CN109777262A - A kind of modified antibacterial anticorrosive paint of graphene - Google Patents
A kind of modified antibacterial anticorrosive paint of graphene Download PDFInfo
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- CN109777262A CN109777262A CN201910089622.9A CN201910089622A CN109777262A CN 109777262 A CN109777262 A CN 109777262A CN 201910089622 A CN201910089622 A CN 201910089622A CN 109777262 A CN109777262 A CN 109777262A
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- anticorrosive paint
- nano silver
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- antibacterial anticorrosive
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
- 239000003973 paint Substances 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 229910001431 copper ion Inorganic materials 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 241001474374 Blennius Species 0.000 claims description 7
- 241000276489 Merlangius merlangus Species 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- -1 silver ions Chemical class 0.000 claims description 6
- 229940070527 tourmaline Drugs 0.000 claims description 6
- 229910052613 tourmaline Inorganic materials 0.000 claims description 6
- 239000011032 tourmaline Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000000053 physical method Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 9
- 241000894006 Bacteria Species 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 230000003260 anti-sepsis Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 241001417490 Sillaginidae Species 0.000 description 3
- 238000005703 Whiting synthesis reaction Methods 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000001408 fungistatic effect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- 241000228197 Aspergillus flavus Species 0.000 description 1
- 241001515917 Chaetomium globosum Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The present invention relates to antibacterial anticorrosive paint product scopes, in particular to a kind of modified antibacterial anticorrosive paint of graphene, the raw material of the antibacterial anticorrosive paint include: 30-50 parts of epoxy resin, 15-35 parts of modification infusorial earth, 0.5-10 parts of grapheme material, 0.5-1 parts of nano silver particles, 8-20 parts of filler, 1.5-6 parts of auxiliary agent, 13-15 parts and water 16-25 parts of POSS base resin of nano silver copper load by weight.The modified antibacterial anticorrosive paint of a kind of graphene prepared by the present invention is able to solve the practical problem that ship, oceanographic equipment, silo etc. need antibacterial corrosion-resistant field, there is good economic benefit, energy saving material；Steel construction, in terms of there is excellent adhesive force, wearability is good, can be subjected to high/low temperature, high salinity, can resistant bacteria corrosion very well, reach antibacterial antisepsis.
Description
Technical field
The present invention relates to antibacterial anticorrosive paint product scope, in particular to a kind of modified antibacterial anticorrosive paint of graphene.
Background technique
The whole world every year because corrosion caused by economic loss account for about the 4%~5% of GDP, wherein marine corrosion accounts for 1/3,
Hamper the development of marine economy, large ship every 5a that is averaged just needs depressed place to carry out primary antibacterial anticorrosive coating, March maintenance interval
More than, a large amount of antiseptic and inhibiting bacteria function material is consumed, the normal operation of ship has also been delayed, other marine facilities are also such；Also
It lives closely bound up silo with us, most of is all to have the materials such as particulate metal plate, tubing, mixed territory structure to constitute, suppression
Bacterium and anti-corrosion are even more to have strict requirements.
And the antibacterial anti-corrosion material much haveing excellent performance on the market at present is more or less all containing the heavy metals such as lead, chromium, mesh
Before be substantially limited or static, in order to guarantee the long-acting bacteriostatic antiseptic property of coating, usually by increasing paint thickness
Method extends antibacterial anticorrosion time limit, there are also many coating because hardness is low, poor solvent resistance, poor heat resistance or fungistatic effect
The disadvantages of poor, which limits, to be applied and development.
Therefore, for some urgent problems in industry, this invention is proposed.
Summary of the invention
It is an object of the invention to contain heavy metal to solve existing antibacterial anti-corrosion material, and paint thickness is big, hardness
It is low, poor solvent resistance, the defects of poor heat resistance or fungistatic effect are poor and provide it is a kind of have good wearability, water resistance,
Salt fog resistance, flexibility are good, adhesive force is high and the modified antibacterial anticorrosive paint of the graphene of long-term excellent antibacterial anti-corrosive properties.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of modified antibacterial anticorrosive paint of graphene, the raw material of the antibacterial anticorrosive paint includes: epoxy resin by weight
30-50 parts, 15-35 parts of modification infusorial earth, 0.5-10 parts of grapheme material, 0.5-1 parts of nano silver particles, 8-20 parts of filler, help
1.5-6 parts of agent, 13-15 parts and water 16-25 parts of POSS base resin of nano silver copper load.In the technical scheme, diatomite is to apply
Feed additives product has the characteristics that porosity is big, absorbability is strong, chemical property is stable, wear-resisting, heat-resisting, can provide for coating
Excellent surface property, increase-volume, thickening and raising adhesive force.Since it has biggish pore volume, film can be made to shorten dry
The dry time.The dosage that resin can also be reduced, reduces cost, and the present invention is modified diatomite, and diatomite can be improved and applying
Dispersibility in material.Graphene has many advantages, such as light weight, high chemical stability and high-specific surface area, and the resistance to of coating can be improved
Mill property, salt fog resistance.Nano silver has extremely strong oxidisability for microorganism, and therefore nano silver has good antibacterial or kills
Bacterium effect.And since nano silver has good antibacterial or biocidal efficacies, the present invention is negative using nano silver particles+nano silver copper
The method that POSS base resin mutually cooperates with is carried to realize the antibacterial purpose of the present invention.
