CN106465711A - A kind of preparation method of multifunctional aqueous inorganic coating - Google Patents
A kind of preparation method of multifunctional aqueous inorganic coating Download PDFInfo
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- CN106465711A CN106465711A CN201610748866.XA CN201610748866A CN106465711A CN 106465711 A CN106465711 A CN 106465711A CN 201610748866 A CN201610748866 A CN 201610748866A CN 106465711 A CN106465711 A CN 106465711A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 title claims abstract description 22
- 238000013019 agitation Methods 0.000 claims abstract description 68
- 239000000243 solution Substances 0.000 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 17
- 230000003115 biocidal effect Effects 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 239000002562 thickening agent Substances 0.000 claims abstract description 8
- 239000000049 pigment Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000013530 defoamer Substances 0.000 claims abstract description 4
- 239000000945 filler Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 151
- 229910021389 graphene Inorganic materials 0.000 claims description 135
- 239000002096 quantum dot Substances 0.000 claims description 126
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000011787 zinc oxide Substances 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 35
- 239000000725 suspension Substances 0.000 claims description 34
- 239000004332 silver Substances 0.000 claims description 33
- 229910052709 silver Inorganic materials 0.000 claims description 33
- 239000004408 titanium dioxide Substances 0.000 claims description 27
- 229910001923 silver oxide Inorganic materials 0.000 claims description 25
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 229950000845 politef Drugs 0.000 claims description 16
- 239000012456 homogeneous solution Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 238000005253 cladding Methods 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 241000894006 Bacteria Species 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013538 functional additive Substances 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 49
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 34
- 235000010215 titanium dioxide Nutrition 0.000 description 22
- -1 phosphate compound Chemical class 0.000 description 17
- 239000002245 particle Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical group CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012531 culture fluid Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Ceramic Engineering (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Dentistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of preparation method of multifunctional aqueous inorganic coating, it comprises the following steps：（1）Kieselguhr is scattered in aqueous solution, the Deca antibiotic complex aqueous dispersions in ultrasonic agitation；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；（2）At room temperature, first by water, defoamer mix and blend, add pigment and filler, after being sufficiently stirred for, obtain solution A；（3）By Ludox and polymer solution mixing, it is sufficiently stirred for；Add kieselguhr/antibiotic complex, stir to obtain solution B；（4）In step（3）In resulting solution B, add coalescents and thickening agent, be sufficiently stirred for obtaining solution C；（5）By solution C, it is added dropwise in solution A, is sufficiently stirred for, filter.The present invention so that inorganic coating has excellent antibacterial and anti-formaldehyde characteristic, meets multi-functional demand, widens the application of inorganic coating further through rational arrange in pairs or groups kieselguhr and antimicrobial composite material, the synergism between functional additive.
Description
Technical field
The present invention relates to technical field of coatings, a kind of more particularly to preparation side of multifunctional aqueous inorganic coating
Method.
Background technology
Inorganic coating is primarily referred to as, using silicate and phosphate compound as binding agent, adding various face, filler, helping
The coating that agent, firming agent are formulated, wherein silicate macromolecular compound can be divided into alkali silicate and Ludox again.This
Coating kind using inorganic binder as film forming matter has that film-forming temperature is low, its film has excellent weatherability, in ultraviolet
Highly stable under light action, good thermostability, meet fire and do not fire, preferable stain resistance, be difficult to inhale ash, lucid and lively dress can be kept
Adorn effect, non-volatility Organic substance produces, do not pollute the environment during making and using, raw material resourceses enrich, cost
The series of advantages such as cheap, thus be widely used.But existing aqueous inorganic paint function more single it is more difficult to full
The multi-functional feature of foot.
Content of the invention
The technical problem to be solved there is provided a kind of preparation method of multifunctional aqueous inorganic coating.
The technical problem to be solved is achieved by the following technical programs：
A kind of preparation method of multifunctional aqueous inorganic coating, it comprises the following steps：
（1）2 ~ 5 parts of kieselguhr are scattered in aqueous solution, side ultrasonic agitation（100 ~ 300W ultrasonic power, 100 ~ 300rpm stirs
Speed）Side Deca 3 ~ 8mL concentration is the antibiotic complex aqueous dispersions of 0.01 ~ 0.1mol/L；Standing 90min, multiple sucking filtration is clear
Wash, dry kieselguhr/antibiotic complex.
