CN114479238A - Antibacterial polyethylene material and preparation method thereof - Google Patents
Antibacterial polyethylene material and preparation method thereof Download PDFInfo
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- CN114479238A CN114479238A CN202210075218.8A CN202210075218A CN114479238A CN 114479238 A CN114479238 A CN 114479238A CN 202210075218 A CN202210075218 A CN 202210075218A CN 114479238 A CN114479238 A CN 114479238A
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- -1 polyethylene Polymers 0.000 title claims abstract description 133
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 131
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 93
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 126
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims abstract description 90
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 70
- 239000011787 zinc oxide Substances 0.000 claims abstract description 63
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 32
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims description 68
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims 4
- 244000005700 microbiome Species 0.000 abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 10
- 210000000170 cell membrane Anatomy 0.000 abstract description 7
- 230000035755 proliferation Effects 0.000 abstract description 6
- 210000002421 cell wall Anatomy 0.000 abstract description 3
- 238000001243 protein synthesis Methods 0.000 abstract description 3
- 230000014616 translation Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000003115 biocidal effect Effects 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application relates to the field of polyethylene, and particularly discloses an antibacterial polyethylene material and a preparation method thereof. The antibacterial polyethylene material comprises the following raw materials; high-density polyethylene, calcium carbonate, polyethylene wax, tetrapod-like zinc oxide whiskers, cinnamyl alcohol, toner and a coupling agent; the preparation method comprises the following steps: and (3) uniformly stirring all the raw materials, and extruding and granulating to obtain the antibacterial polyethylene material. According to the application, the tetrapod-like zinc oxide whiskers and the cinnamyl alcohol are adopted, the zinc ions on the tetrapod-like zinc oxide whiskers can penetrate through cell membranes and cell walls of microorganisms to destroy protein synthesis in the microorganisms, the tetrapod-like zinc oxide whiskers can release active oxygen and can destroy the proliferation capacity of the microorganisms, the cinnamyl alcohol can absorb and anchor the microorganisms contacting polyethylene materials, and then the microorganisms are fixed, so that the active oxygen and the zinc ions released by the tetrapod-like zinc oxide whiskers can act on the microorganisms continuously, the proliferation system of the microorganisms is further destroyed, and the antibacterial performance of the polyethylene materials is improved in a synergistic manner.
Description
Technical Field
The application relates to the field of polyethylene, in particular to an antibacterial polyethylene material and a preparation method thereof.
Background
In the market, containers for holding chemical products and plastic package of food are mostly made of polyethylene, and polyethylene has excellent low-temperature resistance, good chemical stability, resistance to corrosion of most of acid and alkali, excellent electrical insulation performance and wide application in multiple fields.
However, in the process of storing chemical products or food, bacteria are bred on the surface of the polyethylene material, so that the chemical products or food are easily polluted, and the quality of the chemical products or food is further influenced, and needs to be improved.
Disclosure of Invention
In order to solve the problem that the antibacterial performance of a polyethylene material is insufficient, the application provides an antibacterial polyethylene material and a preparation method thereof.
In a first aspect, the present application provides an antibacterial polyethylene material, which adopts the following technical scheme:
an antibacterial polyethylene material comprises the following raw materials in parts by weight;
75-85 parts of high-density polyethylene;
10-15 parts of calcium carbonate;
6-10 parts of polyethylene wax;
8-10 parts of tetrapod-like zinc oxide whiskers;
5-6 parts of cinnamyl alcohol;
3-5 parts of toner;
2-3 parts of a coupling agent.
By adopting the technical scheme, the tetrapod-like zinc oxide whisker has a three-dimensional tetrapod-like three-dimensional structure, a three-dimensional network framework is formed inside the polyethylene material after mixing, when a microorganism contacts any part of the framework, zinc ions penetrate through cell membranes and cell walls of the microorganism, and then protein synthesis in the microorganism is damaged, and the tetrapod-like zinc oxide whisker can release active oxygen, the active oxygen has extremely strong oxidizing capacity, when the active oxygen acts on the microorganism, the multiplication capacity of the microorganism can be damaged, and the antibacterial effect of the polyethylene material is comprehensively improved through the action of the active oxygen and the zinc ions.