Preferably, grapheme material is the graphene film being prepared by physical method.In the technical scheme, of the invention
Used in graphene be the graphene film obtained by physical method, cost is lower, can be met different by different preparation conditions
The needs of occasion.
Preferably, the modification infusorial earth is that silane coupling agent KH570 is modified diatomite, modifying agent matter
Amount is the 3% of diatomite.
Preferably, the auxiliary agent is dispersing agent, film auxiliary agent, defoaming agent, PH stabilizer, levelling agent and anti-settling agent.
Preferably, the filler is nano-tourmaline powder, nano-titanium dioxide, talcum powder, mica powder, coarse whiting and sea
The mixture of one or more of phycocolloid powder.
Preferably, the described nano silver copper load POSS base resin the preparation method is as follows:
(1) preparation of POSS pre-polymerization liquid: taking 60~85 parts of ammonium hydroxide to be dissolved in 110 parts of isopropanols in parts by weight, and stirring is equal
Temperature is increased after even to 85~95 DEG C, and γ -10~25 parts of acryloxypropyl trimethoxy silane is added dropwise thereto, is stirred to react
75~80min is obtained, and obtains POSS pre-polymerization liquid；
(2) silver ammino solution nano silver copper ion load POSS base resin suspension: is added dropwise in the POSS pre-polymerization liquid in step (1)
With 20~25 parts of mixed liquor of copper ammon solution, then the reaction was continued under ultrasound condition 70~120min, obtain nano silver copper from
Son load POSS base resin suspension；
(3) it restores: formalin is slowly added dropwise in the nano silver copper ion load POSS base resin suspension in step (2)
30~50 parts, after continuing ultrasonic reaction 1~3 hour, filter cake is filtered to obtain, nano silver copper load POSS base is obtained after washing and drying
Resin.
In the technical scheme, by nano silver copper ion load in POSS resin, since POSS resin is a kind of porous
Half organic half inorganic compound, nano silver and Nanometer Copper, which can adhere to, to be entered in its hole, can be effectively by nano silver
It is fixed with Nanometer Copper, effective component will not be made to remove and cause to fail, while the organic group in POSS base resin can be with
Other organic compounds carry out the connection of chemical bond, further enhance its fixing intensity.
Being formed first by ammonia-catalyzed γ-acryloxypropyl trimethoxy silane in the present invention has γ-propylene
The POSS base resin of monomethacryloxypropyl, will under ultrasonic state then in the mixed liquor that silver ammino solution and copper ammon solution is wherein added
Silver ion and copper ion attachment enter in the hole in POSS base resin, can be significantly more efficient by silver ion and copper under ultrasound
Ion dispersion, prevents it from agglomeration occurs, and then restore to silver ammino solution and copper ammon solution with formalin again
To nano silver particles and nanometer copper particle.Unlike the prior art, the nano silver in the present invention and Nanometer Copper pass through reduction
The phenomenon that silver ammino solution is obtained with copper ammon solution, and that disperses under the alkaline condition of ammonium hydroxide is more uniform, is not in precipitating,
Meanwhile finally obtained nano silver can be more small with nanometer copper particle, so that bactericidal effect is more excellent.
Preferably, the concentration of ammonium hydroxide is 45~55% in the step (1).
Preferably, in the step (2) in the mixed liquor of silver ammino solution and copper ammon solution concentration of silver ions and copper from
The ratio of sub- concentration is 4~5: 7.
Preferably, the concentration of formalin is 45~55% in the step (3).
Beneficial effects of the present invention:
(1) a kind of modified antibacterial anticorrosive paint of graphene prepared by the present invention is able to solve the needs such as ship, oceanographic equipment, silo
The practical problem of antibacterial corrosion-resistant field has good economic benefit, energy saving material；
(2) graphene used in the present invention is the graphene film obtained by physical method, and cost is lower, can pass through different preparations
Condition meets the needs of different occasions；
(3) present invention steel construction, in terms of have excellent adhesive force, wearability is good, can be subjected to high/low temperature, height
Salinity resistant bacteria can corrode very well, reach antibacterial antisepsis.
