CN115572413A - Nano-boehmite zinc-loaded inorganic composite antibacterial agent and preparation method thereof - Google Patents
Nano-boehmite zinc-loaded inorganic composite antibacterial agent and preparation method thereof Download PDFInfo
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- CN115572413A CN115572413A CN202110760943.4A CN202110760943A CN115572413A CN 115572413 A CN115572413 A CN 115572413A CN 202110760943 A CN202110760943 A CN 202110760943A CN 115572413 A CN115572413 A CN 115572413A
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 112
- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 90
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 58
- 239000011701 zinc Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 23
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005469 granulation Methods 0.000 claims abstract description 20
- 230000003179 granulation Effects 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000013329 compounding Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001694 spray drying Methods 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 229920002413 Polyhexanide Polymers 0.000 claims description 5
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- DLNWMWYCSOQYSQ-UHFFFAOYSA-M benzyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 DLNWMWYCSOQYSQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- OBFSQMXGZIYMMN-UHFFFAOYSA-N 3-chloro-2-hexadecylpyridine Chemical compound CCCCCCCCCCCCCCCCC1=NC=CC=C1Cl OBFSQMXGZIYMMN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006011 modification reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 31
- 238000010438 heat treatment Methods 0.000 abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 6
- 241000894006 Bacteria Species 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000001804 emulsifying effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OCXRVDQYXZSPBP-UHFFFAOYSA-N 2-(16-chlorohexadecyl)pyridine Chemical compound ClCCCCCCCCCCCCCCCCC1=CC=CC=N1 OCXRVDQYXZSPBP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Abstract
The invention discloses a nano-boehmite zinc-loaded inorganic composite antibacterial agent and a preparation method thereof, wherein the preparation method of the nano-boehmite zinc-loaded inorganic composite antibacterial agent comprises the following steps: a. dissolving high-purity pseudo-boehmite into a nitric acid aqueous solution system to prepare a boehmite precursor; b. adding zinc ions into a boehmite precursor aqueous solution to carry out a pre-adsorption process; c. putting the boehmite precursor aqueous solution pre-adsorbed with zinc ions into a high-pressure reaction kettle for full adsorption and ion exchange of the zinc ions; d. compounding the zinc-loaded antibacterial agent discharged from the kettle with an organic antibacterial agent; e. and (4) taking out the solution from the kettle, and carrying out modification and spray granulation to obtain the nano-boehmite zinc-loaded inorganic composite antibacterial agent. The preparation method of the invention adopts high-purity pseudo-boehmite as a raw material, and the product does not need purification and high-temperature heat treatment; the hydrothermal synthesis method improves the ion exchange capacity, the adhesion strength and the zinc ion loading capacity of zinc ions in the boehmite powder, and ensures the long-acting antibacterial stability of the antibacterial agent to bacteria and mould.
Description
Technical Field
The invention relates to the field of antibacterial agent materials, and particularly relates to a nano-boehmite zinc-loaded inorganic composite antibacterial agent and a preparation method thereof.
Background
The existing inorganic antibacterial agents can be divided into the following substances with antibacterial effect: metal (silver, copper, zinc, nickel), photocatalytic (titanium dioxide) and oxide (zinc oxide, tin oxide, copper oxide). The nano inorganic antibacterial agent utilizes the strong ion exchange capacity and adsorption characteristic of the carrier and the antibacterial effect of the effective antibacterial ingredients to compound the nano inorganic carrier and the effective antibacterial ingredients to obtain the nano inorganic antibacterial agent.
The boehmite synthesis method comprises a sol-gel method, a carbon separation method and a hydrothermal synthesis method. The hydrothermal synthesized boehmite powder has uniform particle size distribution, large specific surface area and adjustable pore volume within a certain range. The hydrothermal synthesis boehmite is widely applied to various fields such as resin fillers, ceramics, ink absorption pigments, inorganic flame retardants, adsorbents, catalysts and the like in industry, and the nano-boehmite zinc-loaded inorganic composite antibacterial agent combines the advantages of wide use, zinc ion antibacterial broad spectrum and sterilization immediate effect of organic antibacterial agents, and can be widely applied to various antibacterial materials, such as: fabrics, plastics, ceramic glazes, coatings, and the like.
