CN115594908A - Antibacterial plastic and preparation method thereof - Google Patents
Antibacterial plastic and preparation method thereof Download PDFInfo
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- CN115594908A CN115594908A CN202211265919.4A CN202211265919A CN115594908A CN 115594908 A CN115594908 A CN 115594908A CN 202211265919 A CN202211265919 A CN 202211265919A CN 115594908 A CN115594908 A CN 115594908A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 123
- 239000004033 plastic Substances 0.000 title claims abstract description 123
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 74
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 69
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- -1 polyethylene Polymers 0.000 claims description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- 239000004698 Polyethylene Substances 0.000 claims description 22
- 239000005543 nano-size silicon particle Substances 0.000 claims description 22
- 229920000573 polyethylene Polymers 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 230000000845 anti-microbial effect Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 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
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 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
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 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
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- BKRJTJJQPXVRRY-UHFFFAOYSA-M dodecyl-(2-hydroxyethyl)-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCO BKRJTJJQPXVRRY-UHFFFAOYSA-M 0.000 claims description 3
- 229940049292 n-(3-(dimethylamino)propyl)octadecanamide Drugs 0.000 claims description 3
- WWVIUVHFPSALDO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCN(C)C WWVIUVHFPSALDO-UHFFFAOYSA-N 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 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
- 239000004599 antimicrobial Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- JRFBNCLFYLUNCE-UHFFFAOYSA-N zinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Zn+2] JRFBNCLFYLUNCE-UHFFFAOYSA-N 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
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- 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-silica and photocatalytic activity nano-particles, the modified nano-silica is modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano-silica. The modified nano-silica has positive charges on the surface, so that the adsorption force of the silica on bacteria can be improved, meanwhile, the nano-silica modified by the cationic surfactant can be better combined with photocatalytic activity nano-particles, and the obtained product has the inherent antibacterial effect and the light-mediated antibacterial effect, so that the long-acting antibacterial effect and the good biological safety are realized. Meanwhile, the silica is modified, so that the silica has better compatibility with plastic base materials. In addition, the photocatalytic activity of the nanoparticles can absorb ultraviolet rays, and thus 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 becomes a necessity in daily life. The antibacterial plastic can inhibit or kill bacteria, mold and the like stained on the antibacterial plastic, and keeps the antibacterial plastic clean by inhibiting the propagation of microorganisms. At present, antibacterial plastics are applied to the fields of daily necessities, home appliances, furniture, building materials, interior decoration materials and the like.
The inorganic antibacterial agent used in the antibacterial plastic is mainly an antibacterial agent containing metal ions such as silver, copper and the like, but the inorganic antibacterial agent has heavy metal pollution, the compatibility of the antibacterial agent and a plastic base material is poor, and in addition, the inorganic antibacterial agent only plays an antibacterial role in the plastic and has a single function.
Disclosure of Invention
Therefore, the antibacterial plastic and the preparation method thereof are needed to solve the problems of heavy metal pollution, poor compatibility of the antibacterial agent and the plastic base material and single function of the antibacterial agent in the antibacterial plastic.
One of the purposes of the invention is to provide an antibacterial plastic, and the scheme is as follows:
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-silica and photocatalytic activity nanoparticles, the modified nano-silica is modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano-silica.
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 nanoparticles are selected from at least one of nano-titania and nano-zinc oxide.
In one embodiment, the cationic surfactant is selected from one or more of hydroxyethyl lauryl dimethyl ammonium chloride, dimethyl diallyl ammonium chloride, stearamidopropyl dimethylamine, benzyl triethyl ammonium chloride, cetyl trimethyl ammonium bromide, and stearyl dimethyl benzyl ammonium chloride, dodecyl trimethoxy silane.
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 nano-particles is 1: 1 to 1: 5.
In one embodiment, the nano-silica has a particle size of 20nm to 100nm.
In one embodiment, the photocatalytically active nanoparticles have a particle size of 20nm to 100nm.
The invention also aims to provide a preparation method of the antibacterial plastic, which comprises the following steps:
a preparation method of 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-silica to obtain a modified liquid containing modified nano-silica;
adding photocatalytic active nano particles into the modified solution, stirring and mixing, and drying to obtain an antibacterial agent;
and 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 material to form a shape comprises:
mixing the antibacterial agent with part of the plastic base material, and extruding and granulating to obtain antibacterial master batch;
and mixing the antibacterial master batch with the rest of the plastic base material, and performing hot press molding.