Specific embodiment
Technical solution of the present invention is made to further describe explanation below by specific embodiment.
If saying that the raw material of use is raw material commonly used in the art without specified otherwise, in the embodiment of the present invention, implement
Method employed in example, is the conventional method of this field.
The filler used in the present invention is nano-tourmaline powder, nano-titanium dioxide, talcum powder, mica powder, coarse whiting and sea
The mixture of one or more of phycocolloid powder is that can be commercially available.
The auxiliary agent used in the present invention is dispersing agent, film auxiliary agent, defoaming agent, PH stabilizer, levelling agent and anti-settling agent,
It is conventional use of dispersing agent, film auxiliary agent, defoaming agent, PH stabilizer, levelling agent and anti-settling agent, is commercially available；In this hair
In bright, dispersing agent, film auxiliary agent, defoaming agent, PH stabilizer, levelling agent and anti-settling agent it is identical in quality.
Grapheme material used in the present invention is the graphene film being prepared by physical method.
Nano silver particles used in the present invention, are commercially available.
Embodiment 1
A kind of modified antibacterial anticorrosive paint of graphene, the raw material of the antibacterial anticorrosive paint includes: epoxy resin by weight
30 parts, 15 parts of modification infusorial earth, 0.5 part of grapheme material, 0.5 part of nano silver particles, 8 parts of filler, 1.5 parts of auxiliary agent, nano silver
Copper loads 13 parts and 16 parts of water of POSS base resin.
Filler includes 1 part of nano-tourmaline powder, 1 part of nano-titanium dioxide, 2 parts of mica powders, 2 parts of coarse whitings and 2 parts of seaweed glues
Powder；The partial size of coarse whiting and seaweed rubber powder is 200 mesh.
The described nano silver copper load POSS base resin the preparation method is as follows:
(1) preparation of POSS pre-polymerization liquid: 60 parts of ammonium hydroxide are taken to be dissolved in 110 parts of isopropanols in parts by weight, after mixing evenly
Temperature is increased to 85 DEG C, γ -10 parts of acryloxypropyl trimethoxy silane is added dropwise thereto, is stirred to react 75min, obtains,
Obtain POSS pre-polymerization liquid；The concentration of ammonium hydroxide is 45%；
(2) silver ammino solution nano silver copper ion load POSS base resin suspension: is added dropwise in the POSS pre-polymerization liquid in step (1)
With 20 parts of mixed liquor of copper ammon solution, then the reaction was continued under ultrasound condition 70min, obtain nano silver copper ion load POSS
Base resin suspension；The ratio of concentration of silver ions and copper ion concentration is 4: 7 in the mixed liquor of silver ammino solution and copper ammon solution；
(3) it restores: formalin 30 is slowly added dropwise in the nano silver copper ion load POSS base resin suspension in step (2)
Part, after continuing ultrasonic reaction 1 hour, filter cake is filtered to obtain, nano silver copper load POSS base resin is obtained after washing and drying；Formaldehyde
The concentration of aqueous solution is 45%.
Embodiment 2
A kind of modified antibacterial anticorrosive paint of graphene, the raw material of the antibacterial anticorrosive paint includes: epoxy resin by weight
42 parts, 21 parts of modification infusorial earth, 7 parts of grapheme material, 0.7 part of nano silver particles, 15 parts of filler, 5 parts of auxiliary agent, nano silver copper it is negative
Carry 14 parts and 20 parts of water of POSS base resin.
Filler includes 2 parts of nano-tourmaline powder, 2 parts of nano-titanium dioxides, 1 part of mica powder, 5 parts of coarse whitings and 5 parts of seaweed glues
Powder；The partial size of coarse whiting and seaweed rubber powder is 300 mesh.
The described nano silver copper load POSS base resin the preparation method is as follows:
(1) preparation of POSS pre-polymerization liquid: 70 parts of ammonium hydroxide are taken to be dissolved in 110 parts of isopropanols in parts by weight, after mixing evenly
Temperature is increased to 88 DEG C, γ -18 parts of acryloxypropyl trimethoxy silane is added dropwise thereto, is stirred to react 77min, obtains,
Obtain POSS pre-polymerization liquid；The concentration of ammonium hydroxide is 48%；
(2) silver ammino solution nano silver copper ion load POSS base resin suspension: is added dropwise in the POSS pre-polymerization liquid in step (1)
With 22 parts of mixed liquor of copper ammon solution, then the reaction was continued under ultrasound condition 90min, obtain nano silver copper ion load POSS
Base resin suspension；The ratio of concentration of silver ions and copper ion concentration is 5: 7 in the mixed liquor of silver ammino solution and copper ammon solution；
(3) it restores: formalin is slowly added dropwise in the nano silver copper ion load POSS base resin suspension in step (2)
40 parts, after continuing ultrasonic reaction 2 hours, filter cake is filtered to obtain, nano silver copper load POSS base resin is obtained after washing and drying；First
The concentration of aldehyde aqueous solution is 49%.
