CN115594908B - Antibacterial plastic and preparation method thereof - Google Patents
Antibacterial plastic and preparation method thereof Download PDFInfo
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- CN115594908B CN115594908B CN202211265919.4A CN202211265919A CN115594908B CN 115594908 B CN115594908 B CN 115594908B CN 202211265919 A CN202211265919 A CN 202211265919A CN 115594908 B CN115594908 B CN 115594908B
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- 229920003023 plastic Polymers 0.000 title claims abstract description 118
- 239000004033 plastic Substances 0.000 title claims abstract description 118
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 181
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 75
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 61
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 57
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 239000004599 antimicrobial Substances 0.000 claims description 32
- -1 polyethylene Polymers 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 25
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 19
- 230000000845 anti-microbial effect Effects 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 9
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 33
- 241000894006 Bacteria Species 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000002845 discoloration Methods 0.000 abstract description 4
- 230000001404 mediated effect Effects 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229940049292 n-(3-(dimethylamino)propyl)octadecanamide Drugs 0.000 description 2
- WWVIUVHFPSALDO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCN(C)C WWVIUVHFPSALDO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an antibacterial plastic and a preparation method thereof. The antibacterial plastic comprises a plastic base material and an antibacterial agent dispersed in the plastic base material, wherein the antibacterial agent comprises modified nano silicon dioxide and photocatalytic activity nano particles, the modified nano silicon dioxide is nano silicon dioxide modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano silicon dioxide. The surface of the modified nano silicon dioxide is positively charged, so that the adsorption capacity of the silicon dioxide to bacteria can be improved, meanwhile, the nano silicon dioxide modified by the cationic surfactant can be better combined with the photocatalytic active nano particles, and the obtained product has an inherent antibacterial effect and a photo-mediated antibacterial effect, so that a long-acting antibacterial effect and good biosafety are realized. Meanwhile, the silicon dioxide is modified, so that the compatibility with the plastic base stock is better. In addition, the photocatalytic active nano particles can absorb ultraviolet rays, so that the discoloration of the antibacterial plastic is improved.
Description
Technical Field
The invention relates to the technical field of antibiosis, in particular to an antibacterial plastic and a preparation method thereof.
Background
The plastic has the excellent characteristics of light weight, strong toughness, good wear resistance, acid and alkali resistance and the like, and has become a necessity for daily life. The antibacterial plastic can inhibit or kill bacteria, mold and the like stained on the antibacterial plastic, and keeps self-cleaning by inhibiting the propagation of microorganisms. At present, the antibacterial plastic is applied to the fields of daily necessities, household furniture, building materials, interior decoration materials and the like.
The inorganic antibacterial agent used in the antibacterial plastic is mainly an antibacterial agent containing silver, copper and other metal ions, however, heavy metal pollution exists, the compatibility of the antibacterial agent and plastic base materials is poor, and in addition, the antibacterial agent only plays an antibacterial role in the plastic and has a single function.
Disclosure of Invention
Based on the above, it is necessary to provide an antibacterial plastic and a preparation method thereof, so as to solve the problems of heavy metal pollution, poor compatibility of the antibacterial agent and plastic base materials and single function of the antibacterial agent in the antibacterial plastic.
One of the purposes of the invention is to provide an antibacterial plastic, which comprises the following scheme:
An antibacterial plastic comprises a plastic base material and an antibacterial agent dispersed in the plastic base material, wherein the antibacterial agent comprises modified nano silicon dioxide and photocatalytic active nano particles, the modified nano silicon dioxide is nano silicon dioxide modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano silicon dioxide.
In one embodiment, the mass fraction of the antibacterial agent in the antibacterial plastic is 0.1% -10%.
In one embodiment, the plastic base is selected from one or more of polyethylene, polypropylene, polystyrene, ABS resin, polyethylene terephthalate, and polybutylene terephthalate.
In one embodiment, the photocatalytically active nanoparticle is selected from at least one of nano titanium dioxide and nano zinc oxide.
In one embodiment, the cationic surfactant is selected from one or more of hydroxyethyllauryl dimethyl ammonium chloride, dimethyldiallylammonium chloride, stearamidopropyl dimethylamine, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, and octadecyldimethylbenzyl ammonium chloride, dodecyltrimethoxysilane.
In one embodiment, the mass ratio of the nano silicon dioxide to the cationic surfactant is 1:0.5-1:4.
