CN107815193A - Graphene-supported nano silver antimicrobials and graphene in-situ reducing loading nano silvery water anti-bacteria coating - Google Patents
Graphene-supported nano silver antimicrobials and graphene in-situ reducing loading nano silvery water anti-bacteria coating Download PDFInfo
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention discloses a kind of graphene-supported nano silver antimicrobials and graphene in-situ reducing loading nano silvery water anti-bacteria coating and preparation method thereof, the graphene-supported nano silver antimicrobials its be prepared by following component：Graphene oxide, silver nitrate, polyvinylpyrrolidone and sodium borohydride, the graphene in-situ reducing loading nano silvery water anti-bacteria coating are counted in parts by weight, and its raw material composition is：0.5 0.8 parts of 25 35 parts of water, 30 40 parts of acrylic resin, 20 30 parts of polyurethane resin, 23 parts of graphene-supported nano silver antimicrobials, 1.5 2.5 parts of dispersant, 1 1.5 parts of curing agent, 0.8 1 parts of defoamer, 0.5 0.8 parts of coalescents and levelling agent, under the collective effect of graphene and Nano Silver, the antimicrobial efficiency of coating, antibacterial time, anti-microbial property can all greatly improve, coating antibiosis excellent effect, antibacterial time are lasting, and nontoxic, pollution-free, water resistance and good weatherability, adhesive force are strong；Nano Silver original position, which is supported in graphene, to be settled, and be uniformly dispersed in emulsion.
Description
Technical field
The present invention relates to chemistry painting industry field, more particularly to the antiseptic and coating for having graphene-supported Nano Silver and its
Preparation method.
Background technology
For a long time, the Ancient Times in China people can just use the natural oils such as tung oil and rosin to paint development historical origin before more than 3000 years
Fat, resin make paint.Since 18th century, the development of Introgression Lines and the foundation of organic chemistry, for grinding for coating
Study carefully and established solid theoretical foundation, coating formally climbs up industrial scene.19th-century is to twentieth century, with polymer chemistry
Setting-up and development, coating starts progressively to move towards the synthetic resin epoch, occurs epoxy, amino, nitro, polyester, poly- ammonia in succession
The functional paints such as ester, acrylic acid, organosilicon, fluorine carbon.21st century, with the enhancing of people's environmental consciousness, what the energy used
Day be becoming tight, environmental protection, energy-conservation, be efficiently the epoch theme.Coating is just towards energy-conservation, resource-saving, pollution-free, efficiency high direction
Development.Therefore the research and development of the water-based coating of high efficiency are just particularly important.
The antibacterial applications of silver can trace back to B.C., and people at that time are known that silver can accelerate Wound healing, preventing and treating sense
Contaminate, purify water and preservation and antisepsis, can prevent bacterial growth with silverware storage food, extend the food storage phase.Silver element has
There is so-called oligodynamic effect, it is only necessary to minimal amount of silver ion, so that it may kill the bacterium contacted, mould, embrace son and true
The microorganisms such as bacterium.Because the size of Argent grain diminishes, the atomic quantity of particle surface dramatically increases, even more than inside particle
Atomic quantity, so as to show a series of excellent properties different from block silver, obtained in electrocondution slurry, sterilization, catalysis etc.
Extensive use is arrived, silver-colored antibiotic paint is one of product, but silver-colored components utilising rate to be present low for existing silver-colored antibiotic paint, is resisted
Bacterium efficiency, Durability of antimicrobial effect deficiency, the problem of poor dispersion.
Graphene is described as " dark fund ", and scientist even foretells that graphene " will thoroughly change 21 century ".And graphite is dilute is
A kind of two-dimensional sheet material being made up of individual layer sp2 hydbridized carbon atoms, its special structures shape it there is peculiar electricity
Performance, good mechanical property, excellent physical and mechanical properties and gas barrier property, after graphite aoxidizes via strong oxidizer
Graphite oxide can be prepared into, oxidized graphite flake layer contains substantial amounts of hydroxyl etc. so that it has very big on modification application
It is convenient.