Embodiment 3
A kind of modified antibacterial anticorrosive paint of graphene, the raw material of the antibacterial anticorrosive paint includes: epoxy resin by weight
50 parts, 35 parts of modification infusorial earth, 10 parts of grapheme material, 1 part of nano silver particles, 20 parts of filler, 6 parts of auxiliary agent, nano silver copper it is negative
Carry 15 parts and 25 parts of water of POSS base resin.
Filler includes 2 parts of nano-tourmaline powder, 2 parts of nano-titanium dioxides, 1 part of mica powder, 5 parts of coarse whitings and 10 parts of seaweed glues
Powder；The partial size of coarse whiting and seaweed rubber powder is 250 mesh.
The described nano silver copper load POSS base resin the preparation method is as follows:
(1) preparation of POSS pre-polymerization liquid: 85 parts of ammonium hydroxide are taken to be dissolved in 110 parts of isopropanols in parts by weight, after mixing evenly
Temperature is increased to 95 DEG C, γ -25 parts of acryloxypropyl trimethoxy silane is added dropwise thereto, is stirred to react 80min, obtains,
Obtain POSS pre-polymerization liquid；The concentration of ammonium hydroxide is 55%；
(2) silver ammino solution nano silver copper ion load POSS base resin suspension: is added dropwise in the POSS pre-polymerization liquid in step (1)
With 25 parts of mixed liquor of copper ammon solution, then the reaction was continued under ultrasound condition 120min, obtain nano silver copper ion load
POSS base resin suspension；The ratio of concentration of silver ions and copper ion concentration is 5 in the mixed liquor of silver ammino solution and copper ammon solution:
7；
(3) it restores: formalin is slowly added dropwise in the nano silver copper ion load POSS base resin suspension in step (2)
50 parts, after continuing ultrasonic reaction 3 hours, filter cake is filtered to obtain, nano silver copper load POSS base resin is obtained after washing and drying；First
The concentration of aldehyde aqueous solution is 55%.
Comparative example 1, formula used is same as Example 1, and unique difference has been free from grapheme material.
Comparative example 2, formula used is same as Example 1, and unique difference has been free from nano silver copper load POSS base resin.
Comparative example 3, formula used is same as Example 1, and unique difference has been free from modification infusorial earth.
Performance test:
According to the adhesive force and impact resistance of GB1720, GB1732 testing example 1-3 and the coating of comparative example 1-3, as a result see
Table 1.
Table 1, test result
| Adhesive force/grade | Impact resistance/cm | |
| Embodiment 1 | 4 | 72 |
| Embodiment 2 | 5 | 81 |
| Embodiment 3 | 4 | 83 |
| Comparative example 1 | 1 | 42 |
| Comparative example 2 | 2 | 72 |
| Comparative example 3 | 2 | 72 |
As can be seen from Table 1, coating of the invention is better than not adding stone due to joined grapheme material, adhesive force and impact resistance
The comparative example 1 of black alkene material.
Antiseptic property detection is carried out to coating made from embodiment 1-3 and comparative example 1-3, testing result is shown in Table 2.
Alkali resistance, acid resistance, resistance to salt water detection are according to GB/T 9274-88, and salt fog resistance detection is according to GB/T 1771-
91。
As can be seen from Table 2, coating of the invention is substantially better than corrosion resistance the coating of comparative example 1-3 preparation.
Sterilization test: by Chaetomium globosum bacterium, Aspergillus flavus with the glass slide that is coated on embodiment 2 Yu 2 coating of comparative example
On, be gently stained with bacterium solution with swab stick after 0,30,60,120 hour and be placed on physiological saline, vibrate, take 0.5 milliliter in culture dish,
Culture medium is added, 48h is cultivated in incubator, takes out number clump count, sterilizing rate: sterilizing rate=(initial bacterium is calculated according to formula
Fall clump count after number-sterilization)/initial clump count * 100%, it the results are shown in Table 3.
Table 3, testing result
As can be seen from Table 3, nano silver particles of the present invention+nano silver copper load POSS base resin fungistatic effect, hence it is evident that be better than
Only it is added to the comparative example 2 of nano silver particles.