（2）At room temperature, first by 25 ~ 35 parts of water, 0.5 ~ 1 part of defoamer mix and blend, add 5 ~ 10 parts of pigment and 20 ~
30 parts of filleies, after being sufficiently stirred for, are filtrated to get homogeneous solution A；
（3）By described 20 ~ 30 parts of Ludox and 5 ~ 12 parts of polymer solution mixing, it is sufficiently stirred for；1 ~ 5 part of kieselguhr of addition/anti-
Bacterium complex, stirs 30 ~ 60min, obtains homogeneous solution B；
（4）In step（3）In the solution B of gained, add 1 ~ 3 part of coalescents and 0.05 ~ 0.3 part of thickening agent, be sufficiently stirred for, mistake
Filter obtains homogeneous solution C；
（5）By solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, that is, the described High-performance waterborne inorganic paint made.
Preferably, described Ludox is nano level silica dioxide granule（Particle diameter about 10nm）Dispersion liquid in water.
The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol.Described pigment is titanium dioxide or white carbon black.
Described filler is selected from Pulvis Talci, Calcium Carbonate, the combination of one or more of silicon calcium powder.
Described defoamer is selected from isooctanol, the combination of one or more of isopropanol.
Described coalescents be selected from one of ethylene glycol, 2-Butoxyethyl acetate, acetic acid, ethanol, ethyl acetate or
Multiple combinations.
Described thickening agent is PUR40 polyurethane thickener.
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）It is 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（1）Prepared half graphene quantum dot suspension, continues ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, born
The graphene quantum dot of supported with zinc oxide.
（3）The surface treatment of the graphene quantum dot of load zinc oxide：0.005 ~ 0.01g graphite oxide is added to 5 ~
The dispersant of 10mL（DMSO）In, ultrasonic agitation（300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed）And 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
Hydrothermal reaction kettle（50 mL）In, 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）The graphene quantum dot of preparation load silver：Ultrasonic agitation（300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs
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）Graphene quantum dot ultrasonic agitation by 0.1 ~ 0.5g load silver（500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed）It is scattered in ethanol；Add volume ratio 3 ~ 5 afterwards:1 water and ammonia, are stirring evenly and then adding into positive silicon
Acetoacetic ester（Mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1, 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）By 0.1 ~ 0.3mol/L titanium source（Titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride）Plus
Enter in 1 M sulfuric acid solution, mix homogeneously；Add step（5）Prepared SiO2Cladding 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 ~
The dispersant of 10mL（DMSO）In, ultrasonic agitation（300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed）And 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
Hydrothermal reaction kettle（50 mL）In, 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, layer size 100 ~ 500nm）Being configured to concentration is 0.2
The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation（The ultrasonic work(of 500 ~ 1000W
Rate, 600 ~ 800rpm mixing speed）80 ~ 100ml graphene dispersion solution, adds step（3）The stone of prepared load zinc oxide
Black alkene quantum dot and step（7）Prepared load silver/titanium dioxide graphene quantum dot（Both mass ratioes are 2:1~3）Ultrasonic agitation
10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, clearly
Wash, dry to obtain antimicrobial composite material.
The present invention has the advantages that：
The present invention first prepares the graphene quantum dot of load zinc oxide and the graphene quantum dot of load silver/titanium dioxide respectively,
Then it is surface-treated, is finally attached on porous graphene, can preferably load and fixing Nano silver grain and zinc oxide, prevent
Stop its reunion, significantly improve the stability of Nano silver grain and zinc oxide, make Nano silver grain and zinc oxide have more efficient
Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously
Agent has more preferable antibacterial effect, and antibacterial is lasting；
Kieselguhr has absorption in the air harmful gass effect particularly formaldehyde, has the effect of purify air；
, through rational arrange in pairs or groups kieselguhr and antimicrobial composite material, the synergism between functional additive is so that no for the present invention
Machine coating has excellent antibacterial and anti-formaldehyde characteristic, meets multi-functional demand, widens the application of inorganic coating further.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1
A kind of preparation method of antimicrobial composite material, it comprises the following steps：
（1）Prepare graphene quantum dot suspension：Weigh 0.5g C60 powder, measure the dense sulfur that 50ml mass fraction is 98%
Acid, C60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 30min simultaneously, swashs
Photoirradiation power is 2W.
（2）Weigh Zinc oxide quantum dot（Particle diameter about 2 ~ 5nm）It is 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）Prepared one
Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene of zinc oxide
Quantum dot.
