CN115024315A - Synthetic method of antibacterial nano hydrosol - Google Patents
Synthetic method of antibacterial nano hydrosol Download PDFInfo
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- CN115024315A CN115024315A CN202210430934.3A CN202210430934A CN115024315A CN 115024315 A CN115024315 A CN 115024315A CN 202210430934 A CN202210430934 A CN 202210430934A CN 115024315 A CN115024315 A CN 115024315A
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- chitosan
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title description 2
- 229920001661 Chitosan Polymers 0.000 claims abstract description 91
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010936 titanium Substances 0.000 claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 35
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000004332 silver Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000002978 peroxides Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 49
- 239000002244 precipitate Substances 0.000 claims description 36
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 13
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 13
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 13
- 101710134784 Agnoprotein Proteins 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 11
- 239000012467 final product Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004887 air purification Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000700605 Viruses Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
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- 230000009982 effect on human Effects 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
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- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 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
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- 238000004627 transmission electron microscopy Methods 0.000 description 1
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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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- 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
- A01N25/10—Macromolecular compounds
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- 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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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention discloses a method for synthesizing aqueous antibacterial nano sol, which comprises the following steps: 1) preparing water-soluble peroxide chitosan; 2) preparing a chitosan-titanium compound; and 3) preparing the chitosan-titanium dioxide-silver nano hydrosol. Compared with the preparation method reported in the literature, the method adopts chitosan with a specific molecular weight as a carrier, uses hydrogen peroxide as an oxidant, and loads titanium dioxide and silver to form the photo-thermal synergistic antibacterial chitosan-titanium dioxide-silver composite hydrosol nano material with enhanced adsorption.
Description
Technical Field
The invention relates to the field of engineering nano material manufacturing, in particular to a synthesis method of a nano antibacterial water-soluble adhesive material.
Background
Harmful bacteria and viruses in the air are ubiquitous, and in recent years, epidemic situations caused by various bacteria, viruses and the like frequently occur. Seasonal influenza causes 29.1 to 64.6 million people to die every year, and how to safely and effectively disinfect and purify air in hospitals is always a great concern. At present, in the traditional ultraviolet lamp and ozone disinfection method, the common ultraviolet lamp or chemical disinfectant spray disinfection belongs to a static disinfection method, and personnel must leave in the use process because of certain toxic and side effects on human bodies. Therefore, only the microorganisms in the air of the room before work can be eliminated, and the bacterial colony number of bacteria in the air of the room rises due to the activity of people entering the room after disinfection, so that the air is polluted again, and the air disinfection effect is only temporary.
The photocatalytic material can utilize light energy to generate antibacterial and odor-removing functions, has no toxic or side effect on human bodies, and is suitable for air purification and disinfection materials and equipment used in a dynamic environment. However, the photocatalytic material has two defects, namely, the photocatalytic material can only absorb ultraviolet band spectrum and only accounts for 5% of the total energy of solar energy. Secondly, the adsorption capacity is weak, and the mass transfer process for degrading low-concentration pollutants is limited. Therefore, the development of the adsorption enhanced nano photocatalytic material system has important significance.
For example, CN102583634B discloses a nano silver-doped titanium dioxide/chitosan composite microsphere as a water purifying agent for removing phenol in water, which is prepared by first preparing silver-doped titanium dioxide powder through a hydrothermal reaction, then mixing with chitosan, and then performing the hydrothermal reaction to obtain the silver and titanium dioxide loaded chitosan composite powder. CN104725955B discloses a preparation method of a composite silver-loaded chitosan aqueous gloss oil, which comprises (1) mixing chitosan and silver salt, adding acid for treatment, reacting in a dark water bath, then reducing with sodium borohydride and the like to obtain silver-loaded chitosan, and then mixing the silver-loaded chitosan with various auxiliaries to obtain an aqueous gloss oil product.
In the prior art, in order to obtain related materials, methods such as hydrothermal treatment and the like are often adopted for treatment, the energy consumption is high, meanwhile, deep research on chitosan is not carried out, the obtained product is mostly used for degradation catalysis, and the chitosan and a photocatalytic material are compounded to obtain a product capable of realizing a photocatalytic antibacterial effect, which is not reported.