Compared with the traditional scheme, the antibacterial plastic and the preparation method thereof have the following beneficial effects:
the antibacterial plastic and the preparation method thereof disperse the antibacterial agent in the plastic base material, the antibacterial agent adopts the cationic surfactant to modify the nano-silica, the cationic surfactant is combined with the negative charges on the surface of the nano-silica, the modified nano-silica is modified by the cationic surfactant, the surface of the modified nano-silica is positively charged, the adsorption force of the silica to bacteria can be improved, so that the modified nano-silica obtains strong combination capability with the active center of the bacteria and has excellent antibacterial function, meanwhile, the nano-silica modified by the cationic surfactant can be better combined with the photocatalytic active nano-particles, the obtained product has the inherent antibacterial function and the light-mediated antibacterial function, and the long-acting antibacterial effect and the good biological safety are realized. Meanwhile, the silicon dioxide is modified by the cationic surfactant, so that the silicon dioxide has better compatibility with the plastic base material and is beneficial to the uniform dispersion of the antibacterial agent in the plastic base material. In addition, since the photocatalytically active nanoparticles can absorb ultraviolet rays, the antibacterial agent can also play a role in improving discoloration of the antibacterial plastic.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" 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-silica is modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano-silica.
The antibacterial plastic is dispersed with an antibacterial agent in a plastic base material, the antibacterial agent adopts a cationic surfactant to modify nano-silica, the cationic surfactant is combined with negative charges on the surface of the nano-silica, the cationic surfactant is used for modifying the silica, the surface of the modified nano-silica is positively charged, the adsorption force of the silica on bacteria can be improved, the modified nano-silica obtains strong combination ability with the active center of the bacteria and has an excellent antibacterial function, meanwhile, the nano-silica modified by the cationic surfactant can be better combined with photocatalytic active nano-particles, the obtained product has an internal antibacterial effect and a light-mediated antibacterial effect, and the long-acting antibacterial effect and good biological safety are realized.
Meanwhile, the silicon dioxide is modified by the cationic surfactant, so that the silicon dioxide has better compatibility with the plastic base material and is beneficial to the uniform dispersion of the antibacterial agent in the plastic base material.
In addition, since the photocatalytically active nanoparticles can absorb ultraviolet rays, the antibacterial agent can also play a role in improving discoloration of the antibacterial plastic.
In one example, the mass fraction of the antibacterial agent in the antibacterial plastic is 0.1-10%. Further, in one example, the mass fraction of the antibacterial agent in the antibacterial plastic is 0.5-2%. In some specific examples, the mass fraction of the antimicrobial agent in the antimicrobial plastic is 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 antibacterial agent is dispersed in the plastic base material by mixing the antibacterial agent with a part of the plastic base material, extruding and granulating to obtain the antibacterial master batch, mixing the antibacterial master batch with the rest of the plastic base material, and hot-press molding.
In the above example, the antibacterial masterbatch is prepared first, and then the antibacterial masterbatch is mixed with the rest of the plastic base material, and hot-press molding is performed, so that the dispersibility of the antibacterial agent in the plastic can be effectively improved, and the antibacterial effect of the plastic can be further improved.
It is understood that in other examples, the antibacterial agent and the plastic base material may be directly blended according to the ratio, and the molding method is not limited to hot press molding, and may be injection molding, blow molding, compression molding, and the like.
The modified nano-silica is tested for potential by using a Zeta potentiometer, and the surface of the modified nano-silica is measured to be positively charged, so that the adsorption force of the silica on bacteria can be improved by modifying the silica by using the cationic surfactant.
Alternatively, the cationic surfactant may be selected from, but not limited to, one or more of hydroxyethyl lauryl dimethyl ammonium chloride, dimethyl diallyl ammonium chloride, stearamidopropyl dimethylamine, benzyl triethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride, and dodecyl trimethoxy silane.
In one example, the photocatalytically active nanoparticles are selected from nano-titanium dioxide (TiO) 2 ) And at least one of nano zinc oxide (ZnO).
In one example, the mass ratio of the nano-silica to the cationic surfactant is 1: 0.5 to 1: 4.
The above examples can achieve a better antibacterial effect by optimizing the mass ratio of the nanosilica to the cationic surfactant in the antibacterial agent.
Further, in one example, the mass ratio of the nano silicon dioxide to the cationic surfactant is 1: 1 to 1: 3.
The above examples can achieve a better antibacterial effect by further optimizing the mass ratio of the nanosilica to the cationic surfactant in the antibacterial agent.
In one example, the mass ratio of the modified nano-silica to the photocatalytically active nano-particles is 1: 1 to 1: 5.
The above examples can achieve better antibacterial effects by optimizing the mass ratio of the modified nanosilica to the photocatalytically active nanoparticles in the antibacterial agent.
