CN114873572B - Inorganic antibacterial agent with sodium zirconium phosphate as carrier and preparation method thereof - Google Patents
Inorganic antibacterial agent with sodium zirconium phosphate as carrier and preparation method thereof Download PDFInfo
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- CN114873572B CN114873572B CN202210615110.3A CN202210615110A CN114873572B CN 114873572 B CN114873572 B CN 114873572B CN 202210615110 A CN202210615110 A CN 202210615110A CN 114873572 B CN114873572 B CN 114873572B
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- zirconium phosphate
- sodium
- antibacterial agent
- sodium zirconium
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- YHKRPJOUGGFYNB-UHFFFAOYSA-K sodium;zirconium(4+);phosphate Chemical compound [Na+].[Zr+4].[O-]P([O-])([O-])=O YHKRPJOUGGFYNB-UHFFFAOYSA-K 0.000 title claims abstract description 96
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 122
- 239000000843 powder Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 11
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 11
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 11
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 32
- 229910052709 silver Inorganic materials 0.000 claims description 32
- 239000004332 silver Substances 0.000 claims description 32
- 239000011701 zinc Substances 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- -1 zirconium sodium phosphate zinc Chemical compound 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 230000000845 anti-microbial effect Effects 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 7
- 229940039790 sodium oxalate Drugs 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical group CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 claims description 2
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010146 3D printing Methods 0.000 claims description 2
- 239000004831 Hot glue Substances 0.000 claims description 2
- 229920002413 Polyhexanide Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229940073505 ethyl vanillin Drugs 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 238000005187 foaming Methods 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 238000001175 rotational moulding Methods 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- 238000012549 training Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229940043810 zinc pyrithione Drugs 0.000 claims description 2
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 17
- 108091007643 Phosphate carriers Proteins 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- RZTYEUCBTNJJIW-UHFFFAOYSA-K silver;zirconium(4+);phosphate Chemical compound [Zr+4].[Ag+].[O-]P([O-])([O-])=O RZTYEUCBTNJJIW-UHFFFAOYSA-K 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- RUYRJRAIPYPPFH-UHFFFAOYSA-H silver;sodium;zirconium(4+);diphosphate Chemical compound [Na+].[Zr+4].[Ag+].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O RUYRJRAIPYPPFH-UHFFFAOYSA-H 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WNGFSLSVAFJVQG-UHFFFAOYSA-L azanium;zirconium(2+);phosphate Chemical compound [NH4+].[Zr+2].[O-]P([O-])([O-])=O WNGFSLSVAFJVQG-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- SGOVTJSOCUCZKH-UHFFFAOYSA-H [Zn+2].P(=O)([O-])([O-])[O-].[Zr+4].P(=O)([O-])([O-])[O-] Chemical compound [Zn+2].P(=O)([O-])([O-])[O-].[Zr+4].P(=O)([O-])([O-])[O-] SGOVTJSOCUCZKH-UHFFFAOYSA-H 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ULLASJXJTPGSFV-UHFFFAOYSA-H copper zirconium(4+) diphosphate Chemical compound P(=O)([O-])([O-])[O-].[Zr+4].[Cu+2].P(=O)([O-])([O-])[O-] ULLASJXJTPGSFV-UHFFFAOYSA-H 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- 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
-
- 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
- A01N59/20—Copper
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an inorganic antibacterial agent taking sodium zirconium phosphate as a carrier and a preparation method thereof, wherein the preparation method comprises the following steps: s1, mixing sodium dihydrogen phosphate and a template agent with water to obtain a solution A; dissolving zirconium oxychloride in water to obtain a solution B; s2, adding the solution A into the solution B, continuously and strongly stirring in the adding process, and adjusting the pH value of the mixed solution to 1-4 after the solution A is completely added into the solution B to obtain the solution C; s3, heating the solution C to 150-180 ℃ and preserving heat for 0.5-2 hours, cooling the solution C to 95-110 ℃ and stirring for reaction for more than or equal to 15 hours, and filtering, cleaning and drying after the reaction is finished to obtain sodium zirconium phosphate powder; the particle size of the sodium zirconium phosphate carrier prepared by the invention is distributed at 300-800 nm, and the sodium zirconium phosphate carrier has better antibacterial effect when being used for preparing antibacterial agents.
