CN116606502A - PP antibacterial material and preparation method thereof - Google Patents
PP antibacterial material and preparation method thereof Download PDFInfo
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- CN116606502A CN116606502A CN202310753215.XA CN202310753215A CN116606502A CN 116606502 A CN116606502 A CN 116606502A CN 202310753215 A CN202310753215 A CN 202310753215A CN 116606502 A CN116606502 A CN 116606502A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 130
- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 86
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000010457 zeolite Substances 0.000 claims abstract description 86
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 45
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 44
- 239000011701 zinc Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000004332 silver Substances 0.000 claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000002480 mineral oil Substances 0.000 claims abstract description 13
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 33
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 22
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 22
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 22
- 101100501135 Escherichia coli O157:H7 ehaG gene Proteins 0.000 claims description 20
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- -1 silver ions Chemical class 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 description 62
- 238000012360 testing method Methods 0.000 description 18
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004383 yellowing Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012543 microbiological analysis Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
-
- 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
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application relates to the field of PP antibacterial materials, in particular to a PP antibacterial material and a preparation method thereof. The PP antibacterial material comprises the following raw materials in parts by weight: 97-98.5 parts of PP, 0.08-0.12 part of antioxidant, 0.08-0.12 part of white mineral oil, 0.5-0.8 part of dispersing agent and 0.5-0.8 part of antibacterial agent, wherein the antibacterial agent is nano zeolite antibacterial silver-carrying zinc composite antibacterial agent, the Ag mass percentage content is 0.1-0.2%, the Zn mass percentage content is 0.2-0.3%, and the particle size of the nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 70-90 nanometers. The PP antibacterial material obtained by utilizing the composite oxidant and the nano zeolite antibacterial silver-loaded zinc composite antibacterial agent has good antibacterial property and oxidation resistance, does not turn yellow after being boiled, has high production efficiency and low cost, and is suitable for mass production and applied to humidifiers and furniture.
Description
Technical Field
The application relates to the field of PP antibacterial materials, in particular to a PP antibacterial material and a preparation method thereof.
Background
Polypropylene is one of five general plastics in the world today, an important member of the high molecular materials, and is also the first synthetic isotactic polymer for realizing industrial mass production. The polypropylene resin has the advantages of abundant production raw materials, low production cost and light weight, is a thermoplastic resin which is easy to mold and process and has excellent physical and mechanical properties, has very wide application fields, and is widely applied to a plurality of fields such as household appliances, automobiles, office equipment, bathroom products, medical care and the like. Although there are many advantages of PP, there are also disadvantages in that PP must be modified to improve its properties. In addition, the organic polymer material is also easy to be corroded by harmful bacteria and fungi in the using process, so that the product is difficult to clean, the sanitary health standard of the product is influenced, and the humidifier prepared by the PP turns yellow after being boiled for 16 hours under the condition of 80 DEG hot water.
Disclosure of Invention
The application provides a PP antibacterial material and a preparation method thereof, aiming at solving the problems of antibacterial performance and yellowing of the PP material during water boiling.
In a first aspect, the present application provides a PP antibacterial material, which adopts the following technical scheme:
the PP antibacterial material comprises the following raw materials in parts by weight: 97-98.5 parts of PP, 0.08-0.12 part of antioxidant, 0.08-0.12 part of white mineral oil, 0.5-0.8 part of dispersing agent and 0.5-0.8 part of antibacterial agent, wherein the antibacterial agent is nano zeolite antibacterial silver-carrying zinc composite antibacterial agent, the Ag mass percentage content is 0.1-0.2%, the Zn mass percentage content is 0.2-0.3%, and the particle size of the nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 70-90 nanometers.
By adopting the technical scheme, the PP antibacterial material has good antibacterial property and oxidation resistance by selecting proper formula and reasonable proportion, does not turn yellow after being boiled, and is applied to various fields requiring antibacterial property, such as humidifiers and furniture. PP (polypropylene): as a matrix of the material, physical properties and mechanical strength of the material are provided. An antioxidant: is used for inhibiting the oxidation reaction of the polypropylene material and prolonging the service life of the material. White mineral oil: as a plasticizer, the flexibility and ductility of the polypropylene material can be improved. Dispersing agent: the method is used for improving the stability and uniform dispersion of the nano material and ensuring that the antibacterial agent is uniformly distributed in the material. Nano zeolite antibacterial silver-carrying iron composite antibacterial agent: by doping silver and iron simultaneously in the nano zeolite, the antibacterial effect is enhanced. The particle size is 70-90 nanometers, and the product has larger surface area and stronger sterilization capability. In conclusion, the components in the application have the mutual matching effect, and the comprehensive optimization of the antibacterial property and other physical properties of the material is realized through the synergistic effect.
Preferably, the preparation method of the nano zeolite antibacterial silver-zinc composite antibacterial agent comprises the following steps:
s21, adding 1L of silver nitrate solution into 5L of nano zeolite suspension, mixing and stirring to enable silver ions to react with nano zeolite to form silver doped nano zeolite;
s22, adding 1L of zinc nitrate solution into the silver-doped nano zeolite suspension, mixing and stirring to enable iron ions and the silver-doped nano zeolite to react to form silver-zinc composite doped nano zeolite;
s23, performing treatments such as precipitation, washing and the like on the prepared silver-zinc composite doped nano zeolite to remove unreacted salts and impurities; s24, drying the washed sample to enable the sample to be completely dried;
s25, grinding the dried sample to obtain nano zeolite antibacterial silver-zinc composite antibacterial agent with the particle size of 70-90 nanometers.