The content of the invention
It is an object of the invention to provide a kind of graphene-supported nano silver antimicrobials and the load of graphene in-situ reducing to receive
Silver-colored water anti-bacteria coating of rice and preparation method thereof, the antiseptic and its antibacterial effect of coating are more notable, and antibacterial time is more longlasting, energy
Enough it is effectively improved the problem of existing silver-colored antibiotic paint is present.
To achieve the above object, the technical scheme is that：
Graphene-supported nano silver antimicrobials, it is prepared by following component：
Component A：Graphene oxide
B component：Silver nitrate solution
C components：Polyvinylpyrrolidonesolution solution
D components：Sodium borohydride solution
The B component is the 12.5%-20% of component A, and the C components are the 45%-60% of B component, and the D components are
The 27%-35% of B component.
The molar concentration of the silver nitrate solution is 0.002molL-1, the molar concentration of the sodium borohydride solution is
0.005mol·L-1, the mass concentration of the polyvinylpyrrolidonesolution solution is 0.4g/L.
The preparation method of graphene-supported nano silver antimicrobials, step are as follows：
Step 1: prepare graphene oxide using Hummers methods are improved；
The 23-40mL concentrated sulfuric acid is slowly added to be placed with to the beaker of 1-2g crystalline flake graphites at room temperature, stirred；Stirring
3-4.5g potassium permanganate is slowly added in above-mentioned beaker after 15min, stirring reaction 4h；Again by 25-50mL deionization
Water is slowly added in above-mentioned beaker, and hydrogen peroxide then is added dropwise dropwise at room temperature until the liquid in beaker becomes golden yellow；Most
Afterwards with hydrochloric acid and deionized water wash until pH be 7, be freeze-dried 8h, obtain graphene oxide；
Step 2: graphene oxide made from step 1 is carried out at the modification of surface with 3- aminopropyl triethoxysilanes
Reason；Graphene oxide obtained by step 1 is dispersed in ethanol solution, the ethanol solution is mixed by second alcohol and water, institute
The 30%-50% that ethanol content is water is stated, adds 3- aminopropyl triethoxysilanes, the 3- aminopropyl triethoxysilanes are
8-10 times of graphene oxide, 8h is stirred at reflux at 85 DEG C, is centrifuged again after being cooled to room temperature, removed by ethanol solution washing residual
Remaining 3- aminopropyl triethoxysilanes, then dry at 60 DEG C, obtain modified graphene oxide；
Step 3: load of the Nano Silver in graphene：Silver nitrate solution, sodium borohydride solution, the polyvinyl pyrrole of preparation
Alkanone solution, it is standby；Take the modified graphene oxide of step 2 to be dispersed in ethanol solution, ultrasonic 90min, obtain mixing molten
Liquid；Above-mentioned silver nitrate solution is taken to add in mixed solution, shading reaction 2h, obtains first set reaction solution at room temperature, then will
Polyvinylpyrrolidonesolution solution is added dropwise in first set reaction solution, is stirred 30min, is obtained second of reaction solution；So
The speed for taking sodium borohydride solution often to be dripped with 7s afterwards is added in second of reaction solution, is centrifuged immediately after dripping, then uses second
Alcohol and deionized water respectively washing 3 times；15h is finally freeze-dried, obtains graphene-supported nano silver antimicrobials.
Graphene in-situ reducing loading nano silvery water anti-bacteria coating, is counted in parts by weight, and its raw material composition is：Water 25-
35 parts, acrylic resin 30-40 parts, polyurethane resin 20-30 parts, graphene-supported nano silver antimicrobials 2-3 parts, dispersant
1.5-2.5 parts, curing agent 1-1.5 parts, defoamer 0.8-1 parts, coalescents 0.5-0.8 parts and levelling agent 0.5-0.8 parts.
The dispersant is polymers of carboxylic acid salt dispersant.
The curing agent is polyamide-based curing agent.
The defoamer is organic silicon defoamer.
The coalescents are alcohol ethers coalescents.
The levelling agent is polysiloxane-based levelling agent.
The preparation method of graphene in-situ reducing loading nano silvery water anti-bacteria coating, step are as follows：First by above-mentioned
It is standby that the preparation method of graphene-supported nano silver antimicrobials is made graphene-supported nano silver antimicrobials, then by water, propylene
Acid resin, polyurethane resin, dispersant, curing agent, defoamer, coalescents and levelling agent mix in proportion, and finally add
Enter graphene-supported nano silver antimicrobials, acted on using mechanical shearing well mixed.
