CN114403156A - 一种抗菌材料的制备方法及抗菌涂料组合物 - Google Patents
一种抗菌材料的制备方法及抗菌涂料组合物 Download PDFInfo
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- CN114403156A CN114403156A CN202210091274.0A CN202210091274A CN114403156A CN 114403156 A CN114403156 A CN 114403156A CN 202210091274 A CN202210091274 A CN 202210091274A CN 114403156 A CN114403156 A CN 114403156A
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- antibacterial
- titanate
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- silver nitrate
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000008199 coating composition Substances 0.000 title claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 30
- 229940070527 tourmaline Drugs 0.000 claims abstract description 30
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 30
- 239000011032 tourmaline Substances 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 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 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- 230000000845 anti-microbial effect Effects 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007792 addition Methods 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- -1 methyl titanate Chemical compound 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 17
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 6
- 229930003268 Vitamin C Natural products 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000019154 vitamin C Nutrition 0.000 description 6
- 239000011718 vitamin C Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- VZWMKHUMEIECPK-UHFFFAOYSA-M benzyl-dimethyl-octadecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 VZWMKHUMEIECPK-UHFFFAOYSA-M 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
-
- 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
- A01N25/26—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 in coated particulate form
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- 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
- A01N25/30—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 characterised by the surfactants
