CN114903036A - Silicon-based antibacterial agent, antibacterial resin, antibacterial plastic cup and preparation method thereof - Google Patents
Silicon-based antibacterial agent, antibacterial resin, antibacterial plastic cup and preparation method thereof Download PDFInfo
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- CN114903036A CN114903036A CN202110185019.8A CN202110185019A CN114903036A CN 114903036 A CN114903036 A CN 114903036A CN 202110185019 A CN202110185019 A CN 202110185019A CN 114903036 A CN114903036 A CN 114903036A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 70
- 239000010703 silicon Substances 0.000 title claims abstract description 70
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 66
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 239000011347 resin Substances 0.000 title claims abstract description 47
- 239000004033 plastic Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010227 cup method (microbiological evaluation) Methods 0.000 title description 2
- 238000001035 drying Methods 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 230000032683 aging Effects 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000004599 antimicrobial Substances 0.000 claims abstract description 5
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 33
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 17
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims description 10
- -1 silver ions Chemical class 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229920005990 polystyrene resin Polymers 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- RZTYEUCBTNJJIW-UHFFFAOYSA-K silver;zirconium(4+);phosphate Chemical compound [Zr+4].[Ag+].[O-]P([O-])([O-])=O RZTYEUCBTNJJIW-UHFFFAOYSA-K 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/015—Biocides
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Agronomy & Crop Science (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silicon-based antibacterial agent, antibacterial resin, an antibacterial plastic cup and a preparation method thereof. The preparation method of the silicon-based antibacterial agent comprises the following steps: reacting a mixed solution of 1-5% of water-soluble metal salt, 5-10% of hydrolyzable silicon source, 0.5-1% of negative catalyst and 84-93.5% of water, aging, drying and calcining. An antimicrobial resin comprising the following components: 1-3% of silicon-based antibacterial agent and 97-99% of resin. A preparation method of an antibacterial plastic cup comprises the following steps: and (4) extruding and molding the antibacterial resin, and polishing. The silicon-based antibacterial agent has high doping concentration and narrow particle size distribution; the transmittance and the mechanical property of the antibacterial plastic cup are not influenced; the antibacterial plastic cup has excellent antibacterial performance and anti-mildew performance.
Description
Technical Field
The invention relates to a silicon-based antibacterial agent, antibacterial resin, an antibacterial plastic cup and a preparation method thereof.
Background
At present, the inorganic metal antibacterial materials on the market at home mainly comprise four main types, namely zeolite silver-loaded, zirconium phosphate silver-loaded, glass silver-loaded and silicon-based silver-loaded antibacterial agents. The silver-loaded zeolite antibacterial agent and the silver-loaded zirconium phosphate antibacterial agent have high refractive index, so that the transparency of a plastic product can be influenced when the silver-loaded zeolite antibacterial agent and the silver-loaded zirconium phosphate antibacterial agent are added into the plastic product; and the plastic product added with the glass silver-loaded product and the silicon-based silver-loaded antibacterial agent has the advantage of good transparency.
The main production method of the glass silver-carrying antibacterial agent is a fusion heat treatment method (patent CN1323588), which is to mix a basic glass material and a dopant containing silver, zinc and copper ions, to perform high-temperature melting, cooling forming, grinding or crushing into powder, and to control the size and distribution of particles by adjusting the grinding or crushing process. However, this method of preparing powder from top to bottom is prone to large particles of 10 μm or more and is difficult to remove. The grain diameter of the antibacterial agent used in the plastic products is at least below 1 μm, otherwise the transmittance and the mechanical property of the antibacterial finished product are influenced. It is known that silicon-based silver-loaded antibacterial agents are mainly produced by depositing nano silver sol on the surface of silica materials (patent CN 109452309), which has the advantage of small particle size, generally within 0.1 μm, but silver is easily oxidized and discolored because of being distributed on the surface of silica materials.
Disclosure of Invention
The invention aims to overcome the defects of poor light transmittance, mechanical property and yellowing resistance of an antibacterial product prepared from the conventional silicon-based antibacterial agent, and provides a silicon-based antibacterial agent, antibacterial resin, an antibacterial plastic cup and a preparation method thereof.
The invention solves the technical problems through the following technical scheme:
the invention provides a preparation method of a silicon-based antibacterial agent, which comprises the steps of reacting, aging, drying and calcining a mixed solution of 1-5% of water-soluble metal salt, 5-10% of hydrolyzable silicon source, 0.5-1% of negative catalyst and 84-93.5% of water, wherein the percentages are percentages of the mass of all components and the total mass of the mixed solution;
wherein the water-soluble metal salt is a water-soluble salt of silver, zinc or copper; the temperature of the reaction is not higher than 90 ℃.