The molecular structure of cinnamyl alcohol contains hydroxyl, the affinity between the cinnamyl alcohol and cell membranes is good, the cinnamyl alcohol can produce adsorption to the microorganism contacting polyethylene material, and the hydroxyl can enter the cell through the cell membranes and is combined with DNA, thereby producing anchoring effect to the microorganism cells, and further fixing the microorganism, so that the active oxygen released by the tetrapod-like zinc oxide whiskers and the zinc ions can continuously act on the microorganism, and simultaneously the DNA in the microorganism cells can form damage due to combination, further destroying the proliferation system of the microorganism, thereby synergistically improving the antibacterial performance of the polyethylene material.
Preferably, the raw materials also comprise 5-8 parts of sericite powder by weight.
By adopting the technical scheme, the sericite powder is a silicate mineral with a layered structure, and after the sericite powder is mixed with the tetrapod-like zinc oxide whiskers, as the needle point parts of the tetrapod-like zinc oxide whiskers reach the nanometer level, the needle point parts on the tetrapod-like zinc oxide whiskers can be inserted into the layered structure of the sericite powder to form an intercalation structure, so that zinc ions at the needle point parts of the tetrapod-like zinc oxide whiskers are slowly separated out, and the tetrapod-like zinc oxide whiskers can be favorable for generating a restraining effect on microorganisms for a long time.
Preferably, the raw material also comprises 10-15 parts of sulfuric acid solution by weight.
By adopting the technical scheme, hydrogen ions in the sulfuric acid solution replace cations among the sericite powder layers to form pore channels among the sericite powder layers, so that the sericite powder structure is unfolded to form a microporous network structure with a large specific surface area, the sericite powder is modified, the adsorption capacity of the sericite powder is improved, the needle points of the tetrapod-like zinc oxide whiskers easily enter the pore layer structure of the sericite powder, and the antibacterial effect of the polyethylene material is enhanced.
Preferably, the raw materials also comprise 4 to 6 parts of cyclosiloxane and 0.2 to 0.3 part of catalyst by weight part.
By adopting the technical scheme, the microorganisms are wet, the microorganisms are easy to breed in a large amount in a humid environment, and the cyclosiloxane and the cinnamyl alcohol are subjected to hydrosilylation under the action of the catalyst, so that Si-O-Si bonds are introduced into the cinnamyl alcohol, the surface energy of the polyethylene material is reduced, the surface of the polyethylene material is endowed with certain hydrophobic property, the residue of moisture on the surface of the polyethylene material is reduced, the breeding of the microorganisms is inhibited, and the antibacterial effect of the polyethylene material is indirectly improved.
Preferably, the raw material also comprises 6-7 parts of nano titanium dioxide by weight.
By adopting the technical scheme, the particle size of the nano titanium dioxide is nano, and the nano particles have special surface effect and small size effect, so that the nano titanium dioxide is endowed with extremely high catalytic activity, and can catalyze the tetrapod-like zinc oxide whiskers to generate more active oxygen, and the antibacterial performance of the polyethylene material is further improved.
In a second aspect, the present application provides a preparation method of an antibacterial polyethylene material, which adopts the following technical scheme:
a preparation method of an antibacterial polyethylene material comprises the following steps: the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax and the coupling agent are stirred and mixed evenly, and are extruded and granulated at the temperature of 160-170 ℃ to prepare the antibacterial polyethylene material.
Preferably, the raw materials further comprise 5-8 parts of sericite powder, 10-15 parts of sulfuric acid solution, 4-6 parts of cyclosiloxane, 0.2-0.3 part of catalyst and 6-7 parts of nano titanium dioxide in parts by weight;
the preparation method of the antibacterial polyethylene material comprises the following steps: stirring sericite powder and sulfuric acid solution at 80-90 deg.C for 3-4h to obtain modified sericite powder;
adding cinnamyl alcohol, cyclosiloxane and catalyst into solvent, stirring and mixing uniformly, introducing nitrogen, stirring and reacting for 5-6h at the temperature of 110-120 ℃, cooling to room temperature, filtering, and distilling under reduced pressure to obtain a product A;
the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the calcium carbonate, the polyethylene wax, the coupling agent, the modified sericite powder, the product A and the nano titanium dioxide are stirred and mixed uniformly, and are extruded and granulated at the temperature of 160-170 ℃ to prepare the antibacterial polyethylene material.