Disclosure of Invention
According to an aspect of the present invention, it is an object of the present invention to provide a method for manufacturing an antibacterial nanoaquasol material that can have adsorption enhancement.
In order to achieve the above objects of the present invention, the method for preparing the antibacterial nano water-soluble adhesive material according to the present invention comprises the steps of:
1) preparation of water-soluble peroxide chitosan
Adding chitosan into solvent, stirring, and adding 30% H 2 O 2 Uniformly stirring the solution, controlling the temperature not to exceed 50 ℃, and stirring for reacting for 4 hours to obtain a water-soluble peroxide chitosan aqueous solution, wherein the molecular weight of the chitosan is 85kDa to 110kDa, and the mass ratio of hydrogen peroxide to chitosan is 5:1 to 10: 1;
2) preparation of chitosan-titanium composite
Adding an inorganic base or an organic acid to the Ti-containing solution 4+ Adjusting the pH value of the solution to 5-11 in titanium salt precursor aqueous solution with the ion concentration of 0.01-0.50 mol/L to obtain orthotitanic acid precipitate, removing impurities from the obtained precipitate through a purification process, then slowly adding the orthotitanic acid precipitate into the water-soluble peroxide chitosan aqueous solution obtained in the step 1), after the addition is finished, uniformly stirring, controlling the water temperature to be not more than 50 ℃, and stirring for reaction for 4 hours to obtain a chitosan-titanium compound aqueous solution, wherein the mass ratio of titanium to chitosan is 0.5: 1-2: 1;
3) preparation of chitosan-titanium dioxide-silver nano hydrosol
Adding AgNO with the molar concentration of 0.01mol/L into the aqueous solution system of the chitosan-titanium compound obtained in the step 2) 3 Aqueous solution, controlThe molar concentration ratio of Ti to Ag is 10:1 to 0.2:1, and then 20mW/cm 2 And reacting for 30-60 min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
Preferably, the chitosan in step 1) has a molecular weight of 87kDa to 95kDa, more preferably 87kDa to 93 kDa.
Preferably, the solvent in step 1) is selected from one or more of deionized water, methanol, ethanol and propanol, preferably deionized water.
Preferably, the mass ratio of hydrogen peroxide to chitosan in step 1) is from 7:1 to 8:1, more preferably from 7.4:1 to 7.6: 1.
Preferably, the mass ratio of titanium to chitosan in step 2) is from 1:1 to 1.5:1, more preferably from 1.2:1 to 1.3: 1.
Preferably, the titanium salt precursor in step 2) is selected from one or more of titanium tetrachloride, titanyl sulfate, titanium tetrafluoride, titanium nitrate, titanium hydroxide, titanium carbonate and titanium tetrabromide, and more preferably titanium tetrachloride, titanyl sulfate or titanium tetrafluoride.
Preferably, the inorganic base in step 2) is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water, preferably ammonia water; the organic acid may be selected from one or more of acetic acid, citric acid, oxalic acid, succinic acid, malic acid, tartaric acid, etc.
Preferably, the molar concentration ratio of Ti and Ag in step 3) is controlled to be 2:1 to 0.5:1, more preferably 1.5:1 to 1: 1.