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Health & Medical Sciences (AREA)
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- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
本发明公开了一种抗菌材料的制备方法及抗菌涂料,抗菌材料的制备方法为，纳米级电气石分散在极性有机溶剂中，加入阳离子表面活性剂、分散剂、钛酸酯和还原剂，混合均匀，获得混合物；混合液中滴加硝酸银水溶液，滴加完继续搅拌一定时间，过滤，清洗，干燥，煅烧，获得所述抗菌材料。本申请的抗菌材料抗菌性能好、在涂料中较低含量就具有较好的抗菌效果。
Description
技术领域
本发明涉及功能材料领域，尤其是涉及一种抗菌材料的制备方法及抗菌涂料组合物。
背景技术
随着人们对卫生健康越来越重视，抗菌材料，包括抗菌涂料、抗菌面料等产品越受欢迎。抗菌材料通常是在材料中加入具有抗菌性能的添加剂。
在常用的抗菌添加剂中，纳米级二氧化钛是一种较为有效的材料，在紫外光照射下具有较好的对细菌、病毒等微生物的灭杀效果，但实际应用时，比如在房间内，紫外光少、灭杀微生物的效果不好。。
银离子或纳米银材料也是常用的抗菌材料之一。
现有技术中已有将电气石和纳米二氧化钛结合以及纳米二氧化钛和纳米银材料结合起来以提高抗菌性能的报道，但抗菌性能仍然需要提升。
发明内容
为了进一步提升抗菌性能，获得刚好抗菌性能的材料，本申请提供一种抗菌材料的制备方法。
本申请还提供一种抗菌涂料。
本申请提供一种抗菌材料的制备方法，采用如下的技术方案：
一种抗菌材料的制备方法，包括以下步骤，
S1、纳米级电气石分散在极性有机溶剂中，加入阳离子表面活性剂、分散剂、钛酸酯和还原剂，混合均匀，获得混合物；
S2、往步骤S1获得的混合液中滴加硝酸银水溶液，滴加完继续搅拌一定时间，过滤，清洗，干燥，煅烧，获得所述抗菌材料。本发明中煅烧的温度为500-600℃，大气环境。
本发明中，极性有机溶剂可以选自乙酸乙酯、乙酸丁酯、丙酮、乙醇、甲醇、四氢呋喃、环己酮、甲乙酮等。
在本发明优选的方案中，所述纳米级电气石的平均粒径为10-500nm。更优选的方案中，纳米级电气石的平均粒径为50-300nm。
在本发明优选的方案中，步骤S1中所述阳离子表面活性剂选自季铵盐类阳离子表面活性剂。本发明中，阳离子表面活性剂既起到分散稳定的作用，与分散剂一起有助于纳米级电气石的分散稳定，同时也可以为后续钛酸酯的水解缩合提供酸性环境。在试验中还发现阳离子表面活性剂有助于获得更好抗菌性能的抗菌材料。
本发明中，季铵盐类阳离子表面活性剂的结构通式为R1R2R3R4N+X-，其中，R1选自C8-C18的烷基或取代烷基，R2和R3独自的选自C1-C18的烷基或取代烷基或苄基，R4为甲基或乙基，X-为氯离子、溴离子或碘负离子。更具体的，季铵盐类阳离子表面活性剂可以是十八烷基苄基二甲基氯化铵、十八烷基三甲基氯化铵、十八烷基苄基二甲基溴化铵、十八烷基三甲基溴化铵、溴化二甲基苄基十二烷基铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵等。
在本发明优选的方案中，步骤S1中所述分散剂选自高分子聚合物型分散剂中的一种或几种。本发明中对高分子型分散剂无特别的限制，主要起到对粉体颗粒分散后稳定的作用，既包括步骤S1中纳米电气石的分散稳定，也包括硝酸银还原后获得的纳米银颗粒的分散稳定。更具体的，高分子型分散剂可以是聚丙烯酸钠、聚乙烯醇等。
在本发明优选的方案中，步骤S1中所述钛酸酯选自钛酸四异丙酯、钛酸四正丁酯、钛酸四乙酯、钛酸甲酯和钛酸四异丁酯中的一种或几种。
在本发明优选的方案中，步骤S1中所述还原剂选自硼氢化钠、柠檬酸钠、抗坏血酸、水合肼和葡萄糖中的一种或几种。还原剂的目的是为了还原硝酸银获得纳米银颗粒。
在本发明优选的方案中，步骤S1中所述纳米级电气石、阳离子表面活性剂、分散剂、钛酸酯和还原剂的重量比为(1-10):(0.1-2):(0.05-0.5):(0.1-1):(0.05-0.5)。
在本发明优选的方案中，步骤S2中所述硝酸银水溶液的浓度为0.1-10g/L；所述硝酸银的重量与步骤S1中所述钛酸酯的重量比为(0.1-5):(3-20)。更具体的，硝酸银与钛酸酯的重量比为(0.3-2):(5-15)。
在上述方案中，硝酸银与钛酸酯的重量比可以获得抗菌性能更好的抗菌材料。如果硝酸银太多，会导致还原获得的纳米银不能较好的分散，存在沉淀现象，造成浪费。如果硝酸银太少，形成的抗菌材料不能获得纳米银/二氧化钛/纳米电气石的协同作用，抗菌性较差。