By adopting the technical scheme, the modification of the sericite powder, the reaction of the cinnamyl alcohol and the cyclosiloxane and the mixing of other raw materials are separately carried out, so that the interference of the other raw materials on the two reactions is reduced, and the modified sericite powder and the product A are obtained conveniently.
Preferably, the modified sericite powder is ground for 5-10min, then the tetrapod-like zinc oxide whiskers are added and stirred uniformly, then the high-density polyethylene, the toner, the calcium carbonate, the polyethylene wax, the coupling agent, the product A and the nano titanium dioxide are added and stirred uniformly, and extrusion granulation is carried out at 160-170 ℃ to prepare the antibacterial polyethylene material.
By adopting the technical scheme, the particle size of the modified sericite powder is refined by a mechanical means of friction, the internal energy of the modified sericite powder system is increased, the surface activity of the modified sericite powder is enhanced, the modified sericite powder and the tetrapod-like zinc oxide whiskers are attached, and the tetrapod-like zinc oxide whiskers have good dispersibility in polyethylene, so that the dispersion of the modified sericite powder in polyethylene can be promoted, and the improvement of the antibacterial effect of polyethylene is facilitated.
In summary, the present application has the following beneficial effects:
1. because the tetrapod-like zinc oxide whiskers and the cinnamyl alcohol are adopted, zinc ions on the tetrapod-like zinc oxide whiskers can penetrate through cell membranes and cell walls of microorganisms to destroy protein synthesis in the microorganisms, the tetrapod-like zinc oxide whiskers can release active oxygen and can destroy the proliferation capacity of the microorganisms, cinnamyl alcohol can generate an adsorption effect and an anchoring effect on the microorganisms contacting with the polyethylene material, and then the microorganisms are fixed, so that the active oxygen and the zinc ions released by the tetrapod-like zinc oxide whiskers can continuously act on the microorganisms, a proliferation system of the microorganisms is further destroyed, and the antibacterial performance of the polyethylene material is synergistically improved.
2. Sericite powder is preferably adopted in the application, and the needle tip on the tetrapod-like zinc oxide whisker can be inserted into the layered structure of the sericite powder to form an intercalation-like structure, which is beneficial to the lasting inhibition effect of the tetrapod-like zinc oxide whisker on microorganisms.
3. In the application, cyclosiloxane is preferably adopted, and the cyclosiloxane and cinnamyl alcohol are subjected to hydrosilylation under the action of a catalyst, so that the surface of the polyethylene material is endowed with certain hydrophobic property, and the residue of moisture on the surface of the polyethylene material is reduced, thereby being beneficial to inhibiting the breeding of microorganisms and indirectly improving the antibacterial effect of the polyethylene material.
Detailed Description
The present application will be described in further detail with reference to examples.
High density polyethylene was purchased from Suzhou Sunban plastication, Inc. under the designation LD100 AC; the polyethylene wax is purchased from Guangzhou Yifeng chemical and technology Limited company, and has the model of CH-4; the tetrapod-like zinc oxide whisker is purchased from Andi metal materials Co., Ltd, Qinghe county, and has the model of WZX 5; cinnamyl alcohol is purchased from Shandong national chemical Co., Ltd; the toner is titanium dioxide which is purchased from Yino chemical technology Co Ltd of Guangzhou city and has the model of R-350; the coupling agent adopts silane coupling agent KH-550; sericite powder is purchased from Touyi New materials (Guangzhou) Co., Ltd, and the mesh number is 1250 meshes; the concentration of the sulfuric acid solution is 10% (v/v); the catalyst adopts metal platinum; the nanometer titanium dioxide is purchased from Darcy concentrated nanometer technology (Changzhou) limited company, and the particle size is 5-10 nm; the solvent adopts dimethylbenzene; triisopropylsilane is available from Kepler Biotech, Inc. of Shandong under model number kpl-29302; the calcium carbonate crystal whisker is purchased from Shijiazhuang Lishang mineral product processing Co., Ltd, and has a product number of 325.
Note that,% (v/v) refers to volume percent.
The raw materials used in the following embodiments may be those conventionally commercially available unless otherwise specified.
Examples
Example 1
The application discloses antibiotic polyethylene material, including following raw materials: the high-density polyethylene, calcium carbonate, polyethylene wax, tetrapod-like zinc oxide whisker, cinnamyl alcohol, toner and a coupling agent, wherein the contents of the components are shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
and uniformly stirring and mixing the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax and the coupling agent, feeding the mixture into a double-screw extruder, and extruding and granulating at 160 ℃ at the rotating speed of 200RPM to obtain the antibacterial polyethylene material.