Preferably, the manufacturing method according to the present invention is performed as follows:
adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 25ml of solution, controlling the mass ratio of hydrogen peroxide to chitosan to be 7.5:1, controlling the water temperature not to exceed 50 ℃, and stirring for reaction for 4 hours;
dissolving 100g of titanyl sulfate in 500ml of deionized water to obtain a titanyl sulfate aqueous solution; titrating a titanyl sulfate solution by using ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing the precipitate for 3 times by using deionized water to obtain an orthotitanic acid precipitate;
adding 15g of the prepared titanium hydroxide precipitate into the chitosan peroxide solution, dissolving to obtain a transparent solution, and adding AgNO with the molar concentration of 0.01mol/L 3 10ml of the aqueous solution, and stirring the mixed solution at 20mW/cm 2 And reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
Alternatively, preferably, the manufacturing method according to the present invention is performed as follows:
adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 15ml of solution, controlling the mass ratio of hydrogen peroxide to chitosan to be 5:1, controlling the water temperature not to exceed 50 ℃, and stirring for reaction for 4 hours;
firstly, dissolving 10g of titanium tetrachloride by using 500ml of deionized water to obtain a titanium chloride aqueous solution; titrating the titanium chloride solution by ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing the precipitate for 3 times by deionized water to obtain orthotitanic acid;
5g of the prepared titanium hydroxide precipitate is added into the chitosan peroxide solution and dissolved to obtain a transparent solution. Then AgNO with the molar concentration of 0.01mol/L is added 3 5ml of aqueous solution, and mixing the solution at 20mW/cm 2 And (3) reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
Preferably, the manufacturing method according to the present invention is performed as follows:
adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 35ml of solution, controlling the mass ratio of hydrogen peroxide to chitosan to be 10:1, controlling the water temperature not to exceed 50 ℃, and stirring for reaction for 4 hours;
firstly, dissolving 10g of titanium tetrafluoride by using 500ml of deionized water to obtain a titanium fluoride aqueous solution; titrating the titanium fluoride solution with ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing with deionized water for 3 times to obtain orthotitanic acid;
adding 25g of prepared titanium hydroxide precipitate into the chitosan peroxide solution, and dissolving to obtain a transparent solution. Then AgNO with the molar concentration of 0.01mol/L is added 3 5ml of aqueous solution, and mixing the solution at 20mW/cm 2 And (3) reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
According to one aspect of the present invention, it is another object of the present invention to provide the antibacterial nano hydrosol material prepared according to the method for manufacturing the antibacterial nano hydrosol material of the present invention.
According to one aspect of the invention, the invention further aims to provide the application of the antibacterial nano hydrosol material in the aspect of building exterior wall coating.
According to one aspect of the present invention, another object of the present invention is to provide an exterior wall coating material for buildings, which comprises the antibacterial nano water soluble glue material according to the present invention and an auxiliary material selected from, but not limited to, a defoaming agent, a leveling agent, an aqueous coating emulsion, a coloring agent, etc.
Advantageous effects
Compared with the preparation method reported in the literature, the method adopts chitosan with a specific molecular weight as a carrier, uses hydrogen peroxide as an oxidant, and loads titanium dioxide and silver to form the photo-thermal synergistic antibacterial chitosan-titanium dioxide-silver composite hydrosol nano material with enhanced adsorption.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows the results of elemental analysis of the sol obtained in example 1;
FIG. 2 shows the results of transmission electron microscopy of the sol obtained in example 1.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of a range of values or percentages should be considered to cover and specifically disclose all possible subranges and individual values within the range, particularly integer values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the precision of the number of significant digits of the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to encompass a range from 39.50 to 40.49.
The chitosan is a natural high molecular compound with rich content, has the characteristics of antibacterial and bacteriostatic properties, adsorbability, no toxicity, no stimulation, low price and the like, and is widely applied. The invention uses hydrogen peroxide to carry out peroxidation treatment on chitosan, effectively improves the water solubility of chitosan, can further form coordinate bonds with Ti ions by peroxide bonds connected on chitosan molecules, strengthens the combination of Ti ions, and finally can form an effective insulator-semiconductor-conductor composite structure between chitosan-titanium dioxide-silver by adopting an Ag ion induced photochemical synthesis process, and generates a photo-thermal synergistic effect by a plasma effect.