Description
Technical Field
The invention relates to the technical field of antibacterial agents, in particular to an inorganic antibacterial agent taking sodium zirconium phosphate as a carrier and a preparation method thereof.
Background
The inorganic antibacterial agent is a material with antibacterial property, which is obtained by mainly utilizing the antibacterial capability of metals such as silver, copper, zinc and the like, fixing metal ions on the surface or in pore channels of porous materials such as zeolite, silica gel, titanium oxide, zirconium phosphate and the like through physical adsorption, ion exchange and the like, and adding the metal ions into products, and has higher stability and safety, so that the inorganic antibacterial agent is widely applied to the fields of ceramics, glass, plastics, fibers and the like.
Sodium zirconium phosphate is superior to the carrier with larger specific surface area and surface charge density and is often used as silver ion, zinc ion and copper ion to prepare silver zirconium phosphate, zinc zirconium phosphate or copper zirconium phosphate antibacterial agent. In the sodium zirconium phosphate powder, the pore canal provides sufficient conditions for the contact of metal ions and bacteria, so that a better sterilization effect is achieved under the condition of using less antibacterial agent. The smaller the particle size of the antibacterial powder, the larger the specific surface area, and the better antibacterial effect will be exhibited if it is added to a polymer to prepare antibacterial articles such as antibacterial fabrics, antibacterial mats, antibacterial insoles, etc. at the same mass.
However, the particle size of sodium zirconium phosphate prepared by conventional methods is generally large. The range of the D50 of the sodium zirconium phosphate powder prepared by the Chinese patent application CN111498824A is 10-100 mu m; the average grain diameter of the sodium zirconium phosphate prepared by the Chinese patent application CN105401244A is 1-3 mu m; the granularity distribution of the sodium zirconium phosphate powder prepared by the Chinese patent application CN102180455A is concentrated between 1 and 10 mu m. The measurement result of the carrier particle size by a laser particle size analyzer in Chinese patent application CN102763678A is as follows: d50 is less than or equal to 1.0 mu m, and D90 is less than or equal to 2.0 mu m. The particle size test result of the antibacterial powder after silver loading is as follows: d50 is less than or equal to 1.5 mu m, and D90 is less than or equal to 2.5 mu m. Most products sold in domestic market are also over 1 mu m in size. Although nano-scale powder is prepared by the hydrothermal synthesis and characterization of the Chinese patent application CN102239887A and NaZr2 (P04) 3 crystal, the former needs an ultrafiltration process and complex equipment, and the latter adopts ammonium dihydrogen phosphate as a reaction reagent, ammonia gas is easy to generate in the production process, and the ammonium zirconium phosphate is easy to change color after silver is carried, so that the method is not beneficial to industrial production.
Therefore, the industrial production of nano-scale sodium zirconium phosphate and the antibacterial agent taking the nano-scale sodium zirconium phosphate as a carrier still have technical bottlenecks.
Disclosure of Invention
Therefore, the invention aims to solve the problems and provide an inorganic antibacterial agent taking sodium zirconium phosphate as a carrier and a preparation method thereof, and the nano-scale sodium zirconium phosphate carrier is prepared so as to realize better antibacterial effect.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a preparation method of a sodium zirconium phosphate powder material comprises the following preparation steps:
s1, mixing sodium dihydrogen phosphate and a template agent with water to obtain a solution A; dissolving zirconium oxychloride in water to obtain a solution B;
s2, adding the solution A into the solution B, continuously stirring in the adding process, and adjusting the pH value of the mixed solution to 1-4 after the solution A is completely added into the solution B to obtain the solution C;
s3, heating the C solution to 150-180 ℃ and preserving heat for 0.5-2 hours, cooling the C solution to 95-110 ℃ and stirring for reaction for more than or equal to 15 hours, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate powder.