Example 2
The application discloses antibiotic polyethylene material, including following raw materials: the high-density polyethylene, calcium carbonate, polyethylene wax, tetrapod-like zinc oxide whisker, cinnamyl alcohol, toner and a coupling agent, wherein the contents of the components are shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
and uniformly stirring and mixing the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax and the coupling agent, feeding the mixture into a double-screw extruder, and extruding and granulating at 170 ℃ at the screw rotating speed of 200RPM to obtain the antibacterial polyethylene material.
Example 3
The application discloses antibiotic polyethylene material, including following raw materials: the high-density polyethylene, calcium carbonate, polyethylene wax, tetrapod-like zinc oxide whisker, cinnamyl alcohol, toner and a coupling agent, wherein the contents of the components are shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
and uniformly stirring and mixing the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax and the coupling agent, feeding the mixture into a double-screw extruder, and extruding and granulating at 165 ℃ at the screw rotating speed of 200RPM to obtain the antibacterial polyethylene material.
Example 4
The difference from example 1 is that sericite powder is added to the raw materials, and the contents of the components are shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax, the sericite powder and the coupling agent are stirred and mixed uniformly, and then the mixture is sent into a double-screw extruder, the rotating speed of the screw is 200RPM, and the mixture is extruded and granulated at 160 ℃, so that the antibacterial polyethylene material is prepared.
Example 5
The difference from example 4 is that a sulfuric acid solution was added to the raw material, and the contents of the respective components are shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
stirring the sericite powder and a sulfuric acid solution for 4 hours at 80 ℃ to prepare modified sericite powder;
the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax, the modified sericite powder and the coupling agent are stirred and mixed uniformly, and then the mixture is sent into a double-screw extruder, the rotating speed of a screw is 200RPM, and the mixture is extruded and granulated at 160 ℃, so that the antibacterial polyethylene material is prepared.
Example 6
The difference from example 5 is that the contents of the respective components are shown in the following Table 1-1, differing in the preparation method.
The preparation method of the antibacterial polyethylene material comprises the following steps:
stirring the sericite powder and a sulfuric acid solution for 4 hours at 80 ℃ to prepare modified sericite powder;
grinding the modified sericite powder for 5min at the speed of 100RPM, adding the tetrapod-like zinc oxide whiskers, stirring and mixing uniformly, adding the high-density polyethylene, the toner, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax and the coupling agent, stirring and mixing uniformly, feeding the mixture into a double-screw extruder, extruding and granulating at the temperature of 160 ℃ at the screw rotating speed of 200RPM, and thus obtaining the antibacterial polyethylene material.
Example 7
The difference from example 1 is that cyclosiloxane and catalyst are added to the raw materials, and the contents of each component are shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
adding cinnamyl alcohol, cyclosiloxane and catalyst into 300ml of solvent, uniformly stirring, introducing nitrogen, stirring and reacting for 6 hours at 110 ℃, naturally cooling to room temperature, filtering, and distilling under reduced pressure to obtain a product A;
and uniformly stirring and mixing the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the calcium carbonate, the polyethylene wax, the product A and the coupling agent, feeding the mixture into a double-screw extruder, and extruding and granulating at 160 ℃ at the rotating speed of 200RPM of the screws to obtain the antibacterial polyethylene material.
Example 8
The difference from the example 1 is that the nano titanium dioxide is added into the raw material, and the content of each component is shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax, the nano titanium dioxide and the coupling agent are stirred and mixed uniformly, and then the mixture is sent into a double-screw extruder, the rotating speed of the screw is 200RPM, and the mixture is extruded and granulated at 160 ℃, so that the antibacterial polyethylene material is prepared.
Example 9
The application discloses antibiotic polyethylene material, including following raw materials: the high-density polyethylene coating comprises high-density polyethylene, calcium carbonate, polyethylene wax, tetrapod-like zinc oxide whiskers, cinnamyl alcohol, toner, a coupling agent, sericite powder, a sulfuric acid solution, cyclosiloxane, a catalyst and nano titanium dioxide, wherein the content of each component is shown in the following table 1-1.