Claims (9)
1. a kind of modified antibacterial anticorrosive paint of graphene, which is characterized in that the raw material of the antibacterial anticorrosive paint is by weight
Include: 30-50 parts of epoxy resin, 15-35 parts of modification infusorial earth, 0.5-10 parts of grapheme material, 0.5-1 parts of nano silver particles,
8-20 parts of filler, 1.5-6 parts of auxiliary agent, 13-15 parts and water 16-25 parts of POSS base resin of nano silver copper load.
2. a kind of modified antibacterial anticorrosive paint of graphene according to claim 1, which is characterized in that grapheme material be by
The graphene film that physical method is prepared.
3. the modified antibacterial anticorrosive paint of a kind of graphene according to claim 1, which is characterized in that the modification diatom
Soil is that silane coupling agent KH570 is modified diatomite.
4. the modified antibacterial anticorrosive paint of a kind of graphene according to claim 1, which is characterized in that the auxiliary agent is point
Powder, film auxiliary agent, defoaming agent, PH stabilizer, levelling agent and anti-settling agent.
5. the modified antibacterial anticorrosive paint of a kind of graphene according to claim 1, which is characterized in that the filler is to receive
The mixture of one or more of rice tourmaline powder, nano-titanium dioxide, talcum powder, mica powder, coarse whiting and seaweed rubber powder.
6. the modified antibacterial anticorrosive paint of a kind of graphene according to claim 1, which is characterized in that the nano silver copper
Load POSS base resin the preparation method is as follows:
(1) preparation of POSS pre-polymerization liquid: taking 60~85 parts of ammonium hydroxide to be dissolved in 110 parts of isopropanols in parts by weight, and stirring is equal
Temperature is increased after even to 85~95 DEG C, and γ -10~25 parts of acryloxypropyl trimethoxy silane is added dropwise thereto, is stirred to react
75~80min is obtained, and obtains POSS pre-polymerization liquid；
(2) silver ammino solution nano silver copper ion load POSS base resin suspension: is added dropwise in the POSS pre-polymerization liquid in step (1)
With 20~25 parts of mixed liquor of copper ammon solution, then the reaction was continued under ultrasound condition 70~120min, obtain nano silver copper from
Son load POSS base resin suspension；
(3) it restores: formalin is slowly added dropwise in the nano silver copper ion load POSS base resin suspension in step (2)
30~50 parts, after continuing ultrasonic reaction 1~3 hour, filter cake is filtered to obtain, nano silver copper load POSS base is obtained after washing and drying
Resin.
7. the modified antibacterial anticorrosive paint of a kind of graphene according to claim 6, which is characterized in that the step (1)
The concentration of middle ammonium hydroxide is 45~55%.
8. the modified antibacterial anticorrosive paint of a kind of graphene according to claim 6, which is characterized in that the step (2)
The ratio of concentration of silver ions and copper ion concentration is 4~5: 7 in the mixed liquor of middle silver ammino solution and copper ammon solution.
9. the modified antibacterial anticorrosive paint of a kind of graphene according to claim 6, which is characterized in that the step (3)
The concentration of middle formalin is 45~55%.
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| CN111440499A (en) * | 2020-05-30 | 2020-07-24 | 青岛盈海涂料科技有限责任公司 | Water-based antifouling paint and preparation method thereof |
| CN111534138A (en) * | 2020-05-30 | 2020-08-14 | 青岛盈海涂料科技有限责任公司 | Antifouling additive for water-based paint and preparation method thereof |
| WO2022185064A1 (en) * | 2021-03-03 | 2022-09-09 | Ceylon Graphite Corp | Biocidal nanocomposite comprising a photocatalyst |
| CN116716014A (en) * | 2023-06-26 | 2023-09-08 | 江门市皇宙实业有限公司 | Nano-silver graphene composite antibacterial coating material and preparation method thereof |
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| CN111440499A (en) * | 2020-05-30 | 2020-07-24 | 青岛盈海涂料科技有限责任公司 | Water-based antifouling paint and preparation method thereof |
| CN111534138A (en) * | 2020-05-30 | 2020-08-14 | 青岛盈海涂料科技有限责任公司 | Antifouling additive for water-based paint and preparation method thereof |
| WO2022185064A1 (en) * | 2021-03-03 | 2022-09-09 | Ceylon Graphite Corp | Biocidal nanocomposite comprising a photocatalyst |
| CN116716014A (en) * | 2023-06-26 | 2023-09-08 | 江门市皇宙实业有限公司 | Nano-silver graphene composite antibacterial coating material and preparation method thereof |
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