In the scheme, sodium dihydrogen phosphate provides phosphate radical and sodium ion, zirconium oxychloride provides zirconium ion, a hydrothermal synthesis method is adopted to provide energy required by nucleation of sodium zirconium phosphate at high temperature and high pressure, a large number of crystal nuclei are rapidly formed, and then the crystal nuclei slowly grow up at lower temperature and normal pressure. The early nucleation number is large, and the later crystal nucleus growth period is long, so that the obtained sodium zirconium phosphate particles have smaller size and larger specific surface area.
Further, in S1, the mass portion of sodium dihydrogen phosphate is 5-15, the mass portion of the template agent is 1-10, and the mass portion of zirconium oxychloride is 3-8.
Further, the solution A and the solution B in the step S2 are respectively preheated to 50-85 ℃ before being mixed;
the purpose of preheating is to enable the raw materials to be fully dissolved in the solvent, so that the subsequent operation is convenient.
The solution A is added into the solution B in a dropwise adding mode, phosphate radical coordinates with zirconium ions to form zirconium phosphate under the action of a template agent, so that the dropwise adding rate of the solution A can influence the synthesis rate of sodium zirconium phosphate, and if the dropwise adding rate of the solution A is too fast, the formed crystal particle size is too large.
Preferably, the template agent comprises sodium oxalate, oxalic acid and sodium fluoride;
more preferably, the template agent comprises 1 to 5 parts by mass of sodium oxalate, 0.3 to 3 parts by mass of oxalic acid and 0.01 to 0.1 part by mass of sodium fluoride.
The invention also provides a sodium zirconium phosphate powder material which is prepared by the preparation method of the sodium zirconium phosphate powder material, and the average grain diameter of the sodium zirconium phosphate powder material is 300-800 nm.
The invention also provides a preparation method of the inorganic antibacterial agent taking the sodium zirconium phosphate as a carrier, wherein the sodium zirconium phosphate powder is taken as a raw material and is subjected to ion exchange with metal salt.
Further, dissolving the sodium zirconium phosphate powder into pure water to form a sodium zirconium phosphate solution, dissolving the metal salt into the pure water to obtain a solution D, adding the solution D into the sodium zirconium phosphate solution, stirring for 1-3 hours at 95-110 ℃, filtering, cleaning and drying after the reaction is finished to obtain the inorganic antibacterial agent taking the sodium zirconium phosphate as a carrier.
Further, the mass ratio of metal ions in the solution D:
m(Ag + )：m(Zn 2+ )：m(Cu 2+ ) Preparing a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate with the ratio of (100:0:0);
or, m (Ag) + )：m(Zn 2+ )：m(Cu 2+ ) Preparing a zirconium sodium phosphate zinc-loaded inorganic antibacterial agent in a ratio of (0:100:0);
or, m (Ag) + )：m(Zn 2+ )：m(Cu 2+ ) Preparing a sodium zirconium phosphate copper-loaded inorganic antibacterial agent in a ratio of (0:0:100);
or [ m (Ag) + )+m(Zn 2+ )]：m(Cu 2+ ) =100:0, and m (Ag + )：m(Zn 2+ ) =1 to 9: 9-1, preparing the silver/zinc loaded inorganic antibacterial agent of sodium zirconium phosphate;
or [ m (Ag) + )+m(Cn 2+ )]：m(Zn 2+ ) =100:0, and m (Ag + )：m(Cu 2+ ) =1 to 9: 9-1, preparing the silver/copper loaded inorganic antibacterial agent of sodium zirconium phosphate;
or [ m (Cu) 2+ )+m(Zn 2+ )]：m(Ag + ) =100:0, and m (Cu 2+ )：m(Zn 2+ ) =1 to 9: 9-1, preparing the sodium zirconium phosphate copper/zinc carrying inorganic antibacterial agent;
or, m (Ag) + )、m(Cu 2+ )、m(Zn 2+ )]The content is not zero, and the silver/copper/zinc loaded inorganic antibacterial agent of the sodium zirconium phosphate is prepared;
preferably, the silver salt is silver nitrate;
preferably, the zinc salt is zinc nitrate or zinc chloride;
preferably, the copper salt is copper nitrate or copper chloride.