（3）The surface treatment of the graphene quantum dot of load zinc oxide：0.005g graphite oxide is added to the dispersion of 8mL
Agent（DMSO）In, ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）And add 0.2g to load the Graphene of zinc oxide
Quantum dot, continues ultrasonic agitation 20min, moves to the microwave hydrothermal reaction kettle that liner is politef（50 mL）In, 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）The graphene quantum dot of preparation load silver：Ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）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）Graphene quantum dot ultrasonic agitation by 0.1g load silver（1000W ultrasonic power, 500rpm mixing speed）
It is scattered in ethanol；Add volume ratio 5 afterwards:1 water and ammonia, are stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, 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）By 0.3mol/L titanium source（Titanium source is potassium fluotitanate）It is added in 1 mol/L sulfuric acid solution, mix homogeneously；Plus
Enter step（5）Prepared SiO2Cladding 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
Powder（DMSO）In, ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）And add 0.3g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves to the microwave hydrothermal reaction kettle that liner is politef（50 mL）In, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 200W, at 240 DEG C react 60min；Cooling, filters, dries
The load silver/titanium dioxide graphene quantum dot of surface treatment.
（8）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm）Being configured to concentration is
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation（1000W ultrasonic power,
800rpm mixing speed）100ml graphene dispersion solution, adds step（3）The graphene quantum dot of prepared load zinc oxide
And step（7）Prepared load silver/titanium dioxide graphene quantum dot（Both mass ratioes are 1:1）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.
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）It is 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）Prepared
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
（3）The surface treatment of the graphene quantum dot of load zinc oxide：0.008g graphite oxide is added to dividing of 10mL
Powder（DMSO）In, ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）And add 0.1g to load the graphite of zinc oxide
Alkene quantum dot, continues ultrasonic agitation 20min, moves to the microwave hydrothermal reaction kettle that liner is politef（50 mL）In, 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）The graphene quantum dot of preparation load silver：Ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）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）Graphene quantum dot ultrasonic agitation by 0.3g load silver（1000W ultrasonic power, 500rpm mixing speed）
It is scattered in ethanol；Add volume ratio 4 afterwards:1 water and ammonia, are stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, 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）By 0.2mol/L titanium source（Titanium source is ammonium titanium fluoride）It is added in 1 mol/L sulfuric acid solution, mix homogeneously；Plus
Enter step（5）Prepared SiO2Cladding 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
Powder（DMSO）In, ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）And add 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves to the microwave hydrothermal reaction kettle that liner is politef（50 mL）In, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300W, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
（8）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm）Being configured to concentration is
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation（1000W ultrasonic power,
800rpm mixing speed）80ml graphene dispersion solution, adds step（3）The graphene quantum dot of prepared load zinc oxide and
Step（7）Prepared load silver/titanium dioxide graphene quantum dot（Both mass ratioes are 2:3）Ultrasonic agitation 30min, then moves to
In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps：
（1）Prepare graphene quantum dot suspension：Weigh 0.8g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, C60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 5h；Rapidly join 100ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 60min simultaneously, swashs
Photoirradiation power is 1W.
（2）Weigh Zinc oxide quantum dot（Particle diameter about 2 ~ 5nm）It is 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, Deca step（1）Prepared half
Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene amount of zinc oxide
Sub- point.
（3）The surface treatment of the graphene quantum dot of load zinc oxide：0.01g graphite oxide is added to the dispersion of 5mL
Agent（DMSO）In, ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）And add 0.3g to load the Graphene of zinc oxide
Quantum dot, continues ultrasonic agitation 20min, moves to the microwave hydrothermal reaction kettle that liner is politef（50 mL）In, 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）The graphene quantum dot of preparation load silver：Ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）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）Graphene quantum dot ultrasonic agitation by 0.5g load silver（1000W ultrasonic power, 500rpm mixing speed）
It is scattered in ethanol；Add volume ratio 3 afterwards:1 water and ammonia, are stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, 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）By 0.1mol/L titanium source（Titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride）It is added to
In 1 mol/L sulfuric acid solution, mix homogeneously；Add step（5）Prepared SiO2Cladding 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
Agent（DMSO）In, ultrasonic agitation（500W ultrasonic power, 300rpm mixing speed）And add 0.1g to carry silver/titanium dioxide Graphene
Quantum dot, continues ultrasonic agitation 30min, moves to the microwave hydrothermal reaction kettle that liner is politef（50 mL）In, after sealing
It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface
The load silver/titanium dioxide graphene quantum dot processing.