In one embodiment, the mass ratio of the modified nano-silica to the photocatalytically active nanoparticles is 1:1-1:5.
In one embodiment, the nano silicon dioxide has a particle size of 20 nm-100 nm.
In one embodiment, the particle size of the photocatalytic active nanoparticle is 20 nm-100 nm.
The invention also aims to provide a preparation method of the antibacterial plastic, which comprises the following steps:
the preparation method of the antibacterial plastic comprises the following steps:
Dispersing nano silicon dioxide in water to obtain a dispersion liquid;
adding a cationic surfactant into the dispersion liquid to modify the nano silicon dioxide to obtain a modified liquid containing modified nano silicon dioxide;
Adding photocatalytic active nano particles into the modified liquid, stirring, mixing and drying to obtain an antibacterial agent;
Blending and molding the antibacterial agent and the plastic base material to obtain the antibacterial plastic.
In one embodiment, the step of blending the antimicrobial agent with the plastic base comprises:
Mixing the antibacterial agent with part of the plastic base material, extruding and granulating to obtain antibacterial master batch;
mixing the antibacterial master batch with the rest plastic base material, and hot-press molding.
Compared with the traditional scheme, the antibacterial plastic and the preparation method thereof have the following beneficial effects:
according to the antibacterial plastic and the preparation method thereof, the antibacterial agent is dispersed in the plastic base material, the cationic surfactant is used for modifying the nano silicon dioxide, the cationic surfactant is combined with negative charges on the surface of the nano silicon dioxide, the surface of the modified nano silicon dioxide is positively charged through the cationic surfactant, so that the adsorption capacity of the silicon dioxide to bacteria can be improved, the modified nano silicon dioxide has excellent antibacterial function due to the strong combination capacity with the active center of the bacteria, meanwhile, the nano silicon dioxide modified by the cationic surfactant can be better combined with the photocatalytic active nano particles, and the obtained product has an internal antibacterial effect and a photo-mediated antibacterial effect, so that the long-acting antibacterial effect and good biological safety are realized. Meanwhile, the silicon dioxide is modified by the cationic surfactant, so that the compatibility of the silicon dioxide and the plastic base material is better, and the antibacterial agent is uniformly dispersed in the plastic base material. In addition, since the photocatalytic active nano particles can absorb ultraviolet rays, the antibacterial agent can also play a role in improving discoloration of antibacterial plastics.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The antibacterial plastic of one embodiment of the invention comprises a plastic base material and an antibacterial agent dispersed in the plastic base material.
The antibacterial agent comprises modified nano silicon dioxide and photocatalytic active nano particles. The modified nano silicon dioxide is nano silicon dioxide modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano silicon dioxide.
According to the antibacterial plastic, the antibacterial agent is dispersed in the plastic base material, the cationic surfactant is used for modifying the nano silicon dioxide, the cationic surfactant is combined with negative charges on the surface of the nano silicon dioxide, the surface of the modified nano silicon dioxide is positively charged through the cationic surfactant for modifying the silicon dioxide, so that the adsorption capacity of the silicon dioxide to bacteria can be improved, the modified nano silicon dioxide has excellent antibacterial function due to the strong combination capacity with the active center of the bacteria, meanwhile, the nano silicon dioxide modified by the cationic surfactant can be better combined with the photocatalytic active nano particles, and the obtained product has an inherent antibacterial effect and a photo-mediated antibacterial effect, so that the long-acting antibacterial effect and good biological safety are realized.
Meanwhile, the silicon dioxide is modified by the cationic surfactant, so that the compatibility of the silicon dioxide and the plastic base material is better, and the antibacterial agent is uniformly dispersed in the plastic base material.
In addition, since the photocatalytic active nano particles can absorb ultraviolet rays, the antibacterial agent can also play a role in improving discoloration of antibacterial plastics.
In one example, the mass fraction of the antimicrobial agent in the antimicrobial plastic is 0.1% -10%. Further, in one example, the mass fraction of the antimicrobial agent in the antimicrobial plastic is 0.5% -2%. In some specific examples, the antimicrobial agent is present in the antimicrobial plastic at a mass fraction of 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, etc.
Alternatively, the plastic base may be selected from, but not limited to, one or more of Polyethylene (PE), polypropylene (PP), polystyrene (PS), ABS resin, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT).