The invention also provides an antibacterial composition, which comprises the inorganic antibacterial agent taking sodium zirconium phosphate as a carrier and 0.001-90 wt% of organic antibacterial agent;
preferably, the organic antibacterial agent is at least one of polyhexamethylene guanidine, polyhexamethylene biguanide, zinc pyrithione, acylaniline, imidazoles, thiazoles, isothiazolone derivatives, vanillin, ethyl vanillin and quaternary ammonium salts.
The invention also provides an application of the antibacterial composition, and 0.01-10wt% of the antibacterial composition is added into a product.
Further, the article includes a component of polymeric material, the antimicrobial composition being added to the polymer to form a hybrid material in a melt blending manner;
further, the article is a toy, medical device, film, tubing, profile, 3D printed article, sheet, coating, tape, strip, molding, pipe, foam, tape, fabric, thread, filament, ribbon, fiber, web, sealant, automotive interior trim, impregnated article, sheet molding, hot melt adhesive, tie layer, film, insole, yoga mat, floor mat, or training mat;
further, the article is formed by injection molding, overmolding, dipping, extrusion, rotomolding, slush molding, fiber spinning, film forming, 3D printing, or foaming.
The technical scheme provided by the invention has the following beneficial effects:
1. the particle size distribution of the sodium zirconium phosphate powder prepared by the preparation method of the sodium zirconium phosphate powder material is 300-800 nm, the technical obstruction of preparing nano sodium zirconium phosphate powder in the prior art is overcome, and the prepared sodium zirconium phosphate powder has larger specific surface area and better antibacterial effect when being used for preparing inorganic antibacterial agents by silver/zinc/copper.
2. Compared with the prior art, the ammonium ions are replaced by safer sodium ions, so that the prepared product is converted from zirconium ammonium phosphate to zirconium sodium phosphate, ammonia gas is avoided in the production process, the sodium ions are replaced by metal ions more easily, and the difficulty of subsequent exchange with the metal ions is reduced.
Drawings
FIG. 1 is an XRD pattern of sodium zirconium phosphate powder of example 1 of the present invention;
FIG. 2 is an XPS chart of experimental example 1 of the present invention;
FIG. 3 is an SEM image of a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate of example 5 of the present invention, the scale of the drawing being 200nm;
FIG. 4 is an SEM image of a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate of example 6 of the present invention, the scale of the drawing being; 200nm;
FIG. 5 is an SEM image of a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate of example 7 of the present invention, the scale of the drawing being 1 μm;
FIG. 6 is an SEM image of a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate of comparative example 1, the scale of the drawing being 1 μm;
FIG. 7 is an SEM image of a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate of comparative example 2, which is shown on a scale of 1. Mu.m;
FIG. 8 is an SEM image of a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate of comparative example 3, which is shown on a scale of 10. Mu.m.
Detailed Description
The invention will be described in further detail with reference to the drawings and the detailed description.
Example 1. A sodium zirconium phosphate powder material and its preparation method, the preparation method is as follows:
s1, dissolving 10 parts of sodium dihydrogen phosphate, 2 parts of sodium oxalate, 1 part of oxalic acid and 0.05 part of sodium fluoride in pure water according to parts by mass to obtain a solution A, and dissolving 8 parts of zirconium oxychloride in pure water to obtain a solution B;
s2, preheating the solution A and the solution B to 85 ℃ respectively, then adding the solution A into the solution B, continuously and strongly stirring in the adding process, and after the solution A is completely added into the solution B, regulating the pH value of the mixed solution to 2.5 by using a sodium hydroxide solution to obtain a solution C;
s3, transferring the C solution into a polytetrafluoroethylene reaction kettle, heating to 160 ℃, preserving heat for 2 hours, cooling the C solution to 95 ℃, stirring and reacting for 18 hours, and filtering, cleaning and drying after the reaction is finished to obtain the zirconium sodium phosphate powder with the average particle size of 300-800 nm.