By using above-mentioned technical proposal, the beneficial effects of the invention are as follows：
Nano Silver in-situ reducing is carried on more folds and anti-microbial property by the present invention by improving traditional component
In graphene, this is different from general physical mixed but by in-situ chemical reduction loading nano silvery on graphene, made
In the graphene-supported nano silver antimicrobials obtained, the load capacity of Nano Silver (nanometer Ag) is 7%-9%, because of the work of graphene fold
With the protective effect not only acted as to nanometer Ag, moreover it is possible to which playing fixed nanometer Ag makes it not settle, and slows down to a certain extent
The rate of release of nanometer Ag make it that the antibacterial time of the coating is more longlasting efficiently；Limitation and its original position due to graphene fold are also
Former preparation process, the size of control nanometer Ag generation, size controlled only 3-5 nanosizeds, the control of nanometer Ag are received
Rice Ag slowly discharges so that the dispersiveness of nano Ag particles improves, particle diameter reduces, and considerably increases the ratio surface of nanometer Ag
Product；And nanometer Ag is prepared under this methodology to be not susceptible to reunite, dispersiveness greatly improves in the solution, moreover graphene
Inherently there is anti-microbial property, under the collective effect of graphene and nanometer Ag, antimicrobial efficiency, antibacterial time, the antibacterial of coating
Performance can all greatly improve；
Antibiotic paint prepared by the present invention, antibacterial effect is excellent, antibacterial time is lasting, and water paint is without formaldehyde, mercury
With other heavy metals, nontoxic, pollution-free, water resistance and good weatherability, adhesive force are strong；Nano Silver original position is supported in graphene not
It can settle, be uniformly dispersed in emulsion.
Brief description of the drawings
Fig. 1 is the minimum bactericidal concentration test of graphene-supported nano silver antimicrobials；
Fig. 2 is graphene-supported Nano Silver SEM and the TEM of graphene-supported Nano Silver and graphene figure；
Fig. 3 is graphene, graphene oxide, graphene/nano silver XRD.
Embodiment
In order to which technical scheme is explained further, the present invention is explained in detail below by specific embodiment
State.
A kind of graphene-supported nano silver antimicrobials disclosed by the invention, it is prepared by following component：
Component A：Graphene oxide
B component：Silver nitrate solution
C components：Polyvinylpyrrolidonesolution solution
D components：Sodium borohydride solution
The B component is the 12.5%-20% of component A, and the C components are the 45%-60% of B component, and the D components are
The 27%-35% of B component.
The molar concentration of the silver nitrate solution is 0.002molL-1, the molar concentration of the sodium borohydride solution is
0.005mol·L-1, the mass concentration of the polyvinylpyrrolidonesolution solution is 0.4g/L.
The preparation method step of the graphene-supported nano silver antimicrobials is as follows：
Step 1: prepare graphene oxide using Hummers methods are improved；It is at room temperature that the 23-40mL concentrated sulfuric acid is slow
The beaker for being placed with 1-2g crystalline flake graphites is added, is stirred；3-4.5g potassium permanganate is slowly added after stirring 15min
State in beaker, stirring reaction 4h；25-50mL deionized water is slowly added in above-mentioned beaker again, then at room temperature dropwise
Hydrogen peroxide is added dropwise until the liquid in beaker becomes golden yellow；Finally washed with hydrochloric acid and deionized water until pH is 7, freezing is dry
Dry 8h, obtains graphene oxide；
Step 2: graphene oxide made from step 1 is carried out at the modification of surface with 3- aminopropyl triethoxysilanes
Reason；Graphene oxide obtained by step 1 is dispersed in ethanol solution, the ethanol solution is mixed by second alcohol and water, institute
The 30%-50% that ethanol content is water is stated, adds 3- aminopropyl triethoxysilanes, the 3- aminopropyl triethoxysilanes are
8-10 times of graphene oxide, 8h is stirred at reflux at 85 DEG C, is centrifuged again after being cooled to room temperature, removed by ethanol solution washing residual
Remaining 3- aminopropyl triethoxysilanes, then dry at 60 DEG C, obtain modified graphene oxide；
Step 3: load of the Nano Silver in graphene：Silver nitrate solution, sodium borohydride solution, the polyvinyl pyrrole of preparation
Alkanone solution, it is standby；Take the modified graphene oxide of step 2 to be dispersed in ethanol solution, ultrasonic 90min, obtain mixing molten
Liquid；Above-mentioned silver nitrate solution is taken to add in mixed solution, shading reaction 2h, obtains first set reaction solution at room temperature, then will
Polyvinylpyrrolidonesolution solution is added dropwise in first set reaction solution, is stirred 30min, is obtained second of reaction solution；So
The speed for taking sodium borohydride solution often to be dripped with 7s afterwards is added in second of reaction solution, is centrifuged immediately after dripping, then uses second
Alcohol and deionized water respectively washing 3 times；15h is finally freeze-dried, obtains graphene-supported nano silver antimicrobials.