（8）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm）Being configured to concentration is
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation（1000W ultrasonic power,
800rpm mixing speed）80ml graphene dispersion solution, adds step（3）The graphene quantum dot of prepared load zinc oxide and
Step（7）Prepared load silver/titanium dioxide graphene quantum dot（Both mass ratioes are 2:1）Ultrasonic agitation 30min, then moves to
In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Comparative example 1
A kind of preparation method of antimicrobial composite material, comprises the following steps：
（1）Prepare graphene quantum dot suspension：Weigh 0.5g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, C60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension.
（2）The 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）Graphene quantum dot ultrasonic agitation by 0.5g load silver（1000W ultrasonic power, 500rpm mixing speed）
It is scattered in ethanol；Add volume ratio 3 afterwards:1 water and ammonia, are stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, adjusting pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain SiO under C2Coat is negative
Carry the graphene quantum dot of silver.
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm）Being configured to concentration is
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation（1000W ultrasonic power,
800rpm mixing speed）100ml graphene dispersion solution, adds step（3）Prepared SiO2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of antimicrobial composite material, comprises the following steps：Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~
6nm, layer size 100 ~ 500nm）It is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan
Base sulfoxide；Ultrasonic agitation（1000W ultrasonic power, 800rpm mixing speed）100ml graphene dispersion solution, Deca concentration is
0.003mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and Deca concentration is 0.04mol/L two citric acid monohydrate trisodiums,
Continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene antibiosis material that must load silver.
The detailed process that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated and step are as follows：
The antibacterial of test is respectively staphylococcus aureuses and escherichia coli；With reference to minimal inhibitory concentration（minimal
inhibitory concentration, MIC）Method of testing（Xiang Cai, Shaozao Tan,Aili Yu,
Jinglin Zhang, Jiahao Liu, Wenjie Mai, Zhenyou Jiang. Sodium1-
naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver
nanoparticles with lower cytotoxicity and long-term antibacterial
activity.Chemistry-An Asian Journal. 2012, 7(7):1664-1670.）, first weighed with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with MH meat soup to serial dilute again
Release variable concentrations, be added separately in the MH culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/mL,
Then shaken cultivation 24h at 37 DEG C, observes as a result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, no
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of not long tube.
Table 1：Embodiment 1 ~ 3 and the anti-microbial property of 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：Embodiment 1 ~ 3 and the long acting antibiotic activity of comparative example 1,2 antimicrobial composite materials
Embodiment 4
A kind of preparation method of multifunctional aqueous inorganic coating, it comprises the following steps：
（1）2 parts of kieselguhr are dispersed in the aqueous solution of 120ml, side ultrasonic agitation（200W ultrasonic power, 100rpm stirring speed
Degree）Side Deca 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.08mol/L；Standing 90min, multiple sucking filtration is clear
Wash, dry kieselguhr/antibiotic complex.
（2）At room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of Calcium Carbonate, fill
After dividing stirring, it is filtrated to get homogeneous solution A；
（3）By described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；3 parts of kieselguhr/antibacterials are added to be combined
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is nano level silica dioxide granule（Particle diameter about 10nm）In water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
（4）In step（3）In the solution B of gained, add 2 parts of coalescents and 0.1 part of PUR40 polyurethane thickener, fully stir
Mix, be filtrated to get homogeneous solution C；
（5）By solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, that is, the described High-performance waterborne inorganic paint made.
Embodiment 5
A kind of preparation method of multifunctional aqueous inorganic coating, it comprises the following steps：
（1）3 parts of kieselguhr are dispersed in the aqueous solution of 120ml, side ultrasonic agitation（200W ultrasonic power, 100rpm stirring speed
Degree）Side Deca 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.05mol/L；Standing 90min, multiple sucking filtration is clear
Wash, dry kieselguhr/antibiotic complex.
（2）At room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of Calcium Carbonate, fill
After dividing stirring, it is filtrated to get homogeneous solution A；
（3）By described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；3 parts of kieselguhr/antibacterials are added to be combined
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is nano level silica dioxide granule（Particle diameter about 10nm）In water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
（4）In step（3）In the solution B of gained, add 2 parts of coalescents and 0.1 part of PUR40 polyurethane thickener, fully stir
Mix, be filtrated to get homogeneous solution C；
（5）By solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, that is, the described High-performance waterborne inorganic paint made.