The metal ion sterilization mechanism is to interfere the cell metabolic process or interfere the action of various enzymes, so that the enzymes lose the due biological functions and finally cause the death of cells. The antibacterial ability of silver ion is better than that of zinc ion, but the silver-carrying inorganic antibacterial agent has poor color stability in the storage and use process, and the copper-carrying inorganic antibacterial agent has light blue or dark blue, so that the application range of the copper-carrying inorganic antibacterial agent is limited. Although the antibacterial ability of the zinc-loaded inorganic antibacterial agent is lower than that of silver ions, the zinc-loaded inorganic antibacterial agent has better chemical stability and environmental and human friendliness than silver and copper, and can be popularized and applied in various antibacterial fields.
The existing zinc-loaded inorganic antibacterial agent is obtained only by a simple physical adsorption method, the carrier is easy to agglomerate in the granulation forming process, and the zinc ion load in the carrier is small, so that the long-time and efficient antibacterial effect on bacteria can not be realized. Therefore, there is a need for the development of an antibacterial agent having long-lasting antibacterial properties, namely, efficacy and safety.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a nano-boehmite zinc-loaded inorganic composite antibacterial agent and a preparation method thereof, and solves the problem that the zinc ion loading capacity in a zinc-loaded inorganic antibacterial agent carrier in the prior art is small, and long-time and efficient antibacterial effect on bacteria cannot be realized.
The invention is realized by the following technical scheme:
a method for preparing a nano-boehmite zinc-loaded inorganic antibacterial agent, wherein the nano-boehmite zinc-loaded inorganic composite antibacterial agent is prepared by taking high-purity pseudo-boehmite, soluble zinc salt, an organic antibacterial agent, a dispersing agent and a modifying agent as raw materials, and comprises the following steps:
(a) Preparation of boehmite precursor: dissolving high-purity pseudoboehmite into an acidic aqueous solution at normal temperature, wherein the pH value in the aqueous solution is adjusted to be 2-4;
(b) Pre-adsorption process: adding soluble zinc salt into a boehmite precursor water solution, fully mixing, and simultaneously adding a water-soluble dispersant into the mixed solution, wherein the soluble zinc salt is zinc nitrate;
(c) Synthesizing the nano-boehmite zinc-loaded inorganic antibacterial agent: putting the boehmite precursor aqueous solution pre-adsorbed with zinc ions into a high-pressure reaction kettle for full adsorption and ion exchange of the zinc ions;
(d) Preparing a composite antibacterial agent: compounding the zinc-loaded antibacterial agent discharged from the kettle with an organic antibacterial agent;
(e) Collecting the composite antibacterial agent: and (4) taking out the solution from the kettle, and carrying out modification and spray granulation to obtain the nano-boehmite zinc-loaded inorganic composite antibacterial agent.
In the recommended boehmite precursor embodiment, the dispersibility of the high-purity pseudo-boehmite in the aqueous solution can be promoted by adjusting the pH value of the aqueous solution to be acidic, and the pH value is adjusted to be 2-4; na in the high-purity pseudo-boehmite adopted 2 O content is less than 150ppm 2 The content is less than 150ppm 2 O 3 The content is less than 100ppm and the CaO content is less than 100ppm.
In the recommended zinc ion pre-adsorption embodiment, the water-soluble zinc salt is zinc nitrate, the weight ratio of the zinc nitrate to the high-purity pseudo-boehmite is 1-9, one or more of Tween-80 (Tween-80), span-60 (Span-60), polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG) and Methyl Cellulose (MC) are added as water-soluble dispersing agents for preventing feed liquid from agglomerating, and the pre-adsorption process is carried out at room temperature for 1-2h.
In the recommended synthesis embodiment of the nano boehmite zinc-loaded inorganic composite antibacterial agent, the temperature of a high-temperature high-pressure reaction kettle is raised to 200-220 ℃, the temperature is kept for 2-4 hours, and the reaction is finished to obtain the nano boehmite zinc-loaded inorganic antibacterial agent.