Further, in one example, the mass ratio of the modified nano-silica to the photocatalytically active nano-particles is 1: 2 to 1: 4.
The above examples can achieve a better antibacterial effect by further optimizing 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 thereof, the nano silica has a particle size of 40nm to 60nm.
In one example, the photocatalytically active nanoparticles have a particle size of 25nm to 60nm. Further, in one example, the photocatalytically active nanoparticles have a particle size of 40nm to 50nm.
Further, the invention also provides a preparation method of the antibacterial plastic, which comprises the following steps:
step one, dispersing nano silicon dioxide in water to obtain a dispersion liquid.
And secondly, adding a cationic surfactant into the dispersion liquid to modify the nano silicon dioxide to obtain a modified liquid.
And step three, adding the photocatalytic active nano particles into the modified solution, stirring, mixing and drying to obtain the antibacterial agent.
And step four, blending the antibacterial agent and the 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 antibacterial agent adopts the cationic surfactant to modify the nano-silica, the cationic surfactant is combined with negative charges on the surface of the nano-silica, the modified nano-silica is modified by the cationic surfactant, the surface of the modified nano-silica is positively charged, the adsorption force of the silica on bacteria can be improved, the modified nano-silica obtains strong combination capability with the active center of the bacteria and has an excellent antibacterial function, meanwhile, the nano-silica modified by the cationic surfactant can be better combined with the photocatalytic active nano-particles, the obtained product has an inherent antibacterial effect and a light-mediated antibacterial effect, and the long-acting antibacterial effect and good biological safety are realized.
Meanwhile, the silicon dioxide is modified by the cationic surfactant, so that the silicon dioxide has better compatibility with the plastic base material and is beneficial to the uniform dispersion of the antibacterial agent in the plastic base material.
In addition, since the photocatalytically active nanoparticles can absorb ultraviolet rays, the antibacterial agent can also play a role in improving discoloration of the antibacterial plastic.
The preparation method has the advantages of easy operation and high yield.
In one example, in the second step, stirring and mixing are performed, and the stirring speed is 500rpm to 800rpm.
In one example, the reaction time of the second step is 1-4 h. 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 place the product in an oven for drying.
In one example, the reaction time of step three is 4h to 6h. In some specific examples, the reaction time of step three is 4h, 5h, 6h, etc.
In one example, in the fourth step, the step of blending the antibacterial agent with the plastic base material for molding comprises the following steps:
mixing the antibacterial agent with part of the plastic base material, and extruding and granulating to obtain antibacterial master batch;
mixing the antibacterial master batch with the rest plastic base material, and hot-press molding.
In the above example, the antibacterial masterbatch is prepared, then the antibacterial masterbatch is mixed with the rest of the plastic base material, and the mixture is hot-pressed, so that the dispersibility of the antibacterial agent in the plastic can be effectively improved, and the antibacterial effect of the plastic can be further improved.
In step four, extrusion granulation is carried out using an extruder, for example a twin-screw extruder.
The temperature of the extruder is 175-185 ℃, the granulating feeding speed is 20-80 rpm, and the granulating speed is 5-10 rpm in the manufacturing process of the antibacterial master batch.
In one example, the hot-press molding temperature is 190-210 ℃, and the pressure is 14-16T. In one specific example, the temperature of the hot press molding is 200 ℃ and the pressure is 15T.
It is understood that in other examples, the antibacterial agent and the plastic base material may be directly blended according to the ratio, and the molding method is not limited to the hot press molding, and may be injection molding, blow molding, compression molding, or the like.
The following examples are provided to further illustrate the present invention, but the invention is not limited to the examples described below, it being understood that the scope of the invention is outlined by the appended claims, and it will be appreciated by those skilled in the art that certain changes may be made in the embodiments of the invention in view of the above description, without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
The embodiment prepares the antibacterial plastic, and the preparation method comprises the following steps:
step 1, adding nano silicon dioxide into water, and stirring and dispersing at the speed of 550rpm by using a magnetic stirrer to obtain a dispersion liquid. Wherein, the surface of the nano silicon dioxide has negative charge and the particle size is about 50nm.
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. And stirring for about 2 hours, and modifying the nano-silica by using the cationic surfactant to obtain a modified solution containing the modified nano-silica.
And 3, adding a nano titanium dioxide solution into the modified solution obtained in the step 2, wherein the particle size of the nano titanium dioxide is about 50nm. The mass ratio of the modified nano silicon dioxide to the nano titanium dioxide is 1: 2. Stirring for 5h, centrifuging, collecting and drying in an oven to obtain the antibacterial agent.