Preferably, the water-soluble metal salt is one or more of silver nitrate, zinc nitrate, copper chloride and copper sulfate; more preferably one or more of silver nitrate, zinc nitrate and copper nitrate.
Optionally, the water soluble metal salt is used in an amount of 2%, 4%, or 5%.
In the present invention, the hydrolyzable silicon source may be a silicon source that can generate silicon oxide through hydrolysis reaction, which is conventional in the art; preferably TEOS.
The TEOS is, for example, tetraethoxysilane which is conventional in the art, such as tetraethoxysilane commercially available from the chemical industry ltd.
Alternatively, the hydrolyzable silicon source is used in an amount of 7%, 8%, or 9.2%.
In the invention, the negative catalyst refers to a catalyst capable of slowing down the hydrolysis speed of the silicon source; preferably an ammonium salt surfactant; more preferably sodium dodecylbenzene sulfonate, such as sodium dodecylbenzene sulfonate commercially available from alatin biochemistry science and technology limited.
Alternatively, the negative catalyst is used in an amount of 0.5%, 0.7%, or 0.8%.
In the present invention, the water may be deionized water which is conventional in the art.
Optionally, the amount of water is 86.5%, 88%, or 88.3%.
In the present invention, the operation of the reaction may be conventional in the art; stirring of the reaction is preferred.
Preferably, the reaction temperature is 25-90 ℃, such as 60 ℃, 70 ℃ or 80 ℃.
In the present invention, one skilled in the art can adjust the reaction time according to the silicon source; preferably, the reaction time is 10 to 20 hours; for example 15 hours.
In the invention, the person skilled in the art can adjust the aging time according to the silicon source; preferably, the aging time is 10 to 20 hours; for example 15 hours.
In the present invention, the reaction and the aging environment may be conventional in the art, and preferably, the reaction and the aging are carried out in a reaction vessel.
In the present invention, it is known to those skilled in the art that filtration is generally included before the drying.
In the present invention, the drying environment may be conventional in the art, and is preferably dried in a vacuum oven.
In the invention, the appropriate drying temperature is known to those skilled in the art, and preferably, the drying temperature is 70-80 ℃.
In the present invention, the person skilled in the art knows suitable conditions for calcination.
Preferably, the calcining temperature is 700-800 ℃.
Preferably, the calcining time is 5-10 hours; for example 6 hours or 8 hours.
In one embodiment of the present invention, the water-soluble metal salt is silver nitrate, the amount of silver nitrate is 2%, the hydrolyzable silicon source is TEOS, the amount of TEOS is 9.2%, the negative catalyst is sodium dodecylbenzenesulfonate, the amount of sodium dodecylbenzenesulfonate is 0.8%, the reaction time is 20 hours, the reaction temperature is 80 ℃, the aging time is 20 hours, the drying is drying in a vacuum drying oven, the drying temperature is 80 ℃, the calcining temperature is 800 ℃, and the calcining time is 5 hours.
In another embodiment of the present invention, the water-soluble metal salt is zinc nitrate, the amount of zinc nitrate is 5%, the hydrolyzable silicon source is TEOS, the amount of TEOS is 8%, the negative catalyst is sodium dodecylbenzenesulfonate, the amount of sodium dodecylbenzenesulfonate is 0.5%, the reaction time is 10 hours, the reaction temperature is 70 ℃, the aging time is 15 hours, the drying is drying in a vacuum drying oven, the drying temperature is 80 ℃, the calcining temperature is 800 ℃, and the calcining time is 6 hours.
In another embodiment of the present invention, the water-soluble metal salt is copper nitrate, the amount of the copper nitrate is 4%, the hydrolyzable silicon source is TEOS, the amount of the TEOS is 7%, the negative catalyst is sodium dodecylbenzenesulfonate, the amount of the sodium dodecylbenzenesulfonate is 0.7%, the time of the reaction is 15 hours, the temperature of the reaction is 60 ℃, the time of the aging is 15 hours, the drying is drying in a vacuum drying oven, the temperature of the drying is 70 ℃, the temperature of the calcining is 800 ℃, and the time of the calcining is 8 hours.
The invention also provides a silicon-based antibacterial agent prepared by the preparation method of the silicon-based antibacterial agent.