Using the 3- aminopropyl triethoxysilanes of small molecule as modifying agent in above-mentioned steps two, its molecular weight is small, often
Amino entrained by mole is more, and enough attachment points can be provided for Ag+, secondly well-known silica in the basic conditions
- OCH3 on alkane is easily hydrolyzed, and is advantageous to improve yield；Using sodium borohydride solution as reduction in above-mentioned steps three
Agent, its nmAg reduced only have 10nm or so, as shown in Fig. 2 a is the SEM of graphene-supported Nano Silver in Fig. 2, c is graphene
The TEM figures of loading nano silvery, and the TEM that b is graphene schemes, Fig. 3 graphenes, graphene oxide, graphene/nano silver XRD,
Therefrom it can be seen that notable difference.
It is a kind of include it is in situ also by the graphenes of graphene-supported nano silver antimicrobials made from above-mentioned preparation method
Former loading nano silvery water anti-bacteria coating, embodiment 1 disclosed by the invention, is counted in parts by weight, and its raw material composition is：
It is a kind of include it is in situ also by the graphenes of graphene-supported nano silver antimicrobials made from above-mentioned preparation method
Former loading nano silvery water anti-bacteria coating, embodiment 2 disclosed by the invention, is counted in parts by weight, and its raw material composition is：
It is a kind of include it is in situ also by the graphenes of graphene-supported nano silver antimicrobials made from above-mentioned preparation method
Former loading nano silvery water anti-bacteria coating, embodiment 3 disclosed by the invention, is counted in parts by weight, and its raw material composition is：
The graphene in-situ reducing loading nano silvery water anti-bacteria coating of the component of 3 kinds of proportionings in above-mentioned 3 embodiments
Preparation method, its step are as follows：
First, graphene-supported Nano Silver is made by the preparation method of above-mentioned graphene-supported nano silver antimicrobials to resist
Microbial inoculum is standby；Then, by water, acrylic resin, polyurethane resin, polymers of carboxylic acid salt dispersant, polyamide-based curing agent,
Organic silicon defoamer, alcohol ethers coalescents and polysiloxane-based levelling agent mix in proportion；Finally, graphene is added
Loading nano silvery antiseptic, acted on using mechanical shearing well mixed.
Comparative example, by weight common nano-silver antibacterial paint, fraction meter, its raw material composition are：
The preparation method of common nano-silver antibacterial paint, first, by water, acrylic resin, polyurethane resin, dispersant,
After curing agent, defoamer, coalescents and levelling agent mix in proportion；Then, nano silver antimicrobials are added inward, are utilized
Mechanical shearing effect is well mixed.
Performance test
1st, minimum bactericidal concentration is tested
Fig. 1 is that to take tetra- parts of concentration of a, b, c, d be respectively 40mgL-1、50mg·L-1、60mg·L-1、80mg·L-1, conversion
Cheng Yin concentration is 3.2mgL-1、4mg·L-1、4.8mg·L-1、6.4mg·L-1Graphene-supported nanometer Ag be separately added into
Bacterium (Escherichia coli) suspension of certain concentration carries out culture observation, the procreation growing state of bacterium is observed after 48h, from Fig. 1
We are clear that the sterilizing situation seen for Escherichia coli, a large amount of bacteriums in a be present, more bacterium in b be present, and
There is a small amount of bacteria living in c after 48 hours, now silver-colored content is 4.8mg/L, almost depositing without bacterium in d
Living, now silver-colored content is 6.4mg/L, more far better than in general nanometer Ag antibacterial effect.The present inventor is by argentiferous 8mg/L's
The coating of the application and traditional argentiferous 8mg/L common nano-silver antibacterial paint carry out anti-microbial property test, test the knot drawn
Fruit, as shown in table 1.