Example 2. A sodium zirconium phosphate powder material and its preparation method, the preparation method is as follows:
s1, dissolving 12 parts of sodium dihydrogen phosphate, 2 parts of sodium oxalate, 3 parts of oxalic acid and 0.1 part of sodium fluoride in pure water according to parts by mass to obtain a solution A, and dissolving 7 parts of zirconium oxychloride in pure water to obtain a solution B;
s2, preheating the solution A and the solution B to 50 ℃, then adding the solution A into the solution B, continuously and strongly stirring in the adding process, and after the solution A is completely added into the solution B, regulating the pH value of the mixed solution to 1.5 by using a sodium hydroxide solution to obtain a solution C;
and S3, heating the solution C to 150 ℃, preserving heat for 1 hour, cooling the solution C to 100 ℃, stirring and reacting for 15 hours, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate powder with the average particle size of about 300-800 nm.
Example 3. A sodium zirconium phosphate powder material and its preparation method, the preparation method is as follows:
s1, 8 parts of sodium dihydrogen phosphate, 3 parts of sodium oxalate, 1 part of oxalic acid and 0.03 part of sodium fluoride are dissolved in pure water according to parts by mass to obtain a solution A, and 8 parts of zirconium oxychloride is dissolved in pure water to obtain a solution B;
s2, preheating the solution A and the solution B to 70 ℃ respectively, then adding the solution A into the solution B, continuously and strongly stirring in the adding process, and after the solution A is completely added into the solution B, regulating the pH value of the mixed solution to 2 by using a sodium hydroxide solution to obtain a solution C;
s3, heating the solution C to 180 ℃ and preserving heat for 1.5 hours, cooling the solution C to 110 ℃ and stirring for reaction for 16 hours, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate powder with the average particle size of about 300-800 nm.
Example 4. A sodium zirconium phosphate powder material and its preparation method, the preparation method is as follows:
s1, dissolving 5 parts of sodium dihydrogen phosphate, 5 parts of sodium oxalate, 0.3 part of oxalic acid and 0.05 part of sodium fluoride in pure water according to parts by mass to obtain a solution A, and dissolving 3 parts of zirconium oxychloride in the pure water to obtain a solution B;
s2, preheating the solution A and the solution B to 50 ℃, then adding the solution A into the solution B, continuously and strongly stirring in the adding process, and after the solution A is completely added into the solution B, regulating the pH value of the mixed solution to 1.5 by using a sodium hydroxide solution to obtain a solution C;
and S3, heating the solution C to 150 ℃, preserving heat for 1 hour, cooling the solution C to 100 ℃, stirring and reacting for 15 hours, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate powder with the average particle size of about 300-800 nm.
Example 5A sodium zirconium phosphate silver-loaded inorganic antibacterial agent and method of preparing the same
S1, preparing a solution A and a solution B in the same manner as in example 1, and dissolving 6 parts of silver nitrate in pure water to obtain a solution D;
s2 and C solutions are prepared in the same way as in the embodiment 1;
s3, transferring the solution C into a polytetrafluoroethylene reaction kettle, heating to 160 ℃, preserving heat for 2 hours, cooling the solution C to 95 ℃, stirring and reacting for 18 hours, adding the solution D, continuously stirring for 2 hours at 100 ℃, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate silver-loaded inorganic antibacterial agent.
Example 6A silver and Zinc loaded sodium zirconium phosphate inorganic antibacterial agent and method for preparing same
S1, preparing a solution A and a solution B in the same way as in the example 2, and dissolving 4 parts of silver nitrate and 2 parts of zinc nitrate in pure water to obtain a solution D;
s2 and C solutions are prepared in the same way as in the embodiment 2;
s3, transferring the solution C into a polytetrafluoroethylene reaction kettle, heating to 150 ℃, preserving heat for 1 hour, cooling the solution C to 100 ℃, stirring and reacting for 15 hours, adding the solution D, continuously stirring for 3 hours at 100 ℃, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate silver-carrying and zinc-carrying inorganic antibacterial agent.