In the recommended embodiment of the composite synthesis of the zinc-carrying antibacterial agent and the organic antibacterial agent, the weight ratio of the organic antibacterial agent to the high-purity pseudo-boehmite is 1-50, and the composite time is 1-2h. The organic antibacterial agent is one or more of chlorocetyl pyridine, hexadecyl dimethyl benzyl ammonium bromide, dioctadecyl dimethyl ammonium chloride and polyhexamethylene biguanide hydrochloride, and the compounding process is carried out at room temperature.
In the recommended embodiment of the inorganic antibacterial agent modification, the lifting powder is added in a modifier for a water-insoluble use environment and the composite antibacterial agent is modified, the weight ratio of the modifier to the high-purity pseudo-boehmite is 1-5, the modifier is one or more of gamma-aminopropyltriethoxysilane (KH 550), gamma-methacryloxypropyltrimethoxysilane (KH 570) and water-soluble titanate (TM-200), the modification process is carried out at the temperature of 60-80 ℃, and the modification reaction time is 1-2h.
The feeding speed of spray granulation is 4.5-5.0L/h, and the spray drying temperature is 110-120 ℃.
The invention also provides the nano boehmite zinc-loaded inorganic composite antibacterial agent prepared according to the preparation method. The particle size of the antibacterial agent powder is 50-100nm, the water content of the antibacterial agent powder is 0.5-2.0%, the pH of the antibacterial agent powder is 2-4, and the zinc content of the nano boehmite antibacterial agent is 1.4-9.6%.
The technical scheme of the invention has the following characteristics:
(1) The boehmite zinc-loaded antibacterial agent prepared by hydrothermal synthesis can be directly prepared into nano-grade powder, the antibacterial powder has uniform particle size distribution, the average particle size after dispersion is less than 100nm, the specific surface area is large, and the pore volume is adjustable within a certain range.
(2) The boehmite zinc-loaded antibacterial agent uses a high-purity pseudo-boehmite raw material, subsequent purification and high-temperature heat treatment on the product are not needed, the zinc content in the antibacterial agent reaches 1.4-9.6%, the loss phenomenon of zinc ions does not exist, the loading capacity of the carrier on the zinc ions can be greatly improved, and the antibacterial stability and the long-acting property are ensured in the later-stage use of the high-content zinc ion loading.
(3) Adding an organic antibacterial agent into the solution discharged from the high-temperature high-pressure reaction kettle so as to compound the inorganic antibacterial powder and the organic antibacterial agent, so that the nano boehmite zinc-loaded antibacterial agent has an immediate antibacterial function.
(4) Adding modifier into the solution from the high temperature high pressure reaction kettle to change the water soluble antibacterial powder from hydrophilic to lipophilic, so that the antibacterial powder can be used in water insoluble system.
(5) The inorganic antibacterial powder is prepared by using boehmite as a carrier and utilizing a hydrothermal synthesis method in one step, and does not need further high-temperature heat treatment and purification processes in the subsequent process, so that the reaction time is shortened, and the production efficiency is improved. Although the zinc-containing inorganic antibacterial agent has poorer antibacterial performance than the silver-based inorganic antibacterial agent, the zinc-containing inorganic antibacterial agent also has the characteristics of low price and no discoloration after long-term storage. The inorganic antibacterial agent is compounded with a small amount of organic antibacterial agent, so that the rapid antibacterial performance of the inorganic antibacterial agent can be improved, and the composition of the organic antibacterial agent and the inorganic antibacterial agent can improve the stability, the immediate effect and the long-acting effect of the antibacterial powder on the antibacterial effect of bacteria.
The preparation method adopts high-purity raw materials, the nano boehmite inorganic antibacterial agent with high zinc ion loading capacity is prepared by a hydrothermal synthesis method in one step, the inorganic antibacterial agent does not need to be purified and subjected to high-temperature heat treatment subsequently, the nano boehmite zinc-loaded inorganic composite antibacterial agent can be applied to water-based paint, oil-based paint, plastic and ceramic glaze through later modification, and the prepared nano boehmite zinc-loaded inorganic composite antibacterial agent can improve the stability, the immediate effect and the long-acting property of the antibacterial powder on the antibacterial effect of bacteria.
