of wear-resistant antibacterial radiation shielding coating according to claim 1 is it is characterised in that described antibacterial is combined
The preparation method of material is as follows:
(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: 0.005 ~ 0.01g graphite oxide is added to 5 ~ 10ml
Dispersant in, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to carry silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~
30min, moves in the microwave hydrothermal reaction kettle that liner is politef, is placed in microwave assisted hydrothermal synthesis apparatus after sealing,
Microwave power is 200 ~ 400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, and dries load silver/bis- that must be surface-treated
Titanium oxide 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 wear-resistant antibacterial radiation shielding coating according to claim 1 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 wear-resistant antibacterial radiation shielding coating according to claim 1 is it is characterised in that described porous graphite
Alkene is 2 ~ 5 layers, the porous graphene of hole size about 3 ~ 6nm.
8. wear-resistant antibacterial radiation shielding coating according to claim 1 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 wear-resistant antibacterial radiation shielding coating according to claim 1 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 wear-resistant antibacterial radiation shielding coating is it is characterised in that by the arbitrary described preparation method system of claim 1 to 9
?.
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| CN117986849A (en) * | 2024-02-02 | 2024-05-07 | 广东中鼎科技发展有限公司 | Stain-resistant sweat-resistant TPU composite film for airplane cushion and preparation process thereof |
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