And 4, mixing the antibacterial agent with polyethylene, adding the mixture into a double-screw extruder for extrusion, and granulating by a granulator to obtain the antibacterial master batch. The temperature of the extruder was 180 ℃, the feeding speed was 20rpm, and the pelletizing rate was 10rpm. And uniformly mixing the antibacterial master batch with polyethylene, performing injection molding, and performing 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 sample plate with the size of 50mm multiplied by 50 mm. The mass ratio of the antibacterial agent to the polyethylene is 1: 99.
Example 2
This example prepared an antibacterial plastic in substantially the same manner as in example 37 except that the mass ratio of the antibacterial agent to polyethylene was 3: 97.
Example 3
This example prepares an antimicrobial plastic in substantially the same manner as example 37, except that the mass ratio of antimicrobial to polyethylene was 5: 95.
Example 4
This example produced an antimicrobial plastic in substantially the same manner as in example 37, except that the mass ratio of the antimicrobial agent to the polyethylene was 7: 93.
Example 5
This example produced an antimicrobial plastic in substantially the same manner as in example 37, except that the mass ratio of the antimicrobial agent to the polyethylene was 10: 90.
Example 6
This example prepares an antibacterial plastic, the preparation method is basically the same as that of example 1, except that in the antibacterial agent, the mass ratio of the nano-silica to the cationic surfactant is 2: 1, and the mass ratio of the modified nano-silica to the nano-titania is 1: 1.
Example 7
This example prepares an antibacterial plastic, the preparation method is basically the same as example 1, except that in the antibacterial agent, the mass ratio of the nano-silica to the cationic surfactant is 1: 2. The mass ratio of the modified nano silicon dioxide to the nano titanium dioxide is 1: 2.
Example 8
This example prepares an antibacterial plastic, the preparation method is basically the same as that of example 1, except that in the antibacterial agent, the mass ratio of the nano-silica to the cationic surfactant is 1: 3, and the mass ratio of the modified nano-silica to the nano-titania is 1: 3.
Example 9
This example prepares an antibacterial plastic, the preparation method is basically the same as that of example 1, except that in the antibacterial agent, the mass ratio of the nano-silica to the cationic surfactant is 1: 4, and the mass ratio of the modified nano-silica to the nano-titania is 1: 5.
Example 10
This example prepares an antimicrobial plastic by a method substantially the same as that of example 1, except that cetyltrimethylammonium chloride is used as the cationic surfactant in the antimicrobial agent.
Example 11
The antibacterial plastic prepared in this example was prepared in substantially the same manner as in example 1, except that benzyltriethylammonium chloride was used as the cationic surfactant in the antibacterial agent.
Example 12
The preparation method of the antibacterial plastic is basically the same as that of the antibacterial plastic prepared in the embodiment 1, except that octadecyl dimethyl benzyl ammonium chloride is selected as the cationic surfactant in the antibacterial agent.
Example 13
This example prepared an antimicrobial plastic in substantially the same manner as in example 1, except that the cationic surfactant in the antimicrobial was dodecyl trimethoxysilane.
Example 14
The embodiment prepares the antibacterial plastic, and the preparation method comprises the following steps:
step 1, adding nano silicon dioxide into water, and stirring and dispersing at the speed of 550rpm by using a magnetic stirrer to obtain a dispersion liquid. Wherein, the surface of the nano silicon dioxide has negative charge and the particle size is about 50nm.
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 for about 2h, and modifying the nano silicon dioxide by the cationic surfactant to obtain a modified liquid containing the modified nano silicon dioxide.
And 3, adding a nano zinc oxide solution into the modified solution obtained in the step 2, wherein the particle size of the nano zinc oxide titanium dioxide is about 50nm. The mass ratio of the modified nano silicon dioxide to the nano zinc oxide is 1: 2. Stirring for 5h, centrifuging, collecting and drying in an oven to obtain the antibacterial agent.
And 4, mixing the antibacterial agent and polyethylene, adding the mixture into a double-screw extruder for extrusion, and granulating by using a granulator to obtain the antibacterial master batch. The temperature of the extruder was 180 ℃, the feeding speed was 20rpm, and the pelletizing rate was 10rpm. And uniformly mixing the antibacterial master batch with polyethylene, performing injection molding, and performing 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 sample plate with the size of 50mm multiplied by 50 mm. The mass ratio of the antibacterial agent to the polyethylene is 1: 99.
Example 15
This example prepared an antimicrobial plastic in substantially the same manner as in example 2, except that the mass ratio of the antimicrobial agent to the polyethylene was 0.7: 99.3.