Specifically, the chitosan used in step 1) of the method for preparing an antibacterial nano-sized water-gel material according to the present invention has a molecular weight of 85kDa to 110kDa, preferably 87kDa to 95kDa, more preferably 87kDa to 93kDa, such as 85kDa, 86kDa, 87kDa, 88kDa, 89kDa, 90kDa, 91kDa, 92kDa, 93kDa, 94kDa, 95kDa, 96kDa, 97kDa, 98kDa, 99kDa, 100kDa, 102kDa, 104kDa, 106kDa, 108kDa, 110kDa, and the inventors found that, if the molecular weight of chitosan is less than 85kDa, the cleavage of chitosan molecules easily occurs in the reaction with hydrogen peroxide, the small molecular weight of chitosan contributes to the improvement of water solubility, but the unavoidable problem is that the influence of external environmental conditions during later use is significant, such as the discoloration easily occurs in long-term sunlight irradiation, and when used in mixture with other photocatalysts or thermocatalysts, the excessively small chitosan molecules are also easily decomposed by the catalyst, and thus the molecular weight of chitosan in the preparation method according to the present invention cannot be lower than 85kDa, preferably not lower than 87 kDa; if the molecular weight of the chitosan is larger than 110kDa, the water solubility of the chitosan is low, and at the relatively low temperature of the invention, the trans-form time is too long, and meanwhile, the reaction time with hydrogen peroxide is too long, which may cause that the part of the chitosan macromolecules is over-oxidized (contains a large amount of peroxide bonds), so that the catalytic performance of the final product prepared at the later stage is not uniform enough.
In addition, the mass ratio of hydrogen peroxide to chitosan in step 1) is controlled to be 5:1 to 10:1, preferably 7:1 to 8:1, more preferably 7.4:1 to 7.6:1, such as 7.1:1, 7.2:1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8: 1. When the mass ratio of the hydrogen peroxide to the chitosan is less than 5, the oxidation of the high molecular weight chitosan cannot be completed to obtain the chitosan with sufficiently improved water solubility; when the mass ratio of hydrogen peroxide to chitosan is greater than 10:1, excess H 2 O 2 Free outside the chitosan substrate, so that the titanium hydroxide in the next step forms core in a heterogeneous mode, and a titanium oxide chitosan compound cannot be formed.
Preferably, the mass ratio of titanium hydroxide to chitosan in step 2) is controlled to be 0.5:1 to 2:1, preferably 1:1 to 1.5:1, more preferably 1.2:1 to 1.3:1, such as 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0: 1. When the mass ratio of the titanium hydroxide to the chitosan is less than 0.5:1, namely the titanium content is insufficient, the photocatalytic function of the final product is insufficient; when the mass ratio of the titanium hydroxide to the chitosan is more than 2:1, namely the content of the chitosan is insufficient, hydrogen peroxide enriched in the chitosan cannot be fully utilized to dissolve orthotitanic acid precipitate, and the nano titanium oxide cannot be obtained in the next photochemical step.
Preferably, the molar concentration ratio of Ti and Ag in step 3) is controlled to 10:1 to 0.2:1, preferably 2:1 to 0.5:1, more preferably 1.5:1 to 1:1, if the molar concentration ratio of Ti and Ag is more than 2:1, i.e., the content of titanium is too large, the crystallization of light-induced Ag ions is insufficient, and if the molar concentration ratio of Ti and Ag is less than 0.5:1, i.e., the content of titanium is too small, the antibacterial effect under the same light irradiation conditions is insufficient. In addition, in the step 3), Ti is also required to be controlled, wherein Ag is crystallized in a photochemical reaction mode, Ag ions are crystallized on the surface of the nano titanium oxide through light induction to form an insulator-semiconductor-conductor composite structure, so that a photo-thermal synergistic catalysis effect is generated through a plasma effect, and if a crystallization product is obtained in a heating mode, a heterogeneous nucleation phenomenon is easy to occur, and an insulator-semiconductor-conductor composite structure with effective electronic recombination cannot be formed.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
Adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 25ml of solution, controlling the mass ratio of hydrogen peroxide to chitosan to be 7.5:1, controlling the water temperature not to exceed 50 ℃, and stirring for reaction for 4 hours.
Dissolving 100g of titanyl sulfate in 500ml of deionized water to obtain a titanyl sulfate aqueous solution; titrating the titanyl sulfate solution by ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing the precipitate for 3 times by deionized water to obtain orthotitanic acid precipitate.