The anti-microbial property table of the argentiferous 8mg/L of table 1 coating
The anti-microbial property of graphene in-situ reducing loading nano silvery water anti-bacteria coating is higher as seen from the above table and antibacterial
Time is more longlasting.
Tested by antibacterial, compared to the nanometer Ag with preferable anti-microbial property to Escherichia coli minimal inhibitory concentration
It is respectively 6.25mgL with minimum bactericidal concentration-1And 12.5mgL-1, this antiseptic is in graphene and the common work of Nano Silver
It is respectively 2.66mgL with lower minimal inhibitory concentration and minimum bactericidal concentration-1-2.95mg·L-1And 6.4mgL-1, carry significantly
High antibacterial effect.
The coating of the application is carried out traditional performance test by the present inventor, tests the result drawn, as shown in table 2
The coating traditional performance of table 2 is tested
| Appearance of film | It is smooth |
| Hardness | >2H |
| Adhesive force | >1 grade |
| Drying time:Surface drying | 30min-40min |
| Drying time:Do solid work | 48h |
| Low-temperature stability | It is without exception |
| Coating temperature-change resistance (5 circulations) | It is without exception |
| Alkali resistance (48h) | It is without exception |
| Tensile strength/% | >1MPa |
| Elongation at break/% | >190% |
The coating of the application as can be seen from the above table, adhesive force is strong, and water resistance and weatherability etc. are preferable.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (7)
1. graphene-supported nano silver antimicrobials, it is characterised in that：It is prepared by following component：
Component A：Graphene oxide
B component：Silver nitrate solution
C components：Polyvinylpyrrolidonesolution solution
D components：Sodium borohydride solution
The B component is the 12.5%-20% of component A, and the C components are the 45%-60% of B component, and the D components are B groups
The 27%-35% of part.
2. graphene-supported nano silver antimicrobials as claimed in claim 1, it is characterised in that：Mole of the silver nitrate solution
Concentration is 0.002molL-1, the molar concentration of the sodium borohydride solution is 0.005molL-1, the polyvinylpyrrolidine
The mass concentration of ketone solution is 0.4g/L.
3. the preparation method of graphene-supported nano silver antimicrobials as claimed in claim 1 or 2, it is characterised in that：Step is such as
Under：
Step 1: prepare graphene oxide using Hummers methods are improved；
The 23-40mL concentrated sulfuric acid is slowly added to be placed with to the beaker of 1-2g crystalline flake graphites at room temperature, stirred；Stirring
3-4.5g potassium permanganate is slowly added in above-mentioned beaker after 15min, stirring reaction 4h；Again by 25-50mL deionization
Water is slowly added in above-mentioned beaker, and hydrogen peroxide then is added dropwise dropwise at room temperature until the liquid in beaker becomes golden yellow；Most
Afterwards with hydrochloric acid and deionized water wash until pH be 7, be freeze-dried 8h, obtain graphene oxide；
Step 2: surface modification treatment is carried out to graphene oxide made from step 1 with 3- aminopropyl triethoxysilanes；Will
Graphene oxide obtained by step 1 is dispersed in ethanol solution, and the ethanol solution is mixed by second alcohol and water, the second
Alcohol content is the 30%-50% of water, adds 3- aminopropyl triethoxysilanes, and the 3- aminopropyl triethoxysilanes are oxidations
8-10 times of graphene, be stirred at reflux 8h at 85 DEG C, centrifuged again after being cooled to room temperature, pass through ethanol solution washing remove it is remaining
3- aminopropyl triethoxysilanes, then dried at 60 DEG C, obtain modified graphene oxide；
Step 3: load of the Nano Silver in graphene：Silver nitrate solution, sodium borohydride solution, the polyvinylpyrrolidone of preparation
Solution, it is standby；Take the modified graphene oxide of step 2 to be dispersed in ethanol solution, ultrasonic 90min, obtain mixed solution；Take
Above-mentioned silver nitrate solution is added in mixed solution, and shading reaction 2h, obtains first set reaction solution, then by polyethylene at room temperature
Pyrrolidone solution is added dropwise in first set reaction solution, is stirred 30min, is obtained second of reaction solution；Then boron is taken
The speed that sodium hydride solution is often dripped with 7s is added in second of reaction solution, is centrifuged immediately after dripping, then with ethanol and is gone
Ionized water respectively washing 3 times；15h is finally freeze-dried, obtains graphene-supported nano silver antimicrobials.
