CN117511117A - Visible light catalytic antibacterial plastic and preparation method and application thereof - Google Patents
Visible light catalytic antibacterial plastic and preparation method and application thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 81
- 229920003023 plastic Polymers 0.000 title claims abstract description 51
- 239000004033 plastic Substances 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 41
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 229910003077 Ti−O Inorganic materials 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 229920001661 Chitosan Polymers 0.000 description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 17
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 11
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 10
- 239000007822 coupling agent Substances 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- MSFSPUZXLOGKHJ-UHFFFAOYSA-N Muraminsaeure Natural products OC(=O)C(C)OC1C(N)C(O)OC(CO)C1O MSFSPUZXLOGKHJ-UHFFFAOYSA-N 0.000 description 1
- 108010013639 Peptidoglycan Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a visible light catalytic antibacterial plastic, and a preparation method and application thereof, and belongs to the technical field of high polymer materials, wherein the antibacterial plastic comprises the following raw materials in parts by weight: 140-160 parts of ABS resin particles and Nano-CTS/Ti O 2 0.5 to 5 parts of composite antibacterial agent, 0.5 to 5 parts of DOP plasticizer, 0.5 to 1 part of calcium-zinc stabilizer and 0.5 to 3 parts of silane coupling agent. Wherein Nano-CTS/TiO 2 The composite antibacterial agent takes CTS as a substrate, takes TPP as a crosslinking agent, prepares Nano-CTS particles by an ionic crosslinking method, and then prepares Nano-CTS and anatase phase Ti-O 2 The composite material is prepared by electrostatic assembly, and has photocatalysis effect and full-effect synergistic antibacterial capability. The prepared plastic can be widely applied to household appliances such as refrigerator cabinets and the like, and meets the health living demands of people on antibiosis and mildew prevention.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a visible light catalytic antibacterial plastic, and a preparation method and application thereof.
Background
Thermoplastic resin ABS (acrylonitrile-butadiene-styrene copolymer) which is one of five general resins in the world (polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS) and acrylonitrile-butadiene-styrene (ABS)) is a terpolymer of acrylonitrile, 1, 3-butadiene and styrene, is an engineering plastic with the largest yield, the most extensive application and excellent performance at present, has excellent performances of high strength, good toughness, easy processing and forming, good dimensional stability, good electrical insulation and the like, and is widely applied to the fields of household appliances, automobiles, mechanical parts and the like.
ABS plastic used as household appliances (e.g., refrigerator cases) has good comprehensive properties, but with the demands of people for safety, durability, stability, etc. of household appliances, there are demands for higher performance of ABS plastic. The household appliances (especially refrigerators, microwave ovens, etc.) have a large amount of microorganisms such as bacteria, mold, etc. in the use environment, which are easy to pollute the surface of the plastic shell and threaten the health of people. Therefore, the antibacterial property of the household appliance shell material is improved, and the antibacterial agent has important significance.
In the prior art, on one hand, the antibacterial property of ABS plastic used for the household appliance shell is improved by adding an antibacterial agent. Wherein, chitosan is used as a natural antibacterial agent, has high broad-spectrum antibacterial activity, is safe and environment-friendly, has wide sources and mature preparation process, and is widely used; however, the solubility is poor, and the antibacterial performance is unstable because the antibacterial agent is easily affected by factors such as molecular weight, deacetylation degree, pH and the like. On the other hand, the photocatalysis antibacterial technique is widely applied in the fields of household appliances, textile, water treatment and the like, and common photocatalysts comprise TiO 2 ZnO, cdS, etc., wherein TiO 2 As a photocatalyst antibacterial catalyst, the photocatalyst has the characteristics of strong chemical stability, excellent photocatalytic performance, high oxidability, safety, no toxicity, no pollution and low price, and has wide application in the fields of antibacterial mildew resistance, dye degradation and the like, and is used in TiO (titanium dioxide) 2 Anatase TiO among various crystal forms of (3) 2 The performance of (2) is most excellent. However, pure TiO 2 The powder is easy to agglomerate and is influenced by the structure of the powder, the photocatalysis and the antibiosis are influenced by illumination conditions, and anatase type TiO is prepared 2 While exhibiting excellent photocatalytic performanceThere are also a number of limitations: tiO (titanium dioxide) 2 Is weak in visible light response, and has a forbidden band width of 3.2eV, so that TiO is 2 Can be excited by light, requires ultraviolet light with the wavelength of light source less than 387nm, and the energy of the ultraviolet light only occupies about 4 percent of the solar energy, thus greatly limiting anatase TiO 2 Is used.