Example 7 sodium zirconium phosphate copper-loaded inorganic antibacterial agent and method for preparing same
S1, preparing a solution A and a solution B in the same way as in the example 3, and dissolving 8 parts of copper nitrate in pure water to obtain a solution D;
s2 and C solutions are prepared in the same way as in example 3;
s3, transferring the solution C into a polytetrafluoroethylene reaction kettle, heating to 180 ℃, preserving heat for 1.5 hours, cooling the solution C to 110 ℃, stirring and reacting for 16 hours, adding the solution D, continuously stirring for 1 hour at 110 ℃, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate copper-carrying inorganic antibacterial agent.
Comparative example 1. Silver-loaded sodium zirconium phosphate inorganic antibacterial agent and method for preparing same
Unlike example 5, the C solution in S3 is kept at 95 ℃ for 10 hours, and after the reaction is finished, the sodium zirconium phosphate silver-loaded inorganic antibacterial agent is obtained after filtration, cleaning and drying.
Comparative example 2A silver-loaded sodium zirconium phosphate inorganic antibacterial agent and method for preparing same
Different from example 5, S3, the prepared solution C is directly transferred into a water bath kettle, stirred and reacted for 18 hours at 95 ℃, solution D is added and continuously stirred for 2 hours at 100 ℃, and after the reaction is finished, the silver-loaded inorganic silver zirconium phosphate antibacterial agent is obtained after filtering, cleaning and drying.
Comparative example 3A silver-loaded sodium zirconium phosphate inorganic antibacterial agent and method for preparing same
Unlike example 5, S1, 10 parts by mass of sodium dihydrogen phosphate was dissolved in pure water to obtain a solution A, and 8 parts by mass of zirconium oxychloride was dissolved in pure water to obtain a solution B;
characterization of results and performance testing
1. Phase analysis
The results of phase analysis and crystal structure determination (XRD experimental parameters: angle: 10 to 80 test speed: 10/min) of the sample obtained in example 1 using an X-ray Diffraction (XRD) apparatus of Japanese electric product LX-57b are shown in FIG. 1, which shows that the sodium zirconium phosphate powder prepared in example 1 matches with the sodium zirconium phosphate standard chart card.
2. Elemental analysis
The sample obtained in example 5 was subjected to elemental analysis using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer, and the results are shown in FIG. 2: in addition to the main constituent elements of sodium zirconium phosphate and some impurities, ag 3d peaks appear at 365.8eV and 371.9eV, indicating the presence of elemental silver.
3. Particle size measurement
The particle size of the crystals was characterized using a bruexploiting 90Plus Zeta high sensitivity particle size analyzer.
The particle size testing method comprises the following steps: 0.0490g of the sample obtained in example 1 was dispersed in 10mL of ethanol, and after 4 hours of sonication, 2mL of the mixed solution was taken out of the cuvette and placed in the instrument, and the particle size was measured using dynamic light scattering. The test methods of examples 2 and 3 were identical.
The particle size distribution of the samples obtained in examples 1, 2 and 3 is shown in Table 1.
TABLE 1
| Sample of | Example 1 | Example 2 | Example 3 |
| D50 | <480nm | <580nm | <500nm |
| D90 | <650nm | <750nm | <720nm |
As is clear from Table 1, the particle size of the sodium zirconium phosphate powder material obtained by the method is 300-800 nm.
4. Microscopic topography analysis
The microscopic morphologies of the samples obtained in examples 5, 6, 7 and comparative examples 1, 2, 3 were analyzed by using a Sigma 500 06-16 Scanning Electron Microscope (SEM), and the results are shown in fig. 3 to 8.
The light cubes in figures 3, 4 and 5 are zirconium sodium phosphate crystals, and it is obvious from three figures that the silver-loaded inorganic antibacterial agent powder of zirconium sodium phosphate prepared by the technical scheme of the invention has the advantages of uniform dispersion, less impurities, regular structure and uniform particle size distribution between 300 and 800nm. In fig. 6, it can be seen that, due to insufficient reaction time, only part of crystal nuclei grow into cubes, the prepared silver-loaded inorganic antibacterial powder of sodium zirconium phosphate has the phenomena of uneven dispersion, easy agglomeration, incomplete formation of cubes and the like, while the sodium zirconium phosphate powder prepared in fig. 7 lacks the process of rapid nucleation at high temperature and high pressure, so that a large amount of substances which are not crystallized show the shape of floccules and are amorphous substances. The silver-loaded inorganic antibacterial agent powder of sodium zirconium phosphate prepared in fig. 8 shows crystals of different shapes, which indicates that the cubic structure cannot be controlled without the template.