本发明还提供一种抗菌涂料组合物，按重量百分比计，所述抗菌涂料组合物中含有0.05-2％上述任一实施方案所述的制备方法获得的抗菌材料。
在本发明优选的方案中，所述抗菌涂料组合物中含有0.1-1.5％的抗菌材料。
本发明在制备抗菌材料中，先将纳米电气石和钛酸酯进行稳定的分散，再滴加硝酸银水溶液，由于还原剂的存在，硝酸银被逐渐还原形成纳米颗粒，同时钛酸酯发生水解缩合，带动形成的纳米银颗粒沉积在纳米电气石表面形成二氧化钛/纳米银颗粒/纳米电气石的结构，经过煅烧后形成抗菌材料，抗菌材料的结构为以纳米电气石为核、纳米二氧化钛包覆纳米银颗粒为壳的核壳结构。
综上所述，本申请包括以下至少一种有益技术效果：
1.本发明中，获得的抗菌材料是一种以纳米电气石为核、纳米二氧化钛包覆纳米银颗粒为壳的核壳结构，结构稳定性好。电气石能随环境温度、压力变化产生极化作用，对于提高纳米TiO2的抗菌性能具有明显的作用；再结合了纳米银颗粒的抗菌作用，协同发挥了纳米电气石、纳米TiO2和纳米银的作用，获得的抗菌材料具有更好的抗菌性能，能实现在更低的浓度下就获得很好的抗菌性能，抗菌范围广。
2.本发明发现采用阳离子表面活性剂和高分子型分散剂共同作为分散稳定剂，对于获得本发明的抗菌材料具有较好的帮助。
3.本发明采用阳离子表面活性剂还起到为钛酸酯水解缩合提供酸性环境的作用，避免了再加入酸性物质导致对后续工序的不良影响或者引入了对抗菌材料的抗菌性能有不良影响的杂质。
具体实施方式
以下结合各具体实施方式对本申请作进一步详细说明。
如无特别指明，以下各实施例中的份数都为重量份数。
实施例1
10份平均粒径80nm的纳米级电气石分散在1000份无水乙醇中，加入1份十八烷基苄基二甲基氯化铵、0.2份聚乙烯醇分散剂、0.5份钛酸四异丙酯和0.15份维生素C，搅拌分散均匀，获得混合液。
往上述混合物中滴加浓度为5g/L的硝酸银水溶液，其中硝酸银与钛酸四异丙酯的重量比为1:10，滴加结束继续搅拌2小时，过滤，滤出固体用去离子水清洗3次，60℃干燥后在550℃煅烧2小时，获得抗菌材料A-1。
实施例2
5份平均粒径100nm的纳米级电气石分散在500份无水乙醇中，加入0.15份十八烷基三甲基氯化铵、0.1份聚丙烯酸钠分散剂、0.2份钛酸正丁酯和0.2份葡萄糖，搅拌分散均匀，获得混合液。
往上述混合物中滴加浓度为10g/L的硝酸银水溶液，其中硝酸银与钛酸正丁酯的重量比为1:5，滴加结束继续搅拌2小时，过滤，滤出固体去离子水清洗3次，60℃干燥后在550℃煅烧2.5小时，获得抗菌材料A-2。
实施例3
8份平均粒径100nm的纳米级电气石分散在1000份无水乙醇中，加入0.3份十八烷基三甲基溴化铵、0.06份聚乙烯醇分散剂、0.4份钛酸四乙酯和0.1份葡萄糖，搅拌分散均匀，获得混合液。
往上述混合物中滴加浓度为10g/L的硝酸银水溶液，其中硝酸银与钛酸四乙酯的重量比为0.5:10，滴加结束继续搅拌2小时，过滤，滤出固体去离子水清洗3次，50℃干燥后在530℃煅烧2小时，获得抗菌材料A-3。
实施例4
10份平均粒径150nm的纳米级电气石分散在1500份无水乙醇中，加入0.5份十八烷基苄基二甲基溴化铵、0.1份聚乙氧基聚丙氧基分散剂、0.3份钛酸正丁酯和0.1份维生素C，搅拌分散均匀，获得混合液。
往上述混合物中滴加浓度为5g/L的硝酸银水溶液，其中硝酸银与钛酸正丁酯的重量比为1:20，滴加结束继续搅拌2小时，过滤，滤出固体去离子水清洗3次，50℃干燥后在550℃煅烧2小时，获得抗菌材料A-4。
实施例5
5份平均粒径100nm的纳米级电气石分散在1000份无水乙醇中，加入0.3份十八烷基苄基二甲基氯化铵、0.1份聚乙烯醇分散剂、0.4份钛酸异丙酯和0.15份维生素C，搅拌分散均匀，获得混合液。
往上述混合物中滴加浓度为10g/L的硝酸银水溶液，其中硝酸银与钛酸正丁酯的重量比为1:8，滴加结束继续搅拌1.5小时，过滤，滤出固体去离子水清洗3次，50℃干燥后在550℃煅烧2小时，获得抗菌材料A-5。
实施例6
以平均粒径200nm的纳米级电气石替代实施例5中平均粒径100nm的纳米级电气石，其余步骤保持不变，获得抗菌材料A-6。
实施例7
实施例5中硝酸银与钛酸正丁酯的重量比为1:5，其余步骤保持不变，获得抗菌材料A-7。
对比例1
实施例5中不加入十八烷基苄基二甲基氯化铵，其余步骤保持不变，获得抗菌材料A-8。
对比例2
实施例5以十二烷基苯磺酸钠替代十八烷基苄基二甲基氯化铵，其余步骤保持不变，获得抗菌材料A-9。
对比例3
实施例5以AEO-9表面活性剂替代十八烷基苄基二甲基氯化铵，其余步骤保持不变，获得抗菌材料A-10。
对比例4
5份平均粒径100nm的纳米级电气石分散在1000份无水乙醇中，加入0.3份十八烷基苄基二甲基氯化铵、0.1份聚乙烯醇分散剂、0.4份钛酸异丙酯和0.15份维生素C，搅拌分散均匀，获得混合液。