Therefore, there is a need for an antibacterial plastic with visible light catalytic function suitable for household appliances, especially refrigerators, and a preparation method thereof to solve the problems of poor solubility of chitosan and TiO 2 The problem of poor photocatalytic response activity is solved, the antibacterial plastic for the household appliances, especially the refrigerator shells, has synergistic antibacterial capability under dark conditions and visible light conditions, and the antibacterial performance of the antibacterial plastic for the household appliances is improved.
Disclosure of Invention
The invention aims to provide visible light catalytic antibacterial plastic and a preparation method and application thereof, which aim to solve the problems of poor chitosan solubility and poor TiO (titanium dioxide) in the background technology 2 The problem of poor photocatalytic response activity is solved, and the antibacterial plastic for the shells of household appliances, especially refrigerator, has synergistic antibacterial capability under dark conditions and visible light conditions.
The aim of the invention can be achieved by the following technical scheme:
the visible light catalytic antibacterial plastic comprises the following raw materials in parts by weight:
140-160 parts of ABS resin particles
Nano-CTS/TiO 2 0.5 to 5 portions of composite antibacterial agent
0.5 to 5 parts of DOP plasticizer (dioctyl phthalate)
0.5 to 1 part of calcium zinc stabilizer
Silane coupling agent 0.5-3 parts
Further, the coupling agent is a silane coupling agent, including KH550, KH560 or KH570, and preferably, KH550 is selected as the silane coupling agent.
Further, the Nano-CTS/TiO 2 The preparation method of the composite antibacterial agent comprises the following steps:
s1. Adding 2% acetic acid into CTS (chitosan) at 80deg.CHeating in a water bath kettle, stirring for 30min at a rotating speed of 500r/min, and uniformly mixing to obtain CTS solution; h was added at a rate of 1 drop (1 drop/4 s) at an interval of 4 seconds at a concentration of 3wt% 2 O 2 Continuously reacting the solution for 3 hours at 40 ℃ under the water bath condition to obtain a reaction solution A;
s2, regulating the pH value of the reaction solution A to be 4, adding Span-80 (Span 80), and stirring at a high speed of 600r/min for 30min to uniformly disperse Span-80 to obtain a reaction solution B;
s3, naturally cooling the reaction solution B to room temperature (25-30 ℃), dripping sodium Tripolyphosphate (TPP) in a molten state at a constant speed by using a needle tube at a dripping speed of 1 drop (1 drop/5 s) at intervals of 5 seconds, continuously stirring at a rotating speed of 400r/min for 30min, and standing for 1h to collect an upper layer solution to obtain a Nano-CTS dispersion;
s4, at room temperature, anatase type TiO 2 Diluting the sol with 2% acetic acid, stirring at 350r/min for 30min to obtain uniformly dispersed TiO 2 A solution; dripping 1 drop (1 drop/3 s) of Nano-CTS dispersion solution at a constant speed at intervals of 3 seconds through a constant pressure funnel, continuously stirring at a rotating speed of 350r/min for reaction for 1 hour, and performing suction filtration, washing and vacuum drying to obtain Nano-CTS/TiO 2 Composite nanomaterial.
Further, the mass fraction of the CTS solution in the S1 is 0.2% -1%.
Further, the CTS solution, H 2 O 2 The dosage ratio of the solution, span-80 and TPP is 1000mL:100mL:2g:0.4g.
Further, in S4, anatase type TiO 2 The volume ratio of the sol to the acetic acid is 1:1.