The preparation method of the antibacterial polyethylene material comprises the following steps:
stirring the sericite powder and a sulfuric acid solution for 4 hours at 80 ℃ to prepare modified sericite powder;
adding cinnamyl alcohol, cyclosiloxane and catalyst into 300ml of solvent, uniformly stirring, introducing nitrogen, stirring and reacting for 6 hours at 110 ℃, naturally cooling to room temperature, filtering, and distilling under reduced pressure to obtain a product A;
grinding the modified sericite powder for 5min at the speed of 100RPM, adding the tetrapod-like zinc oxide whisker, stirring and mixing uniformly, adding the high-density polyethylene, the toner, the calcium carbonate, the polyethylene wax, the coupling agent, the product A and the nano titanium dioxide, stirring and mixing uniformly, feeding the mixture into a double-screw extruder, extruding and granulating at the screw rotating speed of 200RPM at 160 ℃ to obtain the antibacterial polyethylene material.
Example 10
The application discloses antibiotic polyethylene material, including following raw materials: the high-density polyethylene coating comprises high-density polyethylene, calcium carbonate, polyethylene wax, tetrapod-like zinc oxide whiskers, cinnamyl alcohol, toner, a coupling agent, sericite powder, a sulfuric acid solution, cyclosiloxane, a catalyst and nano titanium dioxide, wherein the content of each component is shown in the following table 1-2.
The preparation method of the antibacterial polyethylene material comprises the following steps:
stirring the sericite powder and a sulfuric acid solution for 3 hours at 90 ℃ to prepare modified sericite powder;
adding cinnamyl alcohol, cyclosiloxane and catalyst into 300ml of solvent, uniformly stirring, introducing nitrogen, stirring and reacting for 5 hours at 120 ℃, naturally cooling to room temperature, filtering, and distilling under reduced pressure to obtain a product A;
grinding the modified sericite powder for 10min at the speed of 100RPM, adding the tetrapod-like zinc oxide whiskers, stirring and mixing uniformly, adding the high-density polyethylene, the toner, the calcium carbonate, the polyethylene wax, the coupling agent, the product A and the nano titanium dioxide, stirring and mixing uniformly, feeding the mixture into a double-screw extruder, extruding and granulating at the screw rotating speed of 200RPM at 170 ℃ to obtain the antibacterial polyethylene material.
Example 11
The application discloses antibiotic polyethylene material, including following raw materials: the high-density polyethylene coating comprises high-density polyethylene, calcium carbonate, polyethylene wax, tetrapod-like zinc oxide whiskers, cinnamyl alcohol, toner, a coupling agent, sericite powder, a sulfuric acid solution, cyclosiloxane, a catalyst and nano titanium dioxide, wherein the content of each component is shown in the following table 1-2.
The preparation method of the antibacterial polyethylene material comprises the following steps:
stirring the sericite powder and a sulfuric acid solution at 85 ℃ for 4 hours to prepare modified sericite powder;
adding cinnamyl alcohol, cyclosiloxane and catalyst into 300ml of solvent, uniformly stirring, introducing nitrogen, stirring and reacting for 6 hours at 115 ℃, naturally cooling to room temperature, filtering, and distilling under reduced pressure to obtain a product A;
grinding the modified sericite powder for 8min at the speed of 100RPM, adding the tetrapod-like zinc oxide whisker, stirring and mixing uniformly, adding the high-density polyethylene, the toner, the calcium carbonate, the polyethylene wax, the coupling agent, the product A and the nano titanium dioxide, stirring and mixing uniformly, feeding the mixture into a double-screw extruder, extruding and granulating at the screw rotating speed of 200RPM and 165 ℃ to obtain the antibacterial polyethylene material.
Example 12
The difference from example 4 is that sericite powder was replaced with calcium carbonate and the contents of the respective components are shown in the following tables 1 to 2.
Example 13
The difference from example 7 is that the cyclosiloxane is replaced by triisopropylsilane, and the contents of the respective components are shown in tables 1 to 2 below.
Comparative example
Comparative example 1
The difference from example 1 is that an antibacterial polyethylene material without adding tetrapod-like zinc oxide whiskers and cinnamyl alcohol in the raw materials is used as a blank control group.
Comparative example 2
The difference from example 1 is that cinnamyl alcohol is replaced by ethanol, and the contents of each component are shown in tables 1-2 below.