4. graphene in-situ reducing loading nano silvery water anti-bacteria coating, it is characterised in that：Count in parts by weight, its raw material composition
For：Water 25-35 parts, acrylic resin 30-40 parts, polyurethane resin 20-30 parts, graphene-supported nano silver antimicrobials 2-3 parts,
Dispersant 1.5-2.5 parts, curing agent 1-1.5 parts, defoamer 0.8-1 parts, coalescents 0.5-0.8 parts and levelling agent 0.5-0.8
Part；
The graphene-supported nano silver antimicrobials its be prepared by following component：
Component A：Graphene oxide
B component：Silver nitrate solution
C components：Polyvinylpyrrolidonesolution solution
D components：Sodium borohydride solution.
The B component is the 12.5%-20% of component A, and the C components are the 45%-60% of B component, and the D components are B groups
The 27%-35% of part.
5. graphene-supported nano silver antimicrobials as claimed in claim 4, it is characterised in that：Mole of the silver nitrate solution
Concentration is 0.002molL-1, the molar concentration of the sodium borohydride solution is 0.005molL-1, the polyvinylpyrrolidine
The mass concentration of ketone solution is 0.4g/L.
6. graphene in-situ reducing loading nano silvery water anti-bacteria coating as claimed in claim 4, it is characterised in that：Described point
Powder is polymers of carboxylic acid salt dispersant, and the curing agent is polyamide-based curing agent, and the defoamer disappears for organic silicon
Infusion, the coalescents are alcohol ethers coalescents, and the levelling agent is polysiloxane-based levelling agent.
7. the preparation method of the graphene in-situ reducing loading nano silvery water anti-bacteria coating as described in claim 4,5 or 6, its
It is characterised by：Step is as follows：First, obtained graphene-supported nano silver antimicrobials are standby, and the graphene-supported Nano Silver resists
Its step of the preparation method of microbial inoculum is：
Step 1: prepare graphene oxide using Hummers methods are improved；
The 23-40mL concentrated sulfuric acid is slowly added to be placed with to the beaker of 1-2g crystalline flake graphites at room temperature, stirred；Stirring
3-4.5g potassium permanganate is slowly added in above-mentioned beaker after 15min, stirring reaction 4h；Again by 25-50mL deionization
Water is slowly added in above-mentioned beaker, and hydrogen peroxide then is added dropwise dropwise at room temperature until the liquid in beaker becomes golden yellow；Most
Afterwards with hydrochloric acid and deionized water wash until pH be 7, be freeze-dried 8h, obtain graphene oxide；
Step 2: surface modification treatment is carried out to graphene oxide made from step 1 with 3- aminopropyl triethoxysilanes；Will
Graphene oxide obtained by step 1 is dispersed in ethanol solution, and the ethanol solution is mixed by second alcohol and water, the second
Alcohol content is the 30%-50% of water, adds 3- aminopropyl triethoxysilanes, and the 3- aminopropyl triethoxysilanes are oxidations
8-10 times of graphene, be stirred at reflux 8h at 85 DEG C, centrifuged again after being cooled to room temperature, pass through ethanol solution washing remove it is remaining
3- aminopropyl triethoxysilanes, then dried at 60 DEG C, obtain modified graphene oxide；
Step 3: load of the Nano Silver in graphene：Silver nitrate solution, sodium borohydride solution, the polyvinylpyrrolidone of preparation
Solution, it is standby；Take the modified graphene oxide of step 2 to be dispersed in ethanol solution, ultrasonic 90min, obtain mixed solution；Take
Above-mentioned silver nitrate solution is added in mixed solution, and shading reaction 2h, obtains first set reaction solution, then by polyethylene at room temperature