5. Test of resistance to discoloration
The samples obtained in examples 5, 6, 7 and comparative examples 1, 2, 3 were irradiated with ultraviolet lamps for 24 hours. The results show that the samples obtained in examples 5, 6 and 7 have no obvious discoloration, and the samples in comparative examples 1, 2 and 3 have different degrees of blackening, so that the inorganic antibacterial agent prepared by the technical scheme of the invention and taking sodium zirconium phosphate as a carrier has better discoloration resistance. Silver plays a role in sterilization in the silver-loaded inorganic silver-zirconium phosphate, and after silver is oxidized to form black silver oxide, the silver-loaded inorganic silver-zirconium phosphate has no antibacterial function, so that the color change resistance is closely related to the sterilization effect of the silver-loaded inorganic silver-zirconium phosphate.
6. Sterilization test
Experiments were performed with reference to national standard GB/T31402-2015, staphylococcus aureus (ATCC 25922) was selected as a test strain, and the samples obtained in examples 5, 6 and 7 and comparative examples 1, 2 and 3 were tested, and the results are shown in Table 2:
TABLE 2
As can be seen from Table 2, the inorganic antibacterial agent prepared by the technical scheme of the invention and taking sodium zirconium phosphate as a carrier has a good sterilization effect.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. The preparation method of the sodium zirconium phosphate powder material is characterized by comprising the following preparation steps:
s1, mixing sodium dihydrogen phosphate and a template agent with water to obtain a solution A; dissolving zirconium oxychloride in water to obtain a solution B;
s2, adding the solution A into the solution B, continuously stirring in the adding process, and adjusting the pH value of the mixed solution to 1-4 after the solution A is completely added into the solution B to obtain the solution C;
s3, heating the C solution to 150-180 ℃ and preserving heat for 0.5-2 hours, cooling the C solution to 95-110 ℃ and stirring for reaction for more than or equal to 15 hours, and filtering, cleaning and drying after the reaction is finished to obtain the sodium zirconium phosphate powder.
2. The method for preparing the sodium zirconium phosphate powder material according to claim 1, which is characterized in that: in the S1, the mass part of sodium dihydrogen phosphate is 5-15, the mass part of the template agent is 1-10, and the mass part of zirconium oxychloride is 3-8.
3. The method for preparing the sodium zirconium phosphate powder material according to claim 1, which is characterized in that: the solution A and the solution B in the S2 are respectively preheated to 50-85 ℃ before being mixed; the template agent comprises, by mass, 1-5 parts of sodium oxalate, 0.3-3 parts of oxalic acid and 0.01-0.1 part of sodium fluoride.
4. A sodium zirconium phosphate powder material is characterized in that: a method for producing a sodium zirconium phosphate powder material according to any one of claims 1 to 3, wherein the average particle diameter of the sodium zirconium phosphate powder material is 300 to 800nm.
5. A preparation method of an inorganic antibacterial agent with sodium zirconium phosphate as a carrier is characterized by comprising the following steps: ion-exchanging with the metal salt by using the sodium zirconium phosphate powder as a raw material.
6. The method for preparing the inorganic antibacterial agent with the sodium zirconium phosphate as a carrier according to claim 5, which is characterized in that: dissolving sodium zirconium phosphate powder in pure water to form sodium zirconium phosphate solution, dissolving metal salt in the pure water to obtain solution D, adding the solution D into the sodium zirconium phosphate solution, stirring for 1-3 hours at 95-110 ℃, filtering, cleaning and drying after the reaction is finished to obtain the inorganic antibacterial agent taking sodium zirconium phosphate as a carrier.