Comparative example 3
The difference from example 1 is that the tetrapod-like zinc oxide whiskers were replaced with calcium carbonate whiskers, and the contents of the respective components are shown in tables 1 to 2 below.
Comparative example 4
The difference from example 1 is that no tetrapod-like zinc oxide whiskers were added to the raw material, and the contents of the respective components are shown in tables 1 to 2 below.
Comparative example 5
The difference from comparative example 4 is that cinnamyl alcohol is replaced by ethanol, and the contents of each component are shown in tables 1-2 below.
TABLE 1-1 ingredient content table (unit: g)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | |
| High density polyethylene | 750 | 850 | 800 | 750 | 750 | 750 | 750 | 750 | 750 |
| Calcium carbonate | 100 | 150 | 120 | 100 | 100 | 100 | 100 | 100 | 100 |
| Polyethylene wax | 60 | 100 | 80 | 60 | 60 | 60 | 60 | 60 | 60 |
| Tetrapod-like zinc oxide whisker/calcium carbonate whisker | 80 | 100 | 90 | 80 | 80 | 80 | 80 | 80 | 80 |
| Cinnamyl alcohol/ethanol | 50 | 60 | 55 | 50 | 50 | 50 | 50 | 50 | 50 |
| Toner powder | 30 | 50 | 40 | 30 | 30 | 30 | 30 | 30 | 30 |
| Coupling agent | 20 | 30 | 25 | 20 | 20 | 20 | 20 | 20 | 20 |
| Sericite powder/calcium carbonate | / | / | / | 50 | 50 | 50 | / | / | 50 |
| Sulfuric acid solution | / | / | / | / | 100 | 100 | / | / | 100 |
| Cyclosiloxane/triisopropylsilane | / | / | / | / | / | / | 40 | / | 40 |
| Catalyst and process for preparing same | / | / | / | / | / | / | 2 | / | 2 |
| Nano titanium dioxide | / | / | / | / | / | / | / | 60 | 60 |
TABLE 1-2 ingredient content table (unit: g)
| Example 10 | Example 11 | Example 12 | Example 13 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| High density polyethylene | 850 | 800 | 750 | 750 | 750 | 750 | 750 | 750 |
| Calcium carbonate | 150 | 120 | 100 | 100 | 100 | 100 | 100 | 100 |
| Polyethylene wax | 100 | 80 | 60 | 60 | 60 | 60 | 60 | 60 |
| Tetrapod-like zinc oxide whisker/calcium carbonate whisker | 100 | 90 | 80 | 80 | 80 | 80 | / | / |
| Cinnamyl alcohol/ethanol | 60 | 55 | 50 | 50 | 50 | 50 | 50 | 50 |
| Toner powder | 50 | 40 | 30 | 30 | 30 | 30 | 30 | 30 |
| Coupling agent | 30 | 25 | 20 | 20 | 20 | 20 | 20 | 20 |
| Sericite powder/calcium carbonate | 80 | 60 | 50 | / | / | / | / | / |
| Sulfuric acid solution | 150 | 120 | / | / | / | / | / | / |
| Cyclosiloxane/triisopropylsilane | 60 | 50 | / | 40 | / | / | / | / |
| Catalyst and process for preparing same | 3 | 2 | / | 2 | / | / | / | / |
| Nano titanium dioxide | 70 | 65 | / | / | / | / | / | / |
Performance test
(1) And (3) testing the antibacterial effect: 20g of each of the antibacterial polyethylene materials of examples 1 to 13 and comparative examples 1 to 5 was weighed as a sample, and each sample was immersed in a solution having a concentration of 103Putting the staphylococcus aureus liquid in a 40W lamp for irradiation, shaking for 1h at 25 ℃, measuring the bacterial number by adopting plate counting after finishing, comparing with the sample of the comparative example 1, calculating the bacteriostasis rate, and marking as X1The greater the bacteriostasis rate, the better the antibacterial effect, and the test results are shown in table 2 below.
(2) And (3) testing the durability of the antibacterial effect: the samples of examples 1, 4-5 and 12 which were tested for their antibacterial effect were taken out and washed clean with deionized water, dried at 40 deg.C and left to stand at room temperature for 90hWashing with deionized water, drying at 40 deg.C, naturally cooling to room temperature, and soaking the sample in water with concentration of 103Putting the staphylococcus aureus liquid in a 40W light for irradiation, shaking for 1h at 25 ℃, measuring the bacterial number by adopting plate counting after finishing, comparing with the sample data of the comparative example 1 in the antibacterial effect test, calculating the antibacterial rate, and marking as X2Calculating the difference (X) of the two bacteriostatic rates1-X2) The test results are shown in table 2 below.