Preferably, in step S21, the mass solubility of the silver nitrate solution is 15g/L, the mass ratio of the nano zeolite suspension to deionized water is 1:1, and the mixing and stirring time is 30-50min.
Preferably, in step S22, the mass solubility of the zinc nitrate solution is 40g/L, and the mixing and stirring time is 45-60min.
Preferably, in step S24, the drying process is vacuum drying, and the process parameters are: vacuum degree is 2000-3000Pa, temperature is 60-70deg.C, and time is 1-2 hr.
By adopting the technical scheme, the nano zeolite in the antibacterial agent has larger specific surface area and adsorption capacity, can effectively adsorb and inhibit the growth of bacteria, and has the functions of silver and zinc: silver and zinc in the antibacterial agent have strong antibacterial activity, and can kill and inhibit the growth of bacteria. Silver has broad-spectrum antibacterial properties, and can destroy the cell structure and metabolism of bacteria, while zinc can interfere with the biological metabolic processes of bacteria. The synergistic effect of the two can enhance the antibacterial effect, the particle size is 70-90 nanometers, and the antibacterial agent has larger surface area and stronger bactericidal capacity.
Preferably, the antioxidant is a composition of 3-aminopropyl triethoxysilane and antioxidant H161 in a mass ratio of 1:6-8, and the antioxidant H161 is antioxidant H161 produced by Bulgerman company.
By adopting the technical scheme, the antioxidant has the function of preventing the PP antibacterial material from oxidation reaction under high-temperature long-time exposure, and prolonging the service life of the PP antibacterial material. The 3-aminopropyl triethoxy silane is an organic silicon compound, and the molecule of the organic silicon compound contains an organic group and a silicon oxygen bond, so that the organic silicon compound can form a chemical bond with a PP material, and the high temperature resistance and the oxidation resistance of the material are improved. The antioxidant H161 is an effective non-fading antioxidant and heat stabilizer, can provide outstanding performance, can intercept and neutralize free radicals generated in materials, effectively reduces the occurrence of oxidation reaction, is applied to long-term thermal stability at the temperature of up to 150 ℃, has effective processing stability, resists yellowing and degradation, is completely dissolved, and does not influence the transparency of the PP antibacterial material. The proportion of the 3-aminopropyl triethoxysilane and the antioxidant H161 is accurately controlled, the antioxidant effect can be improved, and no side effect is generated in the preparation process. The antioxidant can effectively inhibit the reaction of free radicals and oxygen in the PP antibacterial material, delay the aging speed of the material, stabilize the structure of the material, inhibit the oxidation reaction, and maintain the performance stability and the aging resistance of the material, thereby preventing the phenomena of color change, surface yellowing, embrittlement and the like of the PP material. Meanwhile, the yellowing problem of the PP antibacterial material after being boiled for 18 hours under the condition of 80 ℃ hot water is effectively inhibited, and the PP antibacterial material does not yellow after being boiled for 18 hours under the condition of 80 ℃ hot water.
Preferably, the dispersing agent is a composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate in a mass percentage of 1:2-4:1-3.
By adopting the technical scheme, the dispersing agent plays roles in promoting the uniform dispersion of raw materials and preventing agglomeration and precipitation of the materials. Specifically, polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate can form better compatibility with PP, the dispersibility of the material is enhanced, agglomeration and precipitation of the nano zeolite antibacterial silver-loaded zinc composite antibacterial agent in the material are prevented, and the quality and stability of the material are ensured. These three dispersants also act synergistically to enhance the dispersibility and stability of the material. The mixed use of the polyvinyl alcohol, the polyvinylpyrrolidone and the polymethyl methacrylate can better control the dispersion state and the particle size distribution of the material and improve the water resistance, the heat resistance and the antibacterial property of the material. Therefore, the dispersing agent plays a key role and cooperates with other raw materials, so that the PP antibacterial material has excellent performance and stability. In addition to enhancing the dispersibility and stability of the material, polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate have the following effects: the polyvinyl alcohol can improve the cohesiveness and viscosity of the material, is beneficial to the forming and processing process of the material, and the polyvinylpyrrolidone has higher solubility and solubility, can be better compatible with PP, reduces interfacial tension, and improves the interfacial adhesion and compatibility of the material. Polymethyl methacrylate has good dispersibility and stability, can effectively disperse nano zeolite antibacterial silver-loaded zinc composite antibacterial agent particles, prevent aggregation and precipitation of the nano zeolite antibacterial silver-loaded zinc composite antibacterial agent particles, and can also increase antibacterial performance and antibacterial effect of materials and improve antibacterial function of products. Therefore, the polyvinyl alcohol, the polyvinylpyrrolidone and the polymethyl methacrylate serve as the dispersing agent in the application to promote the uniform dispersion of various raw materials in the material, improve the stability and antibacterial performance of the material, and cooperate with other raw materials to enable the PP antibacterial material to have excellent performance and excellent antibacterial effect.
In a second aspect, the application provides a preparation method of a PP antibacterial material, which adopts the following technical scheme:
the preparation method of the PP antibacterial material adopts the raw materials of the PP antibacterial material, and comprises the following steps:
s81, adding 97-98.5 parts of PP and 0.08-0.12 part of white mineral oil into a stirring barrel according to parts by weight, and stirring to obtain a mixture A;
s82, adding 0.08-0.12 part of antioxidant, 0.5-0.8 part of dispersing agent and 0.5-0.8 part of antibacterial agent into the mixture A according to parts by weight, and stirring to obtain a mixture B;
s