Further, tiO in S4 2 The volume ratio of the amount of the solution to the amount of the Nano-CTS dispersion was 1:6.
A preparation method of visible light catalytic antibacterial plastic comprises the following steps:
drying ABS resin in a forced air drying oven at 80 ℃ for 10 hours to obtain dried ABS resin granules, weighing the ABS resin granules and Nano-CTS/TiO according to the weight parts of the raw materials 2 Uniformly mixing the composite antibacterial agent, the plasticizer, the stabilizer and the coupling agent at the temperature of 40-60 ℃ to obtain a mixed material from a double screw rodGranulating in an extruder by using a granulator after extrusion to obtain ABS/Nano-CTS/TiO 2 The visible light catalytic antibacterial plastic is used after being dried by a blast drying oven.
Further, the twin-screw extruder is provided with six temperature intervals of 190-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively.
Further, the ABS resin pellet and Nano-CTS/TiO 2 The composite antibacterial agent, the plasticizer, the stabilizer and the coupling agent are stirred for 30min at the temperature of 40-60 ℃ and the rotating speed of 200-300r/min and are uniformly mixed.
The invention provides application of visible light catalytic antibacterial plastic in household appliances.
The invention has the beneficial effects that:
1. the invention provides a visible light catalytic antibacterial plastic and a preparation method and application thereof, wherein the chitosan which is a natural polymer biomass material is used as an antibacterial component, has the advantages of no toxicity, degradability, reproducibility and the like, maintains high affinity to human bodies, has self-cleaning capability while greatly improving the antibacterial effect of the prepared visible light catalytic antibacterial plastic, can generate antibacterial effect under visible light, and overcomes the defects of TiO (titanium dioxide) 2 The photocatalyst has the advantages that the photocatalyst is limited to the ultraviolet light, and the antibacterial activity of chitosan is not influenced by the illumination condition, so that the synergistic antibacterial effect can be generated under the dark condition or visible light, the antibacterial and photocatalytic capabilities of antibacterial plastics are further enhanced, and the national environmental protection and low carbon guidelines are met; the visible light catalytic antibacterial plastic prepared by the invention is applied to household appliances such as refrigerator and cabinet, not only meets the health living demands of people on antibacterial and mildew-proof, but also has important value on reducing the transmission of viruses and diseases.
2. The invention takes natural antimicrobial chitosan as a substrate, takes sodium tripolyphosphate as a cross-linking agent, prepares Nano-CTS particles by an ionic cross-linking method, and then prepares Nano-CTS particles with anatase phase TiO 2 Preparing Nano-CTS/TiO by an electrostatic assembly method 2 The composite nano antibacterial material improves the dissolubility of chitosan and is mixed with ABS resinAfter combination, the ABS/Nano-CTS/TiO with visible light catalysis can be prepared 2 The antibacterial plastic has the visible light catalytic effect on the basis of playing the natural antibacterial activity of chitosan. The antibacterial plastic prepared from the composite material can produce an antibacterial effect under visible light, the antibacterial activity of chitosan is not influenced by light conditions, and a synergistic antibacterial effect can be produced under dark conditions or visible light, so that the antibacterial and photocatalytic capabilities of the plastic are further enhanced.