The hydrothermal synthesis of the boehmite zinc-loaded antibacterial agent can directly obtain the nano-grade antibacterial agent, meanwhile, the loading capacity of the carrier to zinc ions is greatly improved, the antibacterial stability and the long-acting property are ensured in the using process, the high-purity raw materials are used in the synthesis process, so that the antibacterial agent is not required to be further purified and subjected to high-temperature heat treatment in the later period, and the using cost of the antibacterial agent is reduced.
Drawings
FIG. 1 is a scanning electron microscope topography of the nano-boehmite zinc-loaded inorganic composite antibacterial agent.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention. Example 1 preparation of inorganic composite antibacterial agent with zinc loaded nano-boehmite
(a) Dissolving 600g of high-purity pseudo-boehmite in 3000mL of deionized water, dropwise adding dilute nitric acid with the concentration of 5% in the stirring process, and controlling the end-point pH value of the boehmite precursor aqueous solution to be 2-4;
(b) Adding 200g of 20% solid zinc nitrate aqueous solution into the boehmite precursor aqueous solution in the step (a), and uniformly stirring and mixing to obtain boehmite precursor solution;
(c) Adding 2g of PVP and 2g of PVA dispersant into the boehmite precursor water solution in the step (b), and emulsifying and mixing uniformly under high shear;
(d) And (c) putting the uniformly emulsified and mixed solution in a 5000mL high-temperature high-pressure reaction kettle, heating to 200 +/-2 ℃, starting reaction timing, and keeping the temperature for 2-4 hours to obtain the nano boehmite zinc-loaded inorganic antibacterial agent.
(e) And (3) adding 6g of chlorohexadecylpyridine organic antibacterial agent into the solution (d) which is naturally cooled and cooled in the stirring process, then heating the feed liquid to 80 ℃, adding 6g of KH550 modifier, reacting for 1-2h, and stopping heating and stirring after fully mixing.
(f) And (3) carrying out spray drying granulation on the solution in the step (e), wherein the feeding speed of the spray granulation is 4.5-5.0L/h, the spray drying temperature is 110-120 ℃, the water content of the powder is controlled to be 0.5% -2.0%, and the product is packaged for later use.
Example 2 preparation of inorganic composite antibacterial agent with zinc loaded nano-boehmite
(a) Dissolving 600g of high-purity pseudoboehmite in 3000mL of deionized water, dropwise adding dilute nitric acid with the concentration of 5% in the stirring process, and controlling the end point pH value of the boehmite precursor water solution to be 2-4;
(b) Adding 450g of 20% solid zinc nitrate aqueous solution into the boehmite precursor aqueous solution in the step (a), and uniformly stirring and mixing to obtain boehmite precursor solution;
(c) Adding 2g of PVP and 3g of PEG dispersing agent into the boehmite precursor water solution in the step (b), and emulsifying and mixing uniformly by high shearing;
(d) And (c) putting the uniformly emulsified and mixed solution in a 5000mL high-temperature high-pressure reaction kettle, heating to 200 +/-2 ℃, starting reaction timing, and keeping the temperature for 2-4 hours to obtain the nano boehmite zinc-loaded inorganic antibacterial agent.
(e) In the stirring process, 15g of hexadecyl dimethyl benzyl ammonium bromide organic antibacterial agent is added into the solution (d) which is naturally cooled, then the temperature of the feed liquid is raised to 80 ℃, 18g of KH570 modifier is added for reaction for 1-2h, and the heating and the stirring are stopped after the materials are fully mixed.
(f) And (3) carrying out spray drying granulation on the solution in the step (e), wherein the feeding speed of the spray granulation is 4.5-5.0L/h, the spray drying temperature is 110-120 ℃, the water content of the powder is controlled to be 0.5% -2.0%, and the product is packaged for later use.