In one example, the antimicrobial agent is dispersed in the plastic base material by mixing the antimicrobial agent with a portion of the plastic base material, extruding and granulating to obtain an antimicrobial master batch, mixing the antimicrobial master batch with the remaining plastic base material, and hot-press molding.
In the above example, the dispersibility of the antibacterial agent in the plastic can be effectively improved by preparing the antibacterial master batch, mixing the antibacterial master batch with the rest of the plastic base material, and hot-press molding, so that the antibacterial effect of the plastic can be further improved.
It will be appreciated that in other examples, the antimicrobial agent may be blended directly with the plastic base material in proportions, and the molding method is not limited to hot press molding, and may be injection molding, blow molding, compression molding, or the like.
The Zeta potentiometer is used for testing the potential of the modified nano silicon dioxide, and the surface of the modified nano silicon dioxide is positively charged, so that the adsorption capacity of the silicon dioxide to bacteria can be improved through modifying the silicon dioxide by the cationic surfactant.
Alternatively, the cationic surfactant may be selected from, but is not limited to, one or more of hydroxyethyllauryl dimethyl ammonium chloride, dimethyldiallylammonium chloride, stearamidopropyl dimethylamine, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, and octadecyldimethylbenzylammonium chloride, dodecyltrimethoxysilane.
In one example, the photocatalytically active nanoparticle is selected from at least one of nano titanium dioxide (TiO 2) and nano zinc oxide (ZnO).
In one example, the mass ratio of the nano-silica to the cationic surfactant is 1:0.5-1:4.
The above examples can obtain a better antibacterial effect by preferably selecting the mass ratio of the nanosilica to the cationic surfactant in the antibacterial agent.
Further, in one example, the mass ratio of the nanosilica to the cationic surfactant is 1:1 to 1:3.
The above examples can obtain a better antibacterial effect by further preferably selecting the mass ratio of nanosilica to cationic surfactant in the antibacterial agent.
In one example, the mass ratio of the modified nano-silica to the photocatalytically active nanoparticles is 1:1 to 1:5.
The above examples can obtain a better antibacterial effect by preferably selecting the mass ratio of the modified nano-silica to the photocatalytically active nano-particles in the antibacterial agent.
Further, in one example, the mass ratio of the modified nano-silica to the photocatalytically active nanoparticles is 1:2 to 1:4.
The above examples can obtain a better antibacterial effect by further preferably selecting the mass ratio of the modified nano-silica to the photocatalytically active nano-particles in the antibacterial agent.
In one example, the nanosilica has a particle size of 20nm to 100nm. Further, in one example, the nano-silica has a particle size of 40nm to 60nm.
In one example, the particle size of the photocatalytically active nanoparticle is 25nm to 60nm. Further, in one example, the particle size of the photocatalytic active nanoparticle is 40nm to 50nm.
Further, the invention also provides a preparation method of the antibacterial plastic of any example, which comprises the following steps:
step one, dispersing nano silicon dioxide in water to obtain a dispersion liquid.
And step two, adding a cationic surfactant into the dispersion liquid to modify the nano silicon dioxide, thereby obtaining a modified liquid.
And thirdly, adding the photocatalytic active nano particles into the modified liquid, stirring, mixing and drying to obtain the antibacterial agent.
And step four, blending the antibacterial agent with a plastic base material to obtain the antibacterial plastic.
According to the preparation method of the antibacterial plastic, the antibacterial agent is dispersed in the plastic base material, the cationic surfactant is used for modifying the nano silicon dioxide, the cationic surfactant is combined with negative charges on the surface of the nano silicon dioxide, the surface of the modified nano silicon dioxide is positively charged through the cationic surfactant, the adsorption capacity of the silicon dioxide to bacteria can be improved, the modified nano silicon dioxide has excellent antibacterial function due to the strong combination capacity with the active center of the bacteria, meanwhile, the nano silicon dioxide modified by the cationic surfactant can be better combined with the photocatalytic active nano particles, and the obtained product has an internal antibacterial effect and a photo-mediated antibacterial effect, so that the long-acting antibacterial effect and good biological safety are realized.
Meanwhile, the silicon dioxide is modified by the cationic surfactant, so that the compatibility of the silicon dioxide and the plastic base material is better, and the antibacterial agent is uniformly dispersed in the plastic base material.
In addition, since the photocatalytic active nano particles can absorb ultraviolet rays, the antibacterial agent can also play a role in improving discoloration of antibacterial plastics.