3. In the invention, due to the introduction of Nano-CTS particles, the Nano-CTS particles are irradiated with light and then are mixed with TiO 2 Generates LMCT action (complex-electron transfer), and Nano-CTS and TiO 2 The composite effect can effectively prevent TiO 2 The particles are agglomerated, and the small size and quantum effect of the nano material are fully exerted; tiO (titanium dioxide) 2 The medium photo-generated electron-hole can be attracted by a large amount of amino groups in the Nano-CTS, thus preventing TiO 2 Electron-hole of (a) are rapidly recombined, and amino in Nano-CTS can be combined with TiO 2 The hydroxyl groups in the CTS are complexed into bonds, and electrons excited on the CTS can be directly injected into TiO under the visible light 2 Further improving TiO 2 The photocatalytic response activity of (2) greatly broadens the TiO 2 Is free of TiO 2 The photocatalyst has the defect of photocatalysis only under ultraviolet light; the electron energy of the reducibility of the photo-generated electron-hole pair can react with the surrounding oxygen to generate active ionic oxygen, and the hole which is represented as the oxidability can decompose water on the surface of the nano particle and react with O 2 The molecule action generates hydroxyl free radical with extremely high oxidability, and can decompose most organic substances and prevent bacteria or viruses and other invasion so as to realize self-cleaning.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Nano-CTS/TiO 2 The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 2% acetic acid into CTS, heating in a water bath kettle at 80 ℃, stirring at a rotating speed of 500r/min for 30min, and uniformly mixing to obtain 500mL of 1% CTS solution; 50mL of H having a concentration of 3wt% was added dropwise at 1 drop at 4-second intervals 2 O 2 Continuously reacting the solution for 3 hours at 60 ℃ under the water bath condition to obtain a reaction solution A;
s2, regulating the pH value of the reaction solution A to be 4, adding 1g of Span-80, and stirring at a high speed of 600r/min for 30min to uniformly disperse the Span-80 to obtain a reaction solution B;
s3, naturally cooling the reaction solution B to room temperature, dropwise adding 0.2g of TPP in a molten state at uniform speed at intervals of 5 seconds and 1 drop by using a needle tube, continuously stirring at a rotating speed of 400r/min for 30min, standing for 1h, and collecting an upper layer solution to obtain 400mL of Nano-CTS dispersion liquid;
s4, at room temperature, anatase type TiO 2 The sol was diluted with 2% acetic acid, anatase TiO 2 The volume ratio of the sol to the acetic acid is 1:1, and the solution is stirred for 30min at 350r/min to obtain uniformly dispersed TiO 2 A solution; drop into Nano-CTS dispersion solution at constant speed of 1 drop at intervals of 3 seconds through constant pressure funnel, tiO 2 The volume ratio of the solution to the Nano-CTS dispersion is 1:6 (v/v); continuously stirring at a rotating speed of 350r/min for reaction for 1h, and performing suction filtration, washing and vacuum drying to obtain Nano-CTS/TiO 2 Composite nanomaterial.
Example 2
Nano-CTS/TiO 2 The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 2% acetic acid into CTS, heating in a water bath kettle at 80 ℃, stirring at a rotating speed of 500r/min for 30min, and uniformly mixing to obtain 500mL of 0.6% CTS solution; 50mL of H having a concentration of 3wt% was added dropwise at 1 drop at 4-second intervals 2 O 2 Continuously reacting the solution for 3 hours at 80 ℃ under the water bath condition to obtain a reaction solution A;
s2, S3, S4 are as in example 1.
Example 3
Nano-CTS/TiO 2 Preparation of composite antibacterial agentThe method comprises the following steps:
s1, adding 2% acetic acid into CTS, heating in a water bath kettle at 80 ℃, stirring at a rotating speed of 500r/min for 30min, and uniformly mixing to obtain 500mL of 0.2% CTS solution; 50mL of H having a concentration of 3wt% was added dropwise at 1 drop at 4-second intervals 2 O 2 Continuously reacting the solution for 3 hours at 40 ℃ under the water bath condition to obtain a reaction solution A;
s2, S3, S4 are as in example 1.
Example 4
A preparation method of visible light catalytic antibacterial plastic comprises the following steps:
drying ABS resin in 80 deg.C blast drying oven for 10 hr, mixing the dried 160 parts of ABS resin granules and 5 parts of Nano-CTS/TiO prepared in example 1 2 Stirring the composite antibacterial agent, 5 parts of DOP plasticizer, 1 part of calcium zinc heat stabilizer and 3 parts of KH550 coupling agent for 30min at the temperature of 60 ℃ at the rotating speed of 300r/min, extruding the obtained mixed material from a double-screw extruder provided with six temperature ranges of 190-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively; granulating by a granulator after extrusion to obtain ABS/Nano-CTS/TiO 2 The visible light catalytic antibacterial plastic is dried by a blast drying box for standby.