Example 3 preparation of inorganic composite antibacterial agent with zinc loaded nano-boehmite
(a) Dissolving 600g of high-purity pseudo-boehmite in 3000mL of deionized water, dropwise adding dilute nitric acid with the concentration of 5% in the stirring process, and controlling the end-point pH value of the boehmite precursor aqueous solution to be 2-4;
(b) Adding 600g of 20% solid zinc nitrate aqueous solution into the boehmite precursor aqueous solution in the step (a), and uniformly stirring and mixing to obtain a boehmite precursor solution;
(c) Adding 2g of PVA and 2g of Tween-80 dispersing agent into the boehmite precursor aqueous solution in the step (b), and emulsifying and mixing uniformly by high shear;
(d) And (c) putting the solution (c) which is emulsified and mixed uniformly into a 5000mL high-temperature high-pressure reaction kettle, heating to 200 +/-2 ℃, starting reaction timing, and keeping the temperature for 2-4 hours to obtain the nano boehmite zinc-loaded inorganic antibacterial agent.
(e) In the stirring process, 3g of polyhexamethylene biguanide hydrochloride and 3g of dioctadecyl dimethyl ammonium chloride organic antibacterial agent are added into the naturally cooled solution (d), then the temperature of the feed liquid is raised to 80 ℃, 3gKH and 9g of KH570 modifier are added, the reaction time is 1-2h, and the heating and the stirring are stopped after the full mixing.
(f) And (3) carrying out spray drying granulation on the solution in the step (e), wherein the feeding speed of the spray granulation is 4.5-5.0L/h, the spray drying temperature is 110-120 ℃, the water content of the powder is controlled to be 0.5% -2.0%, and the product is packaged for later use.
Example 4 preparation of inorganic composite antibacterial agent with zinc loaded nano-boehmite
(a) Dissolving 600g of high-purity pseudo-boehmite in 3000mL of deionized water, dropwise adding dilute nitric acid with the concentration of 5% in the stirring process, and controlling the end-point pH value of the boehmite precursor aqueous solution to be 2-4;
(b) Adding 1200g of 20% solid zinc nitrate aqueous solution into the boehmite precursor aqueous solution in the step (a), and uniformly stirring and mixing to obtain a boehmite precursor solution;
(c) Adding 3g of MC and 2g of Span-60 dispersing agent into the boehmite precursor aqueous solution in the step (b), and emulsifying and mixing uniformly by high shear;
(d) And (c) putting the uniformly emulsified and mixed solution in a 5000mL high-temperature high-pressure reaction kettle, heating to 200 +/-2 ℃, starting reaction timing, and keeping the temperature for 2-4 hours to obtain the nano boehmite zinc-loaded inorganic antibacterial agent.
(e) In the stirring process, 6g of polyhexamethylene biguanide hydrochloride and 6g of dioctadecyl dimethyl ammonium chloride organic antibacterial agent are added into the solution (d) which is naturally cooled, then the temperature of the feed liquid is raised to 80 ℃, 5gTM200 modifier is added, the reaction time is 1-2h, and the heating and the stirring are stopped after the full mixing.
(f) And (3) carrying out spray drying granulation on the solution in the step (e), wherein the feeding speed of the spray granulation is 4.5-5.0L/h, the spray drying temperature is 110-120 ℃, the water content of the powder is controlled to be 0.5% -2.0%, and the product is packaged for later use.
Comparative example 1
This comparative example is essentially the same as example 1 except that the zinc salt and pyridine organic antibacterial agent are not added. The preparation method comprises the following steps:
(a) Dissolving 600g of high-purity pseudo-boehmite in 3000mL of deionized water, dropwise adding dilute nitric acid with the concentration of 5% in the stirring process, and controlling the end-point pH value of the boehmite precursor aqueous solution to be 2-4;
(b) Adding 2g of PVP and 2g of PVA dispersant into the boehmite precursor aqueous solution in the step (b), and emulsifying and mixing uniformly under high shear;
(d) And (c) putting the uniformly emulsified and mixed solution into a 5000mL high-temperature high-pressure reaction kettle, heating to 200 +/-2 ℃, starting reaction timing, and keeping the temperature for 2-4 hours to obtain the nano boehmite.