The preparation process of the preparation method is easy to operate and has high yield.
In one example, in the second step, stirring and mixing are performed at a speed of 500rpm to 800rpm.
In one example, the reaction time of the second step is 1h to 4h. In some specific examples, the reaction time of step two is 1h, 2h, 3h, 4h, etc.
In one example, in step three, the specific method of drying is to centrifuge the mixed product and then dry it in an oven.
In one example, the reaction time of the third step is 4-6 hours. In some specific examples, the reaction time of step three is 4h, 5h, 6h, etc.
In one example, in step four, the step of blending the antimicrobial agent with the plastic base includes:
mixing the antibacterial agent with part of plastic base material, extruding and granulating to obtain antibacterial master batch;
mixing the antibacterial master batch with the rest plastic base material, and hot-pressing to form.
In the above example, the dispersibility of the antibacterial agent in the plastic can be effectively improved by preparing the antibacterial master batch, mixing the antibacterial master batch with the rest of the plastic base material, and hot-press molding, so that the antibacterial effect of the plastic can be further improved.
In step four, extrusion granulation is performed using an extruder, such as a twin screw extruder.
In the manufacturing process of the antibacterial master batch, the temperature of an extruder is 175-185 ℃, the granulating and feeding rotating speed is 20-80 rpm, and the granulating speed is 5-10 rpm.
In one example, the hot press molding temperature is 190-210 ℃ and the pressure is 14-16T. In a specific example, the hot press molding temperature is 200 ℃ and the pressure is 15T.
It will be appreciated that in other examples, the antimicrobial agent may be blended directly with the plastic base material in proportions, and the molding method is not limited to hot press molding, and may be injection molding, blow molding, compression molding, or the like.
The invention is further illustrated by the following examples, which are not intended to be limiting, it being understood that the appended claims outline the scope of the invention and that certain changes to the various embodiments of the invention will be covered by the spirit and scope of the claims, as directed to the inventive concepts.
Example 1
The preparation method of the antibacterial plastic comprises the following steps:
Step 1, adding nano silicon dioxide into water, and stirring and dispersing at a speed of 550rpm by using a magnetic stirrer to obtain a dispersion liquid. Wherein the nano silicon dioxide has a negative charge on the surface and a particle size of about 50 nm.
And 2, adding a cationic surfactant solution (dimethyl diallyl ammonium chloride) into the dispersion liquid obtained in the step 1. The mass ratio of the nano silicon dioxide to the cationic surfactant is 1:1. Stirring about 2h, and modifying the nano silicon dioxide by using a cationic surfactant to obtain a modified liquid containing the modified nano silicon dioxide.
And 3, adding a nano titanium dioxide solution into the modified liquid obtained in the step 2, wherein the particle size of the nano titanium dioxide is about 50 nm. The mass ratio of the modified nano silicon dioxide to the nano titanium dioxide is 1:2. Stirring 5 h, centrifugally collecting and drying in an oven to obtain the antibacterial agent.
And step 4, mixing the antibacterial agent with polyethylene, adding the mixture into a double-screw extruder for extrusion, and granulating the mixture by a granulator to obtain antibacterial master batches. The extruder temperature was 180 ℃, the feed rate was 20 rpm, and the pelletization rate was 10 rpm. And uniformly mixing the antibacterial master batch with polyethylene, performing injection molding and hot-press molding to obtain the antibacterial plastic, wherein the hot-press temperature is 200 ℃ and the pressure is 15T. The prepared antibacterial plastic is cut into a 50X 50 mm sample plate. The mass ratio of the antibacterial agent to the polyethylene is 1:99.
Example 2
This example produces an antimicrobial plastic in substantially the same manner as example 1, except that the mass ratio of antimicrobial agent to polyethylene is 3:97.
Example 3
This example produces an antimicrobial plastic in substantially the same manner as example 1, except that the mass ratio of antimicrobial agent to polyethylene is 5:95.
Example 4
This example produces an antimicrobial plastic in substantially the same manner as example 1, except that the mass ratio of antimicrobial agent to polyethylene is 7:93.
Example 5
This example produces an antimicrobial plastic in substantially the same manner as example 1, except that the mass ratio of antimicrobial agent to polyethylene is 10:90.