(3) And (3) testing the waterproofness: the samples of examples 1, 7 and 13 were immersed in a water vessel at 25 ℃ for 12 hours, then the samples were taken out, wiped to remove surface water, and weighed (m)1) Then drying the sample at 100 ℃ to constant weight, taking out the sample, putting the sample into a container with a cover, naturally cooling the sample to room temperature, and weighing the sample again (m)2) And calculating the water absorption:
water absorption (%) = (m)1-m2）/m2×100%
The test results are shown in table 2 below.
TABLE 2 test results of examples and comparative examples
| Bacteriostasis rate X1/% | Bacteriostasis rate X2/% | Difference (X)1-X2）/% | Water absorption/%) | |
| Example 1 | 81.4 | 66.2 | 15.2 | 6.2 |
| Example 2 | 83.1 | / | / | / |
| Example 3 | 82.4 | / | / | / |
| Example 4 | 83.3 | 74.5 | 8.8 | / |
| Example 5 | 83.9 | 76.3 | 7.4 | / |
| Example 6 | 85.2 | / | / | / |
| Example 7 | 83.7 | / | / | 4.7 |
| Example 8 | 86.7 | / | / | / |
| Example 9 | 89.4 | / | / | / |
| Example 10 | 91.5 | / | / | / |
| Example 11 | 90.8 | / | / | / |
| Example 12 | 81.8 | 67.4 | 14.4 | / |
| Example 13 | 82.1 | / | / | 5.9 |
| Comparative example 1 | / | / | / | / |
| Comparative example 2 | 62.3 | / | / | / |
| Comparative example 3 | 56.9 | / | / | / |
| Comparative example 4 | 54.6 | / | / | / |
| Comparative example 5 | 42.6 | / | / | / |
In summary, the following conclusions can be drawn:
1. as can be seen from the combination of example 1 and comparative examples 1 to 5 and table 2, the joint addition of cinnamyl alcohol and tetrapod-like zinc oxide whiskers to the raw materials of the antibacterial polyethylene material can synergistically improve the antibacterial effect of the antibacterial polyethylene material, which may be due to: the affinity between cinnamyl alcohol and cell membrane is better, can produce adsorption to the microorganism that contacts the polyethylene material, and hydroxyl can permeate cell membrane entering cell inside and take place to combine with DNA, and then fixed microorganism for the active oxygen and the sustainable effect of zinc ion that four acicular zinc oxide whiskers released are on the microorganism, make the DNA in the microorganism cell form the damage because of combining simultaneously, further destroy the proliferation system of microorganism, thereby improved polyethylene material's antibacterial property in coordination.
2. As can be seen from the combination of examples 1, 4 and 12 and table 2, the addition of sericite powder to the raw materials of the antibacterial polyethylene material can improve the durability of the antibacterial property of the antibacterial polyethylene material, which may be due to: after the raw materials are mixed, the needle tip part of the tetrapod-like zinc oxide whisker can be inserted into the layered structure of the sericite powder to form an intercalation structure, so that zinc ions at the needle tip part of the tetrapod-like zinc oxide whisker are slowly separated out, and the tetrapod-like zinc oxide whisker can be helpful for generating a restraining effect on microorganisms for a long time.
3. It can be seen from the combination of examples 1, 4-5, and 12 and table 2 that the addition of the sericite powder modified by the sulfuric acid solution to the raw materials of the antibacterial polyethylene material is beneficial to improving the durability of the antibacterial property of the antibacterial polyethylene material, and the reason may be that: the hydrogen ions in the sulfuric acid solution replace cations among the sericite powder layers, so that the sericite powder is modified, the adsorption capacity of the sericite powder is improved, and the needle tip parts of the tetrapod-like zinc oxide whiskers are easier to enter the pore layer structure of the sericite powder.