Example 16
This example prepares an antimicrobial plastic in substantially the same manner as example 2, except that the mass ratio of antimicrobial to polyethylene is 0.9: 99.1.
Example 17
This example prepared an antimicrobial plastic in substantially the same manner as in example 2, except that the mass ratio of the antimicrobial agent to the polyethylene was 1: 99.
Example 18
This example prepared an antimicrobial plastic in substantially the same manner as in example 2, except that the mass ratio of the antimicrobial agent to the polyethylene was 2: 98.
Example 19
The antibacterial plastic is prepared by the same method as that of the embodiment 1, except that in the antibacterial agent, the mass ratio of the nano silicon dioxide to the cationic surfactant is 2: 1, and the mass ratio of the modified nano silicon dioxide to the nano zinc oxide is 1: 1.
Example 20
This example prepares an antibacterial plastic, the preparation method is basically the same as example 1, except that in the antibacterial agent, the mass ratio of the nano-silica to the cationic surfactant is 1: 2. The mass ratio of the modified nano silicon dioxide to the nano zinc oxide is 1: 2.
Example 21
This example prepares an antibacterial plastic, the preparation method is basically the same as that of example 1, except that in the antibacterial agent, the mass ratio of the nano-silica to the cationic surfactant is 1: 3, and the mass ratio of the modified nano-silica to the nano-zinc oxide is 1: 3.
Example 22
This example prepares an antibacterial plastic, the preparation method is basically the same as that of example 1, except that in the antibacterial agent, the mass ratio of the nano-silica to the cationic surfactant is 1: 4, and the mass ratio of the modified nano-silica to the nano-zinc oxide is 1: 5.
Control group 1
Weighing polyethylene, extruding the polyethylene by a double-screw extruder, and pelletizing by a pelletizer, wherein the temperature of the extruder is 180 ℃, the feeding rotating speed is 20rpm, and the pelletizing speed is 10rpm.
And uniformly mixing polyethylene particles with polyethylene, performing injection molding, and performing 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 plaques.
The antibacterial plastics obtained in examples 1 to 18 and the plastics of the control group 1 were subjected to bacteriostasis test and ultraviolet aging resistance test, and the test results are shown in table 1.
TABLE 1
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The 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-silica and photocatalytic activity nanoparticles, the modified nano-silica is modified by a cationic surfactant, and the cationic surfactant is combined with negative charges on the surface of the nano-silica.
2. The antibacterial plastic of claim 1, wherein the mass fraction of the antibacterial agent in the antibacterial plastic is 0.1-10%.
3. The antibacterial plastic of claim 1, wherein the plastic base is one or more selected from the group consisting of polyethylene, polypropylene, polystyrene, ABS resin, polyethylene terephthalate, and polybutylene terephthalate.
4. The antibacterial plastic of claim 1, wherein the photocatalytically active nanoparticles are selected from one or both of nano titanium dioxide and nano zinc oxide.
5. The antimicrobial plastic of claim 1, wherein the cationic surfactant is selected from one or more of hydroxyethyl lauryl dimethyl ammonium chloride, dimethyl diallyl ammonium chloride, stearamidopropyl dimethylamine, benzyl triethyl ammonium chloride, cetyl trimethyl ammonium bromide, and stearyl dimethyl benzyl ammonium chloride and dodecyl trimethoxy silane.
6. The antibacterial plastic of claim 1, wherein the mass ratio of the nano silicon dioxide to the cationic surfactant is 1: 0.5-1: 4.
7. The antibacterial plastic of claim 1, wherein the mass ratio of the modified nano-silica to the photocatalytically active nano-particles is 1: 1 to 1: 5.
8. The antibacterial plastic of any one of claims 1 to 7, wherein the nano silica has a particle size of 20nm to 100nm; and/or
The particle size of the photocatalytic activity nano-particles is 20 nm-100 nm.
9. The preparation method of the antibacterial plastic is characterized by 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-silica to obtain a modified liquid containing modified nano-silica;
adding photocatalytic active nano particles into the modified solution, stirring and mixing, and drying to obtain an antibacterial agent;
and blending and molding the antibacterial agent and the plastic base material to obtain the antibacterial plastic.
10. The method for preparing an antibacterial plastic according to claim 9, wherein the step of blending and molding the antibacterial agent and the plastic base material comprises:
mixing the antibacterial agent with part of the plastic base material, and extruding and granulating to obtain antibacterial master batches;
and mixing the antibacterial master batch with the rest of the plastic base material, and performing 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 |
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| 毛勇等: "纳米抗菌材料的研究进展", 《塑料制造》, no. 9, pages 58 - 62 * |
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