Embodiment 6
A kind of preparation method of multifunctional aqueous inorganic coating, it comprises the following steps：
（1）5 parts of kieselguhr are dispersed in the aqueous solution of 120ml, side ultrasonic agitation（200W ultrasonic power, 100rpm stirring speed
Degree）Side Deca 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.01mol/L；Standing 90min, multiple sucking filtration is clear
Wash, dry kieselguhr/antibiotic complex.
（2）At room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of Calcium Carbonate, fill
After dividing stirring, it is filtrated to get homogeneous solution A；
（3）By described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；3 parts of kieselguhr/antibacterials are added to be combined
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is nano level silica dioxide granule（Particle diameter about 10nm）In water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
（4）In step（3）In the solution B of gained, add 2 parts of coalescents and 0.1 part of PUR40 polyurethane thickener, fully stir
Mix, be filtrated to get homogeneous solution C；
（5）By solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, that is, the described High-performance waterborne inorganic paint made.
Comparative example 3
Based on the preparation method of embodiment 6, difference is：Remove step（1）, kieselguhr/antibiotic complex is changed to antibacterial
Complex.
Comparative example 4
Based on the preparation method of embodiment 6, difference is：Remove antibiotic complex.
The main performance index of aqueous inorganic paint such as following table：
Antibacterial Evaluation for Uniformity：Coating is coated uniformly on glass or ceramic wafer, chooses 100 regions and carry out sterilizing test,
Uniformity Analysis are carried out to the data recording, by the uniformity=100* (1- standard deviation/meansigma methodss).When the uniformity is more than
97%, then be labeled as ▲；When the uniformity is more than 90% and is less than 97%, then it is labeled as ☆；When the uniformity is less than 90%, then it is labeled as
╳.
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 (6)
1. a kind of preparation method of multifunctional aqueous inorganic coating, it comprises the following steps：
（1）2 ~ 5 parts of kieselguhr are scattered in aqueous solution, in ultrasonic agitation, Deca 3 ~ 8mL concentration is 0.01 ~ 0.1mol/L's
Antibiotic complex aqueous dispersions；Standing 90min, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；
（2）At room temperature, first by 25 ~ 35 parts of water, 0.5 ~ 1 part of defoamer mix and blend, 5 ~ 10 parts of pigment and 20 ~ 30 parts are added
Filler, after being sufficiently stirred for, is filtrated to get homogeneous solution A；
（3）By described 20 ~ 30 parts of Ludox and 5 ~ 12 parts of polymer solution mixing, it is sufficiently stirred for；1 ~ 5 part of kieselguhr of addition/anti-
Bacterium complex, stirs 30 ~ 60min, obtains homogeneous solution B；
（4）In step（3）In the solution B of gained, add 1 ~ 3 part of coalescents and 0.05 ~ 0.3 part of thickening agent, be sufficiently stirred for, mistake
Filter obtains homogeneous solution C；
（5）By solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, that is, the described High-performance waterborne inorganic paint made.
2. the preparation method of multifunctional aqueous inorganic coating according to claim 1 is it is characterised in that described antibacterial is combined
Thing is obtained by the following method：
（1）Prepare graphene quantum dot suspension：100rpm speed stirs 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, Deca step（1）Prepared half graphene quantum dot suspension, continue ultrasonic agitation 30 ~
60min；Centrifugation, cleaning, dry, obtain loading the graphene quantum dot of zinc oxide；
（3）The surface treatment of the graphene quantum dot of load zinc oxide；
（4）The 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 afterwards:1
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 step（5）Prepared SiO2
Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts pH value to 7 with concentrated ammonia solution, is aged, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
（7）Carry the surface treatment of silver/titanium dioxide graphene quantum dot；
（8）Weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~
100ml graphene dispersion solution, adds step（3）The prepared graphene quantum dot of load zinc oxide and step（7）Prepared
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.
3. the preparation method of multifunctional aqueous inorganic coating according to claim 2 is it is characterised in that described Graphene amount
The preparation method of son point suspension is 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.
4. the preparation method of multifunctional aqueous inorganic coating according to claim 2 is it is characterised in that black alkene is 2 ~ 5 layers,
Hole size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
5. multifunctional aqueous inorganic coating according to claim 2 preparation method it is characterised in that described load silver-colored/bis-
The surface treatment of titanium oxide graphene quantum dot is specially：0.005 ~ 0.01g graphite oxide is added to the dispersant of 5 ~ 10mL
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.
6. the preparation method of multifunctional aqueous inorganic coating according to claim 2 is it is characterised in that described load aoxidizes
The surface treatment of the graphene quantum dot of zinc is specially：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.
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