(e) And d, carrying out spray drying granulation on the solution in the step d, wherein the feeding speed of the spray granulation is 4.5-5.0L/h, the spray drying temperature is 110-120 ℃, the water content of the powder is controlled to be 0.5% -2.0%, and the product is packaged for later use.
Comparative example 2
This comparative example is essentially the same as example 1, except that no pyridine organic antibacterial agent was added. The preparation method comprises the following steps:
(a) Dissolving 600g of high-purity pseudo-boehmite in 3000mL of deionized water, dropwise adding dilute nitric acid with the concentration of 5% in the stirring process, and controlling the end-point pH value of the boehmite precursor aqueous solution to be 2-4;
(b) Adding 200g of 20% solid zinc nitrate aqueous solution into the boehmite precursor aqueous solution in the step (a), and uniformly stirring and mixing to obtain boehmite precursor solution;
(c) Adding 2g of PVP and 2g of PVA dispersant into the boehmite precursor water solution in the step (b), and emulsifying and mixing uniformly under high shear;
(d) And (c) putting the uniformly emulsified and mixed solution in a 5000mL high-temperature high-pressure reaction kettle, heating to 200 +/-2 ℃, starting reaction timing, and keeping the temperature for 2-4 hours to obtain the nano boehmite zinc-loaded inorganic antibacterial agent.
(e) And d, carrying out spray drying granulation on the solution in the step d, wherein the feeding speed of the spray granulation is 4.5-5.0L/h, the spray drying temperature is 110-120 ℃, the water content of the powder is controlled to be 0.5% -2.0%, and packaging the product for later use.
Comparative example 3
This comparative example is essentially the same as example 4 except that no zinc salt is added. The preparation method comprises the following steps: (a) Dissolving 600g of high-purity pseudoboehmite in 3000mL of deionized water, dropwise adding dilute nitric acid with the concentration of 5% in the stirring process, and controlling the end point pH value of the boehmite precursor water solution to be 2-4;
(b) Adding 2g of PVP and 2g of PVA dispersant into the boehmite precursor aqueous solution in the step (a), and emulsifying and mixing uniformly under high shear;
(c) And (b) putting the solution (b) which is emulsified and mixed uniformly into a 5000mL high-temperature high-pressure reaction kettle, heating to 200 +/-2 ℃, starting reaction timing, and keeping the temperature for 2-4 hours to obtain the nano boehmite.
(d) In the stirring process, 3g of polyhexamethylene biguanide hydrochloride and 3g of dioctadecyl dimethyl ammonium chloride organic antibacterial agent are added into the naturally cooled solution (c), then the temperature of the feed liquid is raised to 80 ℃, 3g of KH550 and 9g of KH570 modifying agents are added, the reaction time is 1-2h, and the heating and the stirring are stopped after the materials are fully mixed.
(e) And d, carrying out spray drying granulation on the solution in the step d, wherein the feeding speed of the spray granulation is 4.5-5.0L/h, the spray drying temperature is 110-120 ℃, the water content of the powder is controlled to be 0.5% -2.0%, and the product is packaged for later use.
The nano-boehmite zinc-loaded inorganic composite antibacterial agent powder disclosed by the invention is uniform in particle size distribution, the average particle size after dispersion is smaller than 100nm, and the adsorption strength of boehmite to zinc ions is effectively enhanced due to a larger pore volume and a uniformly distributed pore channel structure. Antibacterial test standard: according to GBT/21510-2008, escherichia coli and Staphylococcus aureus are adopted as probes to perform reaction to evaluate the antibacterial effect of the examples and the comparative examples, within 5min, the antibacterial rate of the antibacterial agent in the examples can reach over 99.9%, the antibacterial activity R value is greater than 3.0, and the specific test results are shown in Table 1.