Pyrrolidone solution is added dropwise in first set reaction solution, is stirred 30min, is obtained second of reaction solution；Then boron is taken
The speed that sodium hydride solution is often dripped with 7s is added in second of reaction solution, is centrifuged immediately after dripping, then with ethanol and is gone
Ionized water respectively washing 3 times；15h is finally freeze-dried, obtains graphene-supported nano silver antimicrobials；
Then, by water, acrylic resin, polyurethane resin, dispersant, curing agent, defoamer, coalescents and levelling agent press than
Example is well mixed, finally, adds graphene-supported nano silver antimicrobials, is acted on using mechanical shearing well mixed.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109096740A (en) * | 2018-07-20 | 2018-12-28 | 山东诺威聚氨酯股份有限公司 | Antibacterial antistatic TPU film material and preparation method thereof |
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| CN109096740A (en) * | 2018-07-20 | 2018-12-28 | 山东诺威聚氨酯股份有限公司 | Antibacterial antistatic TPU film material and preparation method thereof |
| CN109207984A (en) * | 2018-08-20 | 2019-01-15 | 中国科学院金属研究所 | The preparation method of corrosion resistant antibiotic anti-biofouling multifunctional metal-base protective coating |
| CN109385179A (en) * | 2018-09-25 | 2019-02-26 | 临沂大学 | A kind of coating and preparation method thereof containing modified graphene oxide |
| CN111378343A (en) * | 2018-12-27 | 2020-07-07 | 中环海化(厦门)船舶智能涂料有限公司 | Environment-friendly graphene-based water-based antifouling paint and preparation method thereof |
| WO2020193854A1 (en) * | 2019-03-22 | 2020-10-01 | Isku Interior Oy | Antimicrobial furniture coating |
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| CN110041497B (en) * | 2019-05-15 | 2021-06-25 | 安徽大学 | Silver-loaded graphene/waterborne polyurethane-acrylate antibacterial emulsion and preparation method thereof |
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| CN112655714A (en) * | 2020-12-25 | 2021-04-16 | 河南煜和科技集团有限公司 | Graphene multi-composite system sterilization disinfectant |
| CN113501978A (en) * | 2021-06-25 | 2021-10-15 | 浙江衢州巨塑化工有限公司 | Nano antibacterial master batch |
| CN113501978B (en) * | 2021-06-25 | 2023-08-18 | 浙江衢州巨塑化工有限公司 | Nanometer antibacterial master batch |
| CN113712043A (en) * | 2021-07-26 | 2021-11-30 | 李艳红 | Graphene composite system water-based bactericidal disinfectant and preparation method thereof |
| CN113696569A (en) * | 2021-08-27 | 2021-11-26 | 苏州金多利纺织新材料有限公司 | PU (polyurethane) antiviral protective fabric and application thereof |
| CN113684677A (en) * | 2021-09-07 | 2021-11-23 | 广东职业技术学院 | Antibacterial garment fabric and preparation method thereof |
| CN115039769A (en) * | 2022-07-21 | 2022-09-13 | 合肥微晶材料科技有限公司 | Cation modified graphene antibacterial spray and preparation method thereof |
| CN115039769B (en) * | 2022-07-21 | 2023-08-25 | 合肥微晶材料科技有限公司 | Cationic modified graphene antibacterial spray and preparation method thereof |
| CN115386290A (en) * | 2022-08-31 | 2022-11-25 | 高志超 | Antibacterial polyurethane coating and preparation method thereof |
| CN115339172A (en) * | 2022-10-17 | 2022-11-15 | 宁波时代铝箔科技股份有限公司 | Preparation method of antibacterial aluminum foil material, antibacterial aluminum foil and aluminum foil lunch box |
| CN115612330A (en) * | 2022-10-24 | 2023-01-17 | 新化县中润化学科技有限公司 | Preparation and application of sulfydryl modified nano silver particle dispersion liquid |
| CN115612330B (en) * | 2022-10-24 | 2023-08-04 | 新化县中润化学科技有限公司 | Preparation and application of mercapto-modified nano silver particle dispersion liquid |
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