Example 6
The antibacterial plastic is prepared in the same manner as in example 1 except that the mass ratio of the nano silica to the cationic surfactant in the antibacterial agent is 2:1 and the mass ratio of the modified nano silica to the nano titania is 1:1.
Example 7
This example produces an antimicrobial plastic in substantially the same manner as example 1, except that the mass ratio of nanosilica to cationic surfactant in the antimicrobial agent is 1:2. The mass ratio of the modified nano silicon dioxide to the nano titanium dioxide is 1:2.
Example 8
The antibacterial plastic is prepared in the same manner as in example 1 except that the mass ratio of the nano silica to the cationic surfactant in the antibacterial agent is 1:3 and the mass ratio of the modified nano silica to the nano titania is 1:3.
Example 9
The antibacterial plastic is prepared in the same manner as in example 1 except that the mass ratio of the nano silica to the cationic surfactant in the antibacterial agent is 1:4 and the mass ratio of the modified nano silica to the nano titania is 1:5.
Example 10
The preparation method of the antibacterial plastic is basically the same as that of the embodiment 1, except that the cationic surfactant in the antibacterial agent is cetyl trimethyl ammonium chloride.
Example 11
The preparation method of the antibacterial plastic is basically the same as that of the embodiment 1, except that in the antibacterial agent, benzyl triethyl ammonium chloride is selected as the cationic surfactant.
Example 12
The preparation method of the antibacterial plastic is basically the same as that of the embodiment 1, except that the cationic surfactant in the antibacterial agent is octadecyldimethylbenzyl ammonium chloride.
Example 13
The preparation method of the antibacterial plastic is basically the same as that of the embodiment 1, except that the cationic surfactant in the antibacterial agent is dodecyl trimethoxy silane.
Example 14
The preparation method of the antibacterial plastic comprises the following steps:
Step 1, adding nano silicon dioxide into water, and stirring and dispersing at a speed of 550rpm by using a magnetic stirrer to obtain a dispersion liquid. Wherein the nano silicon dioxide has a negative charge on the surface and a particle size of about 50 nm.
And 2, adding a cationic surfactant solution (dimethyl diallyl ammonium chloride) into the dispersion liquid obtained in the step 1. The mass ratio of the nano silicon dioxide to the cationic surfactant is 1:4. Stirring about 2h, and modifying the nano silicon dioxide by using a cationic surfactant to obtain a modified liquid containing the modified nano silicon dioxide.
And 3, adding a nano zinc oxide solution into the modified liquid obtained in the step 2, wherein the particle size of the nano zinc oxide is about 50nm. The mass ratio of the modified nano silicon dioxide to the nano zinc oxide is 1:2. Stirring 5 h, centrifugally collecting and drying in an oven to obtain the antibacterial agent.
And step 4, mixing the antibacterial agent with polyethylene, adding the mixture into a double-screw extruder for extrusion, and granulating the mixture by a granulator to obtain antibacterial master batches. The extruder temperature was 180 ℃, the feed rate was 20 rpm, and the pelletization rate was 10 rpm. And uniformly mixing the antibacterial master batch with polyethylene, performing injection molding and hot-press molding to obtain the antibacterial plastic, wherein the hot-press temperature is 200 ℃ and the pressure is 15T. The prepared antibacterial plastic is cut into a 50X 50 mm sample plate. The mass ratio of the antibacterial agent to the polyethylene is 1:99.
Example 15
This example produces an antimicrobial plastic in substantially the same manner as example 2, except that the mass ratio of antimicrobial agent to polyethylene is 0.7:99.3.
Example 16
This example produces an antimicrobial plastic in substantially the same manner as example 2, except that the mass ratio of antimicrobial agent to polyethylene is 0.9:99.1.
Example 17
This example produces an antimicrobial plastic in substantially the same manner as example 2, except that the mass ratio of antimicrobial agent to polyethylene is 1:99.
Example 18
The preparation method of the antibacterial plastic is basically the same as that of the embodiment 2, except that the mass ratio of the antibacterial agent to the polyethylene is 2:98.
Example 19
The antibacterial plastic is prepared in the same manner as in example 1 except that the mass ratio of the nano silica to the cationic surfactant in the antibacterial agent is 2:1 and the mass ratio of the modified nano silica to the nano zinc oxide is 1:1.
Example 20
This example produces an antimicrobial plastic in substantially the same manner as example 1, except that the mass ratio of nanosilica to cationic surfactant in the antimicrobial agent is 1:2. The mass ratio of the modified nano silicon dioxide to the nano zinc oxide is 1:2.