TABLE 1 antimicrobial Performance test
Although the present invention has been described with reference to the above embodiments, it should be understood that the present invention is not limited thereto, and various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (9)
1. A preparation method of a nano-boehmite zinc-loaded inorganic composite antibacterial agent is characterized in that the nano-boehmite zinc-loaded inorganic composite antibacterial agent is prepared by taking high-purity pseudo-boehmite, soluble zinc salt, an organic antibacterial agent, a dispersing agent and a modifying agent as raw materials, and comprises the following steps:
(a) Preparation of boehmite precursor: dissolving high-purity pseudoboehmite into an acidic aqueous solution at normal temperature, wherein the pH value in the aqueous solution is adjusted to be 2-4;
(b) Pre-adsorption process: adding soluble zinc salt into a boehmite precursor water solution, fully mixing, and simultaneously adding a water-soluble dispersant into the mixed solution, wherein the soluble zinc salt is zinc nitrate;
(c) Synthesizing the nano boehmite-loaded zinc inorganic antibacterial agent: putting the boehmite precursor aqueous solution pre-adsorbed with zinc ions into a high-pressure reaction kettle for full adsorption and ion exchange of the zinc ions;
(d) Preparing a composite antibacterial agent: compounding the zinc-loaded antibacterial agent discharged from the kettle with an organic antibacterial agent;
(e) Collecting the composite antibacterial agent: and (4) taking out the solution from the kettle, and carrying out modification and spray granulation to obtain the nano-boehmite zinc-loaded inorganic composite antibacterial agent.
2. Preparation of nano-boehmite zinc-loaded inorganic composite antibacterial agent according to claim 1The method is characterized in that: na in the high-purity pseudo-boehmite 2 O content is less than 150ppm 2 The content is less than 150ppm 2 O 3 The content is less than 100ppm and the CaO content is less than 100ppm.
3. The method for preparing a nano-boehmite zinc-loaded inorganic composite antibacterial agent according to claim 1, characterized in that: in the step (b), the weight ratio of zinc nitrate to the high-purity pseudo-boehmite is 1-9, the pre-adsorption process is carried out at room temperature, and the pre-adsorption time is 1-2h; the water-soluble dispersant is one or more of tween-80, span-60, polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol and methyl cellulose.
4. The method for preparing a nano-boehmite zinc-loaded inorganic composite antibacterial agent according to claim 1, characterized in that: in the step (c), the temperature of the high-pressure reaction kettle is set to be 200-220 ℃, and the constant temperature duration is 2-4 hours.
5. The method for preparing a nano-boehmite zinc-loaded inorganic composite antibacterial agent according to claim 1, characterized in that: in the step (d), the weight ratio of the organic antibacterial agent to the high-purity pseudo-boehmite is 1-50, and the compounding time is 1-2h; the organic antibacterial agent is one or more of chlorocetyl pyridine, hexadecyl dimethyl benzyl ammonium bromide, dioctadecyl dimethyl ammonium chloride and polyhexamethylene biguanide hydrochloride, and the compounding process is carried out at room temperature.
6. The method for preparing a nano-boehmite zinc-loaded inorganic composite antibacterial agent according to claim 1, characterized in that: in the step (e), the composite antibacterial agent is modified, the weight ratio of the modifier to the high-purity pseudo-boehmite is 1-5, the discharged material liquid modifier is one or more of gamma-aminopropyl triethoxy silicon, gamma-methacryloxypropyl trimethoxy silane and water-soluble titanate, the modification process is carried out at the temperature of 60-80 ℃, and the modification reaction time is 1-2h.
7. The method for preparing a nano-boehmite zinc-loaded inorganic composite antibacterial agent according to claim 1, characterized in that: the feeding speed of spray granulation is 4.5-5.0L/h, and the spray drying temperature is 110-120 ℃.
8. The nano-boehmite zinc-loaded inorganic composite antibacterial agent prepared according to the method for preparing the nano-boehmite zinc-loaded inorganic composite antibacterial agent according to any one of claims 1 to 7.
9. The nano-boehmite zinc-loaded inorganic composite antibacterial agent according to claim 8, characterized in that: the grain diameter of the antibacterial agent powder is 50-100nm, the water content of the antibacterial agent powder is 0.5-2.0%, the pH value of the antibacterial agent powder is 2-4, and the zinc content of the nano boehmite antibacterial agent is 1.4-9.6%.
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