The invention also provides a silicon-based antibacterial agent, which comprises nano silicon oxide and metal cations distributed in the nano silicon oxide; wherein the granularity of the silicon-based antibacterial agent is 0.1-1 mu m; the doping concentration of the metal cations is 5-30%; the particle size of the nano silicon oxide is 50-300 nm; the metal cations include one or more of silver ions, zinc ions, and copper ions.
In the invention, the silicon-based antibacterial agent forms a structure with uniform primary particle size.
Preferably, the particle size of the silicon-based antibacterial agent is 0.3-0.5 μm.
Optionally, the doping concentration of silver ions is 6%, 28% or 29%. The invention also provides an antibacterial resin, which comprises the following components: 1% -3% of the silicon-based antibacterial agent and 97% -99% of resin; the percentage is the percentage of the mass of each component to the total mass of the antibacterial resin.
In the present invention, the resin refers to a transparent resin which is conventional in the art; preferably a polystyrene resin (PS), such as PS commercially available from zhenjiangqimei.
Optionally, the silicon-based antimicrobial agent is present in an amount of 2%.
Optionally, the resin is used in an amount of 98%.
The invention also provides a preparation method of the antibacterial resin, which comprises the following steps: mixing the components of the antibacterial resin and extruding.
In the present invention, the mixing may be conventional in the art, for example, by uniformly mixing with a stirring device.
In the present invention, the extrusion may be conventional in the art, and is generally melt-extruded using a twin-screw extruder.
The invention also provides the antibacterial resin prepared by the preparation method of the antibacterial resin.
The invention also provides an antibacterial plastic cup prepared from the antibacterial resin.
The invention also provides a preparation method of the antibacterial plastic cup, which comprises the following steps: and (3) extruding and molding the antibacterial resin, and polishing.
In the present invention, the extrusion process may be conventional in the art, and is generally extrusion molded in a mold. Wherein the demolding operation is generally performed after the extrusion molding and before the polishing, as is known to those skilled in the art.
In the present invention, the polishing process may be conventional in the art, such as finish grinding polishing.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the silicon-based antibacterial agent disclosed by the invention is high in doping concentration and narrow in particle size distribution, the prepared silicon-based antibacterial agent forms a structure with uniform primary particle size, silver ions are uniformly distributed in nano silicon oxide, the D99 particle size is 0.1-1 mu m, the doping concentration of the silver ions is 5% -30%, and the particle size of the nano silicon oxide is 50-300 nm.
2. The silicon-based antibacterial agent does not affect the transmittance and mechanical property of the antibacterial plastic cup, the transparency can reach more than 90%, the tensile strength can reach 37MPa, and the b value change of the color change of the silicon-based antibacterial agent is lower than 1.28 after the silicon-based antibacterial agent is aged by ultraviolet light for 30 days.
3. The antibacterial plastic cup has excellent antibacterial performance and anti-mildew performance, the sterilization rate in the air for 18 hours can reach 99.9%, and the mildew area is still 0% after the antibacterial plastic cup is cultured in a dark and humid environment for 30 days.
Drawings
Figure 1 is an SEM image of a silicon-based antimicrobial agent made according to example 1 of the present invention.
Figure 2 is an SEM image of a silicon-based antimicrobial agent made according to comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, TEOS used was commercially available from Industrial chemical industries, Ltd, Wuhan Gilg; the negative catalyst used was sodium dodecylbenzenesulfonate commercially available from alatin biochemical technology ltd; the polystyrene used was purchased from Zhenjianqimei; the silver ion doping concentration was detected by a microwave digestion test ICP (reference EPA 3052).
Example 1
(1) Silicon-based antibacterial agents
Stirring a mixed solution of 88% of deionized water, 2% of silver nitrate, 9.2% of TEOS and 0.8% of negative catalyst in a reaction kettle for reaction, aging, filtering, drying and calcining to obtain the silicon-based antibacterial agent; wherein the reaction time is 20 hours; the reaction temperature is 80 ℃; the reaction is carried out under the condition of stirring; the aging time was 20 hours. Wherein the drying is drying in a vacuum drying oven at 80 ℃; the calcining temperature is 800 ℃; the calcination time is 5 hours; each percentage is the percentage of the mass of each component to the total mass of each component in water.
The SEM image of the silicon-based antibacterial agent prepared in this example is shown in fig. 1, and a structure with a uniform primary particle size is formed, and D99 measured by a laser particle sizer is 0.3 to 0.5 μm, silver ions are uniformly distributed inside nano-silica, the doping concentration of the silver ions is 6%, and the particle size of the nano-silica is 50 to 300 nm.