Taking 15g of prepared titanium hydroxide precipitate, adding the titanium hydroxide precipitate into the chitosan peroxide solution, and dissolving to obtain the chitosan peroxideAdding AgNO with the molar concentration of 0.01mol/L into the transparent solution 3 10ml of the aqueous solution, and stirring the mixed solution at 20mW/cm 2 And reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
Fig. 1 is the results of elemental analysis of the sol obtained in this example, and it can be seen from the results of elemental analysis that the main component of the sol is chitosan-titania composite material.
Fig. 2 is a transmission electron microscope result of the sol obtained in this example, and it can be confirmed from the transmission electron microscope result that the chitosan-titania composite in the sol contains nano silver, and the obtained chitosan-titania-silver composite material is confirmed.
Example 2
Adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 15ml of solution, controlling the mass ratio of hydrogen peroxide to chitosan to be 5:1, controlling the water temperature not to exceed 50 ℃, and stirring for reaction for 4 hours.
Firstly, dissolving 10g of titanium tetrachloride by using 500ml of deionized water to obtain a titanium chloride aqueous solution; titrating the titanium chloride solution by ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing the precipitate for 3 times by deionized water to obtain orthotitanic acid.
5g of the prepared titanium hydroxide precipitate is added into the chitosan peroxide solution and dissolved to obtain a transparent solution. Then AgNO with the molar concentration of 0.01mol/L is added 3 5ml of aqueous solution, and mixing the solution at 20mW/cm 2 And reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
Example 3
Adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 35ml of solution, controlling the mass ratio of hydrogen peroxide to chitosan to be 10:1, controlling the water temperature not to exceed 50 ℃, and stirring for reaction for 4 hours.
Firstly, dissolving 10g of titanium tetrafluoride by using 500ml of deionized water to obtain a titanium fluoride aqueous solution; titrating the titanium fluoride solution by ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing the precipitate for 3 times by deionized water to obtain orthotitanic acid.
And (3) adding 25g of prepared titanium hydroxide precipitate into the chitosan peroxide solution, and dissolving to obtain a transparent solution. Then AgNO with the molar concentration of 0.01mol/L is added 3 5ml of aqueous solution, and mixing the solution at 20mW/cm 2 And reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
Comparative example 1
A composite material was prepared in the same manner as in example 1, except that the mass ratio of hydrogen peroxide to chitosan was controlled to be less than 5 (i.e., chitosan excess). The preparation process can not dissolve the titanium hydroxide to obtain the nano titanium oxide crystal, and the purification function of the final product is insufficient.
Comparative example 2
Except that the mass ratio of the titanium peroxide to the chitosan was controlled to be more than 10 (i.e., hydrogen peroxide was excessive), the composite material was prepared in the same manner as in example 2, the titanium dioxide was nucleated out of phase during the preparation process, and the purification function of the final product was insufficient.
Comparative example 3
A composite material was prepared in the same manner as in example 2, except that the mass ratio of the titanium hydroxide to the chitosan was controlled to be less than 0.5. TiO in the obtained product 2 The concentration is too low, and the purification function of the final product is insufficient.
Comparative example 4
A composite material was prepared in the same manner as in example 2, except that the mass ratio of the titanium hydroxide to the chitosan was controlled to be more than 2. Titanium hydroxide can not be completely dissolved, and TiO in the obtained product 2 The crystallization performance is not good, and the purification function of the final product is not sufficient.
Comparative example 5
A composite material was prepared in the same manner as in example 3, except that the final product was crystallized by reacting in an oven at 150 degrees for 2 hours instead of the uv reaction for 30 minutes. TiO in the obtained product 2 The crystallization performance is not good, and the purification function of the final product is not sufficient.
Comparative example 6
A composite material was prepared in the same manner as in example 2, except that chitosan having a molecular weight of 75kDa was used, and the prepared product became noticeably brown after standing for 7 days, while the purification function of the final product was insufficient.
Comparative example 7
Except for using chitosan having a molecular weight of 150kDa, the composite material was prepared in the same manner as in example 2, and a hydrosol product could not be obtained, and the antibacterial effect of the prepared product was not satisfactory.