4. As can be seen from the combination of examples 1, 5-6 and table 2, the grinding of the modified sericite powder before granulation helps to improve the antibacterial performance of the antibacterial polyethylene material, which may be due to: through a mechanical means of friction, the system internal energy of the modified sericite powder is increased, the surface activity of the modified sericite powder is enhanced, the modified sericite powder and the tetrapod-like zinc oxide whiskers are attached, the tetrapod-like zinc oxide whiskers have good dispersibility in polyethylene, the dispersion of the modified sericite powder in polyethylene can be promoted, and the antibacterial effect of the polyethylene can be improved.
5. As can be seen from the combination of examples 1, 7 and 13 and table 2, the addition of cyclosiloxane and catalyst to the raw materials of the antibacterial polyethylene material can improve the water resistance of the antibacterial polyethylene material, which may be due to: the cyclosiloxane and the cinnamyl alcohol are subjected to hydrosilylation under the action of a catalyst, so that Si-O-Si bonds are introduced into the cinnamyl alcohol, the surface energy of the polyethylene material is reduced, and the surface of the polyethylene material is endowed with certain hydrophobic property.
6. As can be seen from the combination of examples 1 and 8 and table 2, the addition of the nano titanium dioxide to the raw materials of the antibacterial polyethylene material can improve the antibacterial performance of the antibacterial polyethylene material, which may be due to: the nano particles have special surface effect and small size effect, endow the nano titanium dioxide with extremely high catalytic activity, can catalyze the tetrapod-like zinc oxide whiskers to generate more active oxygen, and further improve the antibacterial performance of the polyethylene material.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. An antibacterial polyethylene material is characterized by comprising the following raw materials in parts by weight;
75-85 parts of high-density polyethylene;
10-15 parts of calcium carbonate;
6-10 parts of polyethylene wax;
8-10 parts of tetrapod-like zinc oxide whiskers;
5-6 parts of cinnamyl alcohol;
3-5 parts of toner;
2-3 parts of a coupling agent.
2. The antimicrobial polyethylene material according to claim 1, wherein: the raw materials also comprise 5-8 parts of sericite powder by weight.
3. The antimicrobial polyethylene material according to claim 2, wherein: the raw materials also comprise 10-15 parts of sulfuric acid solution by weight.
4. The antimicrobial polyethylene material according to claim 1, wherein: the raw material also comprises 4-6 parts of cyclosiloxane and 0.2-0.3 part of catalyst according to the parts by weight.
5. The antimicrobial polyethylene material according to claim 1, wherein: the raw material also comprises 6-7 parts of nano titanium dioxide by weight.
6. A method for preparing the antibacterial polyethylene material of claim 1, comprising the steps of: the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the cinnamyl alcohol, the calcium carbonate, the polyethylene wax and the coupling agent are stirred and mixed evenly, and are extruded and granulated at the temperature of 160-170 ℃ to prepare the antibacterial polyethylene material.
7. The method for preparing an antibacterial polyethylene material according to claim 6, characterized in that: the raw materials also comprise 5 to 8 parts of sericite powder, 10 to 15 parts of sulfuric acid solution, 4 to 6 parts of cyclosiloxane, 0.2 to 0.3 part of catalyst and 6 to 7 parts of nano titanium dioxide according to parts by weight;
the preparation method of the antibacterial polyethylene material comprises the following steps: stirring sericite powder and sulfuric acid solution at 80-90 deg.C for 3-4h to obtain modified sericite powder;
adding cinnamyl alcohol, cyclosiloxane and catalyst into solvent, stirring and mixing uniformly, introducing nitrogen, stirring and reacting for 5-6h at the temperature of 110-120 ℃, cooling to room temperature, filtering, and distilling under reduced pressure to obtain a product A;
the high-density polyethylene, the toner, the tetrapod-like zinc oxide whiskers, the calcium carbonate, the polyethylene wax, the coupling agent, the modified sericite powder, the product A and the nano titanium dioxide are stirred and mixed uniformly, and are extruded and granulated at the temperature of 160-170 ℃ to prepare the antibacterial polyethylene material.
8. The method for preparing an antibacterial polyethylene material according to claim 7, characterized in that: grinding the modified sericite powder for 5-10min, adding the tetrapod-like zinc oxide whiskers, stirring and mixing uniformly, adding the high-density polyethylene, the toner, the calcium carbonate, the polyethylene wax, the coupling agent, the product A and the nano titanium dioxide, stirring and mixing uniformly, and extruding and granulating at the temperature of 160-170 ℃ to obtain the antibacterial polyethylene material.
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