往上述混合物中滴加5份浓度为10wt％的醋酸水溶液，滴加结束继续搅拌1.5小时，过滤，滤出固体去离子水清洗3次，50℃干燥后在550℃煅烧2小时，获得抗菌材料A-11。
对比例5
在1000份无水乙醇中加入0.3份十八烷基苄基二甲基氯化铵、0.1份聚乙烯醇分散剂、0.4份钛酸异丙酯和0.15份维生素C，搅拌分散均匀，获得混合液。
往上述混合物中滴加浓度为10g/L的硝酸银水溶液，其中硝酸银与钛酸正丁酯的重量比为1:8，滴加结束继续搅拌1.5小时，过滤，滤出固体去离子水清洗3次，50℃干燥后在550℃煅烧2小时，获得抗菌材料A-12。煅烧后发现抗菌材料A-12中纳米二氧化钛和纳米银颗粒的分离较为明显。
对比例6
实施例5中以石墨烯替代纳米电气石，其余步骤保持不变，获得抗菌材料A-13。
对比例7
5份平均粒径100nm的纳米级电气石分散在1000份无水乙醇中，加入0.3份十八烷基苄基二甲基氯化铵、0.1份聚乙烯醇分散剂和0.15份维生素C，搅拌分散均匀，获得混合液。
往上述混合物中滴加浓度为10g/L的硝酸银水溶液，其中硝酸银为0.05份，滴加结束继续搅拌1.5小时，过滤，滤出固体去离子水清洗3次，50℃干燥后在550℃煅烧2小时，获得抗菌材料A-14。煅烧后发现纳米银颗粒与纳米电气石的结合力不是很好，存在很明显的分离。
实施例1-7和对比例1-7抗菌材料A1-1～A-14的抗菌性能测试。
涂料配方：100份丙烯酸改性聚酯树脂、15份丙二醇甲醚醋酸酯、12份正丁醇、10份甲醚化氨基树脂、0.6份聚醚改性硅油流平剂、1份硅油消泡剂、0.7份对甲基苯磺酸和若干份抗菌材料。
按《HG/T 3950-2007抗菌涂料》标准进行抗菌性能测试，测试时间24小时，结果如下表1和表2所示。
表1
由表1的结果可知，本发明的抗菌材料在涂料中添加0.8wt％时具有较好的抗菌性能，对金黄色葡萄球菌和大肠杆菌的抗菌率都能达到99％左右，甚至能超过99.5％，相比对比例具有明显的提升。添加1.0％时抗菌性更好，同时也比对比例的抗菌效果更好。
表2
由表2的结果可知，本发明的抗菌材料在涂料中应用时，随着添加浓度的降低，抗菌率的降低幅度较低，即使在添加浓度为0.1wt％时仍然具有较好的抗菌性，对金黄色葡萄球菌和大肠杆菌的抗菌率都能达到90％左右或者更高。而对比例抗菌材料A-11和A-14随着在涂料中添加浓度的降低抗菌率快速降低。
以上均为本申请的较佳实施例，并非依此限制本申请的保护范围，故：凡依本申请的结构、形状、原理所做的等效变化，均应涵盖于本申请的保护范围之内。
Claims (10)
1.一种抗菌材料的制备方法，其特征在于：包括以下步骤，
S1、纳米级电气石分散在极性有机溶剂中，加入阳离子表面活性剂、分散剂、钛酸酯和还原剂，混合均匀，获得混合物；
S2、往步骤S1获得的混合液中滴加硝酸银水溶液，滴加完继续搅拌一定时间，过滤，清洗，干燥，煅烧，获得所述抗菌材料。
2.根据权利要求1所述的制备方法，其特征在于：所述纳米级电气石的平均粒径为10-500nm。
3.根据权利要求1所述的制备方法，其特征在于：步骤S1中所述阳离子表面活性剂选自季铵盐类阳离子表面活性剂。
4.根据权利要求1所述的制备方法，其特征在于：步骤S1中所述分散剂选自高分子聚合物型分散剂中的一种或几种。
5.根据权利要求1所述的制备方法，其特征在于：步骤S1中所述钛酸酯选自钛酸四异丙酯、钛酸四正丁酯、钛酸四乙酯、钛酸甲酯和钛酸四异丁酯中的一种或几种。
6.根据权利要求1所述的制备方法，其特征在于：步骤S1中所述还原剂选自硼氢化钠、柠檬酸钠、抗坏血酸、水合肼和葡萄糖中的一种或几种。
7.根据权利要求1所述的制备方法，其特征在于：步骤S1中所述纳米级电气石、阳离子表面活性剂、分散剂、钛酸酯和还原剂的重量比为(1-10):(0.1-2):(0.05-0.5):(0.1-1):(0.05-0.5)。
8.根据权利要求1所述的制备方法，其特征在于：步骤S2中所述硝酸银水溶液的浓度为0.1-10g/L；所述硝酸银的重量与步骤S1中所述钛酸酯的重量比为(0.1-5):(3-20)。
9.一种抗菌涂料组合物，其特征在于：按重量百分比计，所述抗菌涂料组合物中含有0.05-2％权利要求1-8任一项所述的制备方法获得的抗菌材料。
10.根据权利要求9所述的抗菌涂料组合物，其特征在于：所述抗菌涂料组合物中含有0.1-1.5％的所述抗菌材料。
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| CN116496679A (zh) * | 2023-06-30 | 2023-07-28 | 广州市哲铭油墨涂料有限公司 | 一种多功能环保涂料及其制备方法 |
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