Test example 1
The polymer foams prepared in examples 1 to 3 and comparative examples 1 to 7 were respectively tested for antibacterial rate according to evaluation of antibacterial performance of GB/T23763-2009 photocatalytic antibacterial materials and articles, and the results are shown in table 1 below.
Table 1: characterization of antibacterial property of chitosan-titanium dioxide-silver material
| Example numbering | Inactivation rate of Escherichia coli |
| Example 1 | 99％ |
| Example 2 | 99％ |
| Example 3 | 99％ |
| Comparative example 1 | 10％ |
| Comparative example 2 | 20％ |
| Comparative example 3 | 21％ |
| Comparative example 4 | 23％ |
| Comparative example 5 | 15％ |
| Comparative example 6 | 37％ |
| Comparative example 7 | 14％ |
As can be seen from the data in Table 1, the antibacterial rate of the chitosan-titanium dioxide-silver material prepared by the preparation method of the invention is more than 99.9%, so that the chitosan-titanium dioxide-silver material prepared by the preparation method of the invention can effectively resist bacteria and has wide application prospect.
Test example 2
The chitosan-titania-silver materials prepared in examples 1 to 3 and comparative examples 1 to 7 were measured for air purification performance according to JC/T1074-2008 standard, and the results are shown in table 2 below.
Table 2: characterization of air purification performance of chitosan-titanium dioxide-silver material
As can be seen from the data of table 2, the chitosan-titania-silver material prepared according to the preparation method of the present invention has good air-purifying performance, whereas the chitosan-titania-silver material obtained in the comparative example has less than ideal air-purifying performance.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of an antibacterial nano water-soluble adhesive material comprises the following steps:
1) preparation of water-soluble peroxide chitosan
Adding chitosan into solvent, stirring, and adding 30% H 2 O 2 Uniformly stirring the solution, controlling the temperature not to exceed 50 ℃, and stirring for reacting for 4 hours to obtain a water-soluble peroxide chitosan aqueous solution, wherein the molecular weight of the chitosan is 85kDa to 110kDa, and the mass ratio of hydrogen peroxide to chitosan is 5:1 to 10: 1;
2) preparation of chitosan-titanium composite
Adding an inorganic base or an organic acid to Ti-containing 4+ Adjusting the pH value of the solution to 5-11 in titanium salt precursor aqueous solution with the ion concentration of 0.01-0.50 mol/L to obtain orthotitanic acid precipitate, removing impurities from the obtained precipitate through a purification process, slowly adding the orthotitanic acid precipitate into the water-soluble peroxide chitosan aqueous solution obtained in the step 1), after the addition is finished, uniformly stirring, controlling the water temperature to be not more than 50 ℃, and stirring for reaction for 4 hours to obtain a chitosan-titanium composite aqueous solution, wherein the mass ratio of titanium to chitosan is 0.5: 1-2: 1;
3) preparation of chitosan-titanium dioxide-silver nano hydrosol
Adding AgNO with the molar concentration of 0.01mol/L into the aqueous solution system of the chitosan-titanium compound obtained in the step 2) 3 And (3) controlling the molar concentration ratio of Ti to Ag to be 10:1 to 0.2:1, and then 20mW/cm 2 And reacting for 30-60 min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
2. The method according to claim 1, wherein the chitosan in step 1) has a molecular weight of 87kDa to 95kDa, more preferably 87kDa to 93 kDa;
preferably, the solvent in step 1) is selected from one or more of deionized water, methanol, ethanol and propanol, preferably deionized water;
preferably, the mass ratio of hydrogen peroxide to chitosan in step 1) is from 7:1 to 8:1, more preferably from 7.4:1 to 7.6: 1.
3. The method according to claim 1, wherein the mass ratio of titanium to chitosan in step 2) is 1:1 to 1.5:1, more preferably 1.2:1 to 1.3: 1;
preferably, the titanium salt precursor in step 2) is selected from one or more of titanium tetrachloride, titanyl sulfate, titanium tetrafluoride, titanium nitrate, titanium hydroxide, titanium carbonate and titanium tetrabromide, more preferably titanium tetrachloride, titanyl sulfate or titanium tetrafluoride;
preferably, the inorganic base in step 2) is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water, preferably ammonia water; the organic acid may be selected from one or more of acetic acid, citric acid, oxalic acid, succinic acid, malic acid, tartaric acid, etc.