(2) Antibacterial resin
And mixing 3% of the silicon-based antibacterial agent and 97% of polystyrene resin, and extruding to obtain the antibacterial resin. Wherein, the mixing is uniform mixing by a stirring device; the extrusion is melt extrusion by adopting a double-screw extruder; the percentage is the percentage of the mass of each component to the total mass of the antimicrobial resin.
(3) Antibacterial plastic cup
Extruding and molding the antibacterial resin in a mold, and demolding to obtain a plastic cup body; and (5) finely grinding and polishing the plastic cup body to obtain the antibacterial plastic cup.
Example 2
(1) Silicon-based antibacterial agents
Stirring a mixed solution of 86.5% of deionized water, 5% of zinc nitrate, 8% of TEOS and 0.5% of negative catalyst in a reaction kettle for reaction, aging, drying and calcining to obtain the silicon-based antibacterial agent; wherein the reaction time is 10 hours; the reaction temperature is 70 ℃; the reaction is carried out under stirring conditions; the aging time was 15 hours. Wherein the drying is drying in a vacuum drying oven at 80 ℃; the calcining temperature is 800 ℃; the calcination time is 6 hours; each percentage is the percentage of the mass of each component to the total mass of each component in water.
The silver ions of the silicon-based antibacterial agent prepared by the embodiment are uniformly distributed in the nano silicon oxide, the doping concentration of the zinc ions is 29%, and the particle size of the nano silicon oxide is 50-300 nm.
(2) Antibacterial resin
Mixing 1% of the silicon-based antibacterial agent and 99% of polystyrene resin, and extruding to obtain the antibacterial resin. Wherein the mixing is uniformly mixing by a stirring device; the extrusion is melt extrusion by adopting a double-screw extruder; the percentage is the percentage of the mass of each component to the total mass of the antimicrobial resin.
(3) Antibacterial plastic cup
Extruding and molding the antibacterial resin in a mold, and demolding to obtain a plastic cup body; and (5) finely grinding and polishing the plastic cup body to obtain the antibacterial plastic cup.
Example 3
(1) Silicon-based antibacterial agent
Stirring a mixed solution of 88.3% of deionized water, 4% of copper nitrate, 7% of TEOS and 0.7% of negative catalyst in a reaction kettle for reaction, aging, drying and calcining to obtain the silicon-based antibacterial agent; wherein the reaction time is 15 hours; the reaction temperature is 60 ℃; the reaction is carried out under the condition of stirring; the aging time was 15 hours. Wherein the drying is drying in a vacuum drying oven at 70 deg.C;
the calcining temperature is 800 ℃; the calcination time is 8 hours; each percentage is the percentage of the mass of each component to the total mass of each component in water.
Silver ions of the silicon-based antibacterial agent prepared by the embodiment are uniformly distributed in nano silicon oxide, the doping concentration of copper ions is 28%, and the particle size of the nano silicon oxide is 50-300 nm.
(2) Antibacterial resin
And mixing and extruding 2% of the silicon-based antibacterial agent and 98% of polystyrene resin to obtain the antibacterial resin. Wherein the mixing is uniformly mixing by a stirring device; the extrusion is melt extrusion by adopting a double-screw extruder; the percentage is the percentage of the mass of each component to the total mass of the antibacterial resin.
(3) Antibacterial plastic cup
Extruding and molding the antibacterial resin in a mold, and demolding to obtain a plastic cup body; and (4) finely grinding and polishing the plastic cup body to obtain the antibacterial plastic cup.
Comparative example 1
The raw materials, the method and the process parameters are the same as those of the example 2, but the addition amount of the negative catalyst is 0.3 percent, and the silicon-based antibacterial agent is prepared.
The SEM image of the silicon-based antibacterial agent prepared by the present comparative example is shown in fig. 2, and a non-uniform structure is formed. The aggregate structure with uneven primary particle size is 8-10 mu m when tested by a laser particle sizer D99.
Comparative example 2
The raw materials, the method and the process parameters are the same as those of example 2, but the addition amount of the negative catalyst is 2 percent, and the silicon-based antibacterial agent cannot be formed because the hydrolysis speed of TEOS is slower than the dissolution speed.
Effect example 1
(1) The plastic cups of examples 1 to 3, the plastic cup of comparative example 1 and a commercially available ordinary plastic cup were placed in the air, respectively, and after 18 hours, the number of escherichia coli on the surface of each plastic cup was measured, and the results are shown in table 1.