7. The method for preparing the inorganic antibacterial agent with the sodium zirconium phosphate as a carrier according to claim 6, wherein the mass ratio of metal ions in the solution D is as follows:
m(Ag + )：m(Zn 2+ )：m(Cu 2+ ) Preparing a silver-loaded inorganic antibacterial agent of sodium zirconium phosphate with the ratio of (100:0:0);
or, m (Ag) + )：m(Zn 2+ )：m(Cu 2+ ) Preparing a zirconium sodium phosphate zinc-loaded inorganic antibacterial agent in a ratio of (0:100:0);
or, m (Ag) + )：m(Zn 2+ )：m(Cu 2+ ) Preparing a sodium zirconium phosphate copper-loaded inorganic antibacterial agent in a ratio of (0:0:100);
or [ m (Ag) + )+m(Zn 2+ )]：m(Cu 2+ ) =100:0, and m (Ag + )：m(Zn 2+ ) =1 to 9: 9-1, preparing the silver/zinc loaded inorganic antibacterial agent of sodium zirconium phosphate;
or [ m (Ag) + )+m(Cn 2+ )]：m(Zn 2+ ) =100:0, and m (Ag + )：m(Cu 2+ ) =1 to 9: 9-1, preparing the silver/copper loaded inorganic antibacterial agent of sodium zirconium phosphate;
or [ m (Cu) 2+ )+m(Zn 2+ )]：m(Ag + ) =100:0, and m (Cu 2+ )：m(Zn 2+ ) =1 to 9: 9-1, preparing the sodium zirconium phosphate copper/zinc carrying inorganic antibacterial agent;
or, m (Ag) + )、m(Cu 2+ )、m(Zn 2+ )]Is not zero, and the silver/copper/zinc loaded inorganic antibacterial agent of the zirconium sodium phosphate is prepared.
8. The method for preparing an inorganic antibacterial agent with sodium zirconium phosphate as a carrier according to claim 7, wherein the solution D comprises Ag + When the Ag is + Is obtained by dissolving silver nitrate in pure water.
9. The method for preparing an inorganic antibacterial agent with sodium zirconium phosphate as a carrier according to claim 7, wherein the solution D comprises Zn 2+ When in use, the Zn 2+ Is obtained by dissolving zinc nitrate or zinc chloride in pure water.
10. The method for preparing an inorganic antibacterial agent with sodium zirconium phosphate as a carrier according to claim 7, wherein the solution D contains Cu 2+ When the Cu is 2+ Is obtained by dissolving copper nitrate or copper chloride in pure water.
11. An antimicrobial composition characterized by: comprising the inorganic antibacterial agent produced by the method for producing an inorganic antibacterial agent on a carrier of sodium zirconium phosphate according to any one of claims 5 to 10 and 0.001 to 90wt% of an organic antibacterial agent; the organic antibacterial agent is at least one of polyhexamethylene guanidine, polyhexamethylene biguanide, zinc pyrithione, acylaniline, imidazoles, thiazoles, isothiazolone derivatives, vanillin, ethyl vanillin and quaternary ammonium salts.
12. Use of an antimicrobial composition characterized by: an antimicrobial composition according to claim 11 is added to the article in an amount of 0.01 to 10 wt%.
13. Use of an antimicrobial composition according to claim 12, characterized in that: the article includes a polymeric component, and the antimicrobial composition is added to the polymer to form a hybrid material in a melt blending manner.
14. Use of an antimicrobial composition according to claim 13, characterized in that: the article is a toy, medical device, film, tubing, profile, 3D printed article, sheet, coating, tape, strip, molding, tube, foam, tape, fabric, thread, filament, ribbon, fiber, web, sealant, automotive interior trim, impregnated article, sheet molded article, hot melt adhesive, tie layer, film, insole, yoga mat, floor mat, or training mat.
15. Use of an antimicrobial composition according to claim 13, characterized in that: the article is formed by injection molding, overmolding, dipping, extrusion, rotomolding, slush molding, fiber spinning, film forming, 3D printing, or foaming.
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| CN114873572A (en) | 2022-08-09 |
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