4. The method according to claim 1, wherein the molar concentration ratio of Ti to Ag in step 3) is controlled to be 2:1 to 0.5:1, more preferably 1.5:1 to 1: 1.
5. The production method according to claim 1, characterized in that the production method is carried out as follows:
adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 25ml of solution, controlling hydrogen peroxide and chitosanThe mass ratio of (1) to (7.5) is controlled to be not more than 50 ℃, and the stirring reaction is carried out for 4 hours;
dissolving 100g of titanyl sulfate in 500ml of deionized water to obtain a titanyl sulfate aqueous solution; titrating a titanyl sulfate solution by using ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing the precipitate for 3 times by using deionized water to obtain an orthotitanic acid precipitate;
adding 15g of prepared titanium hydroxide precipitate into the chitosan peroxide solution, dissolving to obtain a transparent solution, and adding AgNO with the molar concentration of 0.01mol/L 3 10ml of the aqueous solution, and stirring the mixed solution at 20mW/cm 2 And reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
6. The production method according to claim 1, characterized in that the production method is performed as follows:
adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 15ml of solution, controlling the mass ratio of hydrogen peroxide to chitosan to be 5:1, controlling the water temperature not to exceed 50 ℃, and stirring for reaction for 4 hours;
firstly, dissolving 10g of titanium tetrachloride by using 500ml of deionized water to obtain a titanium chloride aqueous solution; titrating the titanium chloride solution by ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing the precipitate for 3 times by deionized water to obtain orthotitanic acid;
adding 5g of prepared titanium hydroxide precipitate into the chitosan peroxide solution, dissolving to obtain a transparent solution, and adding AgNO with the molar concentration of 0.01mol/L 3 5ml of aqueous solution, and mixing the solution at 20mW/cm 2 And reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
7. The production method according to claim 1, characterized in that the production method is performed as follows:
adding 1g of industrial-grade chitosan with the molecular weight of 88kDa into 100mL of distilled water, and then adding H with the mass concentration of 30 percent 2 O 2 35ml of the solution was added to the reaction solution,controlling the mass ratio of hydrogen peroxide to chitosan to be 10:1, controlling the water temperature to be not more than 50 ℃, and stirring for reacting for 4 hours;
firstly, dissolving 10g of titanium tetrafluoride by using 500ml of deionized water to obtain a titanium fluoride aqueous solution; titrating the titanium fluoride solution with ammonia water with the mass concentration of 36% until the PH value is 9 to obtain a precipitate, and washing with deionized water for 3 times to obtain orthotitanic acid;
adding 25g of prepared titanium hydroxide precipitate into the chitosan peroxide solution, dissolving to obtain a transparent solution, and adding AgNO with the molar concentration of 0.01mol/L 3 5ml of aqueous solution, and mixing the solution at 20mW/cm 2 And reacting for 30min under the radiation of an ultraviolet lamp with the wavelength of 254nm to obtain the final chitosan-titanium dioxide-silver composite nano sol.
8. An antibacterial nanoaquasol material, prepared by the manufacturing process according to any one of claims 1 to 7.
9. Use of the antibacterial nano hydrosol material according to claim 8 in the coating of exterior walls of buildings.
10. An exterior wall paint for buildings, which is characterized in that the exterior wall paint for buildings comprises the antibacterial nano water-soluble glue material according to claim 8 and auxiliary materials selected from but not limited to defoaming agents, leveling agents, water-based paint emulsions, coloring agents and the like.
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| CN202210430934.3A CN115024315A (en) | 2022-04-22 | 2022-04-22 | Synthetic method of antibacterial nano hydrosol |
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| CN202210430934.3A CN115024315A (en) | 2022-04-22 | 2022-04-22 | Synthetic method of antibacterial nano hydrosol |
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