TABLE 1
(2) The plastic cups of examples 1 to 3, the plastic cup of comparative example 1 and a common plastic cup purchased in the market were placed in a dark and humid environment (humidity 70% and temperature 40 ℃) respectively and cultured for 30 days, and then the mildew condition of the plastic cup was observed, and the percentage of the mildew area on the surface of the plastic cup in the area of the whole plastic cup was counted.
TABLE 2
(3) Transparency: the plastic cups of examples 1 to 3 and comparative example 1 were cut into sheets having a thickness of 0.2 mm. + -. 0.01mm and tested using a glass-plastic transparency tester.
TABLE 3
| Experimental Material | Transparency% |
| Example 1 | 90.5 |
| Example 2 | 90.8 |
| Example 3 | 91.3 |
| Comparative example 1 | 63.5 |
(4) The plastic cups of examples 1 to 3 and comparative example 1 were each cut into specimens 30mm long, 10mm wide and 0.1mm thick, and the tensile strength test was conducted, and the results are shown in Table 3.
TABLE 4
| Experimental Material | Tensile strength MPa |
| Example 1 | 37 |
| Example 2 | 38 |
| Example 3 | 38 |
| Comparative example 1 | 29 |
(5) Cutting sample pieces with the length of 30mm, the width of 30mm and the thickness of 0.1mm from the plastic cups in the embodiments 1-3 and the comparative example 1 respectively, testing the yellowing resistance, putting the sample pieces into a xenon arc lamp aging test box meeting the GB/T18244 requirement, and testing the accumulated irradiation energy to be 1500MJ 2 /m 2 After (about 720h), the sample was taken out and tested for Lab value by a desktop colorimeter, wherein b is shown in the table.
Lab value: the Lab color model is a color calibration model specified by the international association for lighting, wherein:
l represents brightness, the range is 0-100, the darkest is 0, and the brightest is 100;
a is the color change from green to red, the range is-128 to +128, pure green is-128, pure red is +128, and 256 levels are formed between the pure green and the pure red.
b is the color change from blue to yellow, the range is-128- +128, pure blue is-128, pure yellow is +128, and 256 levels are formed between the pure blue and the pure yellow.
TABLE 5
| Experimental Material | B value before aging | B value after aging |
| Example 1 | 1.76 | 2.65 |
| Example 2 | 1.62 | 2.90 |
| Example 3 | 1.54 | 2.58 |
| Comparative example 1 | 1.88 | 4.78 |
The results in tables 1 to 5 show that the antibacterial resin and the antibacterial tableware prepared from the silicon-based antibacterial agent have excellent bactericidal performance and anti-mildew performance, and also have obviously excellent transparency and tensile strength, and the color change is smaller after the antibacterial resin and the antibacterial tableware are aged by ultraviolet light for 30 days, so that the antibacterial resin and the antibacterial tableware have excellent yellowing resistance.
As can be seen from the effect data in tables 1 to 5, in order to obtain an antibacterial tableware having excellent bactericidal effect, anti-mildew property, transparency, tensile strength and yellowing resistance at the same time, the above components and process conditions need to be matched with each other. For example, in comparative example 1, the content of the negative catalyst was too low, and the sterilizing effect, the anti-mold property, the transparency, the tensile strength and the yellowing resistance were all greatly reduced.
Claims (10)
1. A method for preparing a silicon-based antibacterial agent is characterized by comprising the following steps: reacting, aging, drying and calcining a mixed solution of 1-5% of water-soluble metal salt, 5-10% of hydrolyzable silicon source, 0.5-1% of negative catalyst and 84-93.5% of water, wherein the percentage of the water-soluble metal salt, the hydrolyzable silicon source and the negative catalyst is the percentage of the mass of each component to the total mass of the mixed solution;
wherein the water-soluble metal salt is a water-soluble salt of silver, zinc or copper; the temperature of the reaction is not higher than 90 ℃.
2. The method of claim 1, wherein the water soluble metal salt is one or more of silver nitrate, zinc nitrate, copper chloride, and copper sulfate; preferably one or more of silver nitrate, zinc nitrate and copper nitrate;
and/or the hydrolyzable silicon source is a silicon source which can generate silicon oxide through hydrolysis reaction; preferably TEOS; more preferably TEOS commercially available from GmbH, Industrial upgrading industries, Inc;
and/or the negative catalyst is an ammonium salt surfactant; preferably sodium dodecylbenzene sulfonate; more preferably sodium dodecylbenzenesulfonate commercially available from alatin biochemical technology ltd;
and/or the amount of the water-soluble metal salt is 2%, 4% or 5%;
and/or the hydrolyzable silicon source is used in an amount of 7%, 8%, or 9.2%;
and/or the amount of the negative catalyst is 0.5%, 0.7% or 0.8%;
and/or the amount of water is 86.5%, 88% or 88.3%;
and/or the water is deionized water;
and/or the reaction is a stirring reaction;
and/or the reaction temperature is 25-90 ℃, such as 60 ℃, 70 ℃ or 80 ℃;
and/or the reaction time is 10-20 hours; for example, 15 hours;
and/or the aging time is 10-20 hours; for example, 15 hours;
and/or the reaction and the aging environment is reaction and aging in a reaction kettle;
and/or, the step of drying also comprises filtration before the step of drying;
and/or, the drying environment is drying in a vacuum drying oven;
and/or the drying temperature is 70-80 ℃;
and/or the calcining temperature is 700-800 ℃;
and/or the calcining time is 5-10 hours; for example 6 hours or 8 hours;
and/or, the water-soluble metal salt is silver nitrate, the amount of the silver nitrate is 2%, the hydrolyzable silicon source is TEOS, the amount of the TEOS is 9.2%, the negative catalyst is sodium dodecylbenzenesulfonate, the amount of the sodium dodecylbenzenesulfonate is 0.8%, the reaction time is 20 hours, the reaction temperature is 80 ℃, the aging time is 20 hours, the drying is drying in a vacuum drying oven, the drying temperature is 80 ℃, the calcining temperature is 800 ℃, and the calcining time is 5 hours;
and/or, the water-soluble metal salt is zinc nitrate, the amount of zinc nitrate is 5%, the hydrolyzable silicon source is TEOS, the amount of TEOS is 8%, the negative catalyst is sodium dodecylbenzenesulfonate, the amount of sodium dodecylbenzenesulfonate is 0.5%, the reaction time is 10 hours, the reaction temperature is 70 ℃, the aging time is 15 hours, the drying is drying in a vacuum drying oven, the drying temperature is 80 ℃, the calcining temperature is 800 ℃, and the calcining time is 6 hours;
and/or, the water-soluble metal salt is copper nitrate, the amount of the copper nitrate is 4%, the hydrolyzable silicon source is TEOS, the amount of the TEOS is 7%, the negative catalyst is sodium dodecylbenzenesulfonate, the amount of the sodium dodecylbenzenesulfonate is 0.7%, the reaction time is 15 hours, the reaction temperature is 60 ℃, the aging time is 15 hours, the drying is drying in a vacuum drying oven, the drying temperature is 70 ℃, the calcining temperature is 800 ℃, and the calcining time is 8 hours.
3. A silicon-based antibacterial agent obtainable by the process for the preparation of a silicon-based antibacterial agent according to claim 1 or 2.
4. A silicon-based antibacterial agent, comprising nano-silica and metal cations distributed inside the nano-silica; wherein the D99 particle size of the silicon-based antibacterial agent is 0.1-1 mu m; the doping concentration of the metal cations is 5-30%; the particle size of the nano silicon oxide is 50-300 nm; the metal cations include one or more of silver ions, zinc ions, and copper ions.
5. An antibacterial resin, characterized in that it comprises the following components: 1-3% of a silicon-based antimicrobial agent according to claim 3 or 4 and 97-99% of a resin; the percentage is the percentage of the mass of each component to the total mass of the antibacterial resin.
6. The antimicrobial resin according to claim 5, wherein the resin is a polystyrene resin; preferably PS commercially available from zhenjiangqimei;
and/or the dosage of the silicon-based antibacterial agent is 2 percent;
and/or the amount of the resin is 98%.
7. The preparation method of the antibacterial resin is characterized by comprising the following steps: mixing and extruding the components of the antibacterial resin according to claim 5 or 6.
8. The method for producing an antibacterial resin according to claim 7, wherein the mixing is uniform mixing by a stirring device;
and/or, the extrusion is melt extrusion by a double-screw extruder.
9. An antibacterial resin obtained by the method for producing an antibacterial resin according to claim 7 or 8.
10. The preparation method of the antibacterial plastic cup is characterized by comprising the following steps of: extruding and polishing the antibacterial resin according to claim 9;
preferably, the extrusion molding is extrusion molding in a die; and/or, the polishing process may be conventional in the art, such as finish grinding polishing;
more preferably, a demolding operation is generally performed after the extrusion molding and before the polishing step.
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