Example 5
A preparation method of visible light catalytic antibacterial plastic is the same as that of example 4, except that Nano-CTS/TiO 2 The composite antibacterial agent is prepared in example 2.
Example 6
A preparation method of visible light catalytic antibacterial plastic is the same as that of example 4, except that Nano-CTS/TiO 2 The composite antibacterial agent is prepared in example 3.
Example 7
A preparation method of visible light catalytic antibacterial plastic comprises the following steps:
drying ABS resin in 80 deg.c blast drying oven for 10 hr, and mixing the dried ABS resin pellet in 150 weight portions and ABS resin pellet in 2.5 weight portionsNano-CTS/TiO prepared in example 1 2 The composite antibacterial agent, 2.5 parts of DOP plasticizer, 0.75 part of calcium-zinc heat stabilizer and 1.5 parts of KH550 coupling agent are stirred at the temperature of 50 ℃ for 30min at the rotating speed of 250r/min, the obtained mixed material is extruded from a double screw extruder with six temperature ranges of 190-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively; granulating by a granulator after extrusion to obtain ABS/Nano-CTS/TiO 2 The visible light catalytic antibacterial plastic is dried by a blast drying box for standby.
Example 8
A preparation method of visible light catalytic antibacterial plastic, which is the same as that of example 7, is different in Nano-CTS/TiO 2 The composite antibacterial agent is prepared in example 2.
Example 9
A preparation method of visible light catalytic antibacterial plastic, which is the same as that of example 7, is different in Nano-CTS/TiO 2 The composite antibacterial agent is prepared in example 3.
Example 10
A preparation method of visible light catalytic antibacterial plastic comprises the following steps:
the ABS resin was dried in a forced air drying oven at 80℃for 10 hours, and 140 parts of ABS resin pellets and 0.5 part of Nano-CTS/TiO prepared in example 1 were dried in the above-mentioned proportions 2 Stirring the composite antibacterial agent, 0.5 part of DOP plasticizer, 0.5 part of calcium-zinc heat stabilizer and 0.5 part of KH550 coupling agent for 30min at the temperature of 40 ℃ at the rotating speed of 200r/min, extruding the obtained mixed material from a double-screw extruder with six temperature ranges of 190-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively; granulating by a granulator after extrusion to obtain ABS/Nano-CTS/TiO 2 The visible light catalytic antibacterial plastic is dried by a blast drying box for standby.
Example 11
A preparation method of visible light catalytic antibacterial plastic is the same as example 10, and is different in Nano-CTS/TiO 2 The compound antibacterial agent is an example2, preparing the product.
Example 12
A preparation method of visible light catalytic antibacterial plastic is the same as example 10, and is different in Nano-CTS/TiO 2 The composite antibacterial agent is prepared in example 3.
The photocatalytic antibacterial plastics prepared in examples 4 to 12 and comparative example 1 were subjected to antibacterial performance test under the conditions of continuous irradiation of visible light (natural light) at room temperature for 24 hours (day+night), and the strains selected for the antibacterial test were escherichia coli and staphylococcus aureus required by national standards, and average values were obtained by respectively testing 4 groups, and the test method was tested according to special requirements for antibacterial, degerming and purifying function antibacterial materials of household and similar appliances in GB21551.2-2010, and the results are shown in Table 1:
TABLE 1
As can be seen from the data in the table: by Nano-CTS/TiO 2 ABS/Nano-CTS/TiO prepared from composite material 2 The visible light catalytic antibacterial plastic can generate antibacterial effect under visible light, and more remarkably, the antibacterial activity of chitosan is not influenced by light conditions, and can also generate synergistic antibacterial effect under dark conditions or visible light, so that the antibacterial and photocatalytic capabilities of the plastic are further enhanced, and Nano-CTS/TiO is adopted 2 The antibacterial rate of the antibacterial plastic prepared by the composite material is greatly improved, and the Nano-CTS/TiO is realized within a certain dosage range 2 The concentration of the composite antibacterial agent is increased, the antibacterial effect is better, and the prepared ABS/Nano-CTS/TiO is also available 2 The visible light catalytic antibacterial plastic also has a self-cleaning effect. Wherein, the antibacterial effect of the strain is less than that of staphylococcus aureus under the influence of a thick peptidoglycan layer cell wall on the surface of escherichia coli.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The visible light catalytic antibacterial plastic is characterized by comprising the following raw materials in parts by weight: 140-160 parts of ABS resin particles and Nano-CTS/Ti O 2 0.5 to 5 parts of composite antibacterial agent, 0.5 to 5 parts of DOP plasticizer, 0.5 to 1 part of calcium-zinc stabilizer and 0.5 to 3 parts of silane coupling agent.