Example 21
The antibacterial plastic is prepared in the same manner as in example 1 except that the mass ratio of the nano silica to the cationic surfactant in the antibacterial agent is 1:3 and the mass ratio of the modified nano silica to the nano zinc oxide is 1:3.
Example 22
The antibacterial plastic is prepared in the same manner as in example 1 except that the mass ratio of the nano silica to the cationic surfactant in the antibacterial agent is 1:4 and the mass ratio of the modified nano silica to the nano zinc oxide is 1:5.
Control group 1
The polyethylene is weighed and extruded by a double-screw extruder, and is pelletized by a pelletizer, wherein the temperature of the extruder is 180 ℃, the feeding rotation speed is 20 rpm, and the pelletizing speed is 10 rpm.
And uniformly mixing polyethylene particles with polyethylene, injection molding, and hot-press molding to obtain the plastic, wherein the hot-press temperature is 200 ℃ and the pressure is 15T. The prepared plastic was cut into 50 x 50mm templates.
Antibacterial detection and ultraviolet aging resistance detection are carried out on the antibacterial plastics obtained in examples 1-18 and the plastics in the control group 1, and detection results are shown in table 1.
TABLE 1
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. An antibacterial plastic is characterized by comprising a plastic base material and an antibacterial agent dispersed in the plastic base material, wherein the antibacterial agent comprises modified nano silicon dioxide and photocatalytic active nano particles, the modified nano silicon dioxide is nano silicon dioxide modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano silicon dioxide;
The mass ratio of the nano silicon dioxide to the cationic surfactant is 1:1-1:3;
the mass ratio of the modified nano silicon dioxide to the photocatalytic active nano particles is 1:2-1:4;
The photocatalytic active nano particles are selected from one or two of nano titanium dioxide and nano zinc oxide;
The mass fraction of the antibacterial agent in the antibacterial plastic is 1% -10%;
the cationic surfactant is selected from one or more of dimethyl diallyl ammonium chloride, benzyl triethyl ammonium chloride and cetyl trimethyl ammonium chloride.
2. The antimicrobial plastic of claim 1, wherein the plastic base is selected from one or more of polyethylene, polypropylene, polystyrene, ABS resin, polyethylene terephthalate, and polybutylene terephthalate.
3. The antimicrobial plastic of any one of claims 1-2, wherein the nanosilica has a particle size of 20nm to 100nm; and/or
The particle size of the photocatalytic active nano particles is 20 nm-100 nm.
4. An antimicrobial plastic according to claim 3, wherein the nanosilica has a particle size of from 40nm to 60nm.
5. An antimicrobial plastic according to claim 3, wherein the photocatalytically active nanoparticles have a particle size of 40nm to 50nm.
6. A method for preparing the antibacterial plastic according to any one of claims 1 to 5, comprising the following steps:
Dispersing nano silicon dioxide in water to obtain a dispersion liquid;
adding a cationic surfactant into the dispersion liquid to modify the nano silicon dioxide to obtain a modified liquid containing modified nano silicon dioxide;
Adding photocatalytic active nano particles into the modified liquid, stirring, mixing and drying to obtain an antibacterial agent;
Blending and molding the antibacterial agent and the plastic base material to obtain the antibacterial plastic.
7. The method of manufacturing an antimicrobial plastic according to claim 6, wherein the step of blending the antimicrobial agent with the plastic base comprises:
Mixing the antibacterial agent with part of the plastic base material, extruding and granulating to obtain antibacterial master batch;
mixing the antibacterial master batch with the rest plastic base material, and hot-press molding.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803898A (en) * | 2006-01-12 | 2006-07-19 | 贵州大学 | Nanometer antibacterial plastic |
| CN107383656A (en) * | 2017-07-13 | 2017-11-24 | 台山市心华药用包装有限公司 | A kind of nano antiseptic plastic bottle and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803898A (en) * | 2006-01-12 | 2006-07-19 | 贵州大学 | Nanometer antibacterial plastic |
| CN107383656A (en) * | 2017-07-13 | 2017-11-24 | 台山市心华药用包装有限公司 | A kind of nano antiseptic plastic bottle and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 纳米抗菌材料的研究进展;毛勇等;《塑料制造》(第9期);第58-62页 * |
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