2. The visible light catalytic antibacterial plastic of claim 1, wherein the Nano-CTS/Ti O 2 The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 2% acetic acid into CTS, heating in a water bath kettle at 80 ℃, stirring at a rotating speed of 500r/min for 30min, and uniformly mixing to obtain CTS solution; then H with the concentration of 3wt% is added dropwise at the dropping speed of 1 drop/4 s 2 O 2 Continuously reacting the solution for 3 hours at 40 ℃ under the water bath condition to obtain a reaction solution A;
s2, regulating the pH value of the reaction solution A to be 4, adding Span-80, and stirring at a high speed of 600r/min for 30min to uniformly disperse Span-80 to obtain a reaction solution B;
s3, naturally cooling the reaction solution B to room temperature, dropwise adding molten sodium tripolyphosphate at a uniform speed of 1 drop/5 s, continuously stirring at a rotating speed of 400r/min for 30min, and standing for 1h to collect an upper layer solution to obtain Nano-CTS dispersion;
s4, at room temperature, anatase type TiO 2 Diluting the sol with 2% acetic acid, and dispersing uniformly to obtain Ti O 2 A solution; dripping into Nano-CTS dispersion liquid at a constant speed of 1 drop/3 s, stirring at a rotating speed of 350r/min for reaction for 1h, and performing suction filtration, washing and vacuum drying to obtain Nano-CTS/Ti O 2 Composite nanomaterial.
3. The visible light catalytic antibacterial plastic of claim 2, wherein the mass fraction of CTS solution in S1 is 0.2% -1%.
4. The visible light catalytic antibacterial plastic as set forth in claim 2, wherein said CTS solution, H 2 O 2 The dosage ratio of the solution, span-80 and TPP is 1000mL:100mL:2g:0.4g.
5. The visible light catalytic antibacterial plastic as claimed in claim 2, wherein anatase TiO in S4 2 The volume ratio of the sol to the acetic acid is 1:1.
6. The visible light catalytic antibacterial plastic of claim 2, wherein Ti O in S4 2 The volume ratio of the amount of the solution to the amount of the Nano-CTS dispersion was 1:6.
7. The visible light-catalyzed antimicrobial plastic of claim 1, wherein the silane coupling agent comprises KH550, KH560, or KH570.
8. The method for preparing the visible light catalytic antibacterial plastic according to claim 1, which is characterized by comprising the following steps:
drying ABS resin in 80 deg.c blast drying oven for 10 hr to obtain ABS resin granule, and further mixingWeighing the raw materials in parts by weight, and preparing ABS resin granules and Nano-CTS/Ti O 2 Uniformly mixing the composite antibacterial agent, DOP plasticizer, calcium-zinc stabilizer and silane coupling agent at 40-60 ℃, extruding and granulating the mixed material to obtain ABS/Nano-CTS/Ti O 2 Visible light catalyzed antibacterial plastics.
9. The method for preparing the visible light catalytic antibacterial plastic according to claim 8, wherein the mixture material sequentially passes through six temperature intervals in the extrusion process, and the six temperature intervals are 190-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ in sequence.
10. Use of the visible light-catalyzed antimicrobial plastic according to any one of claims 1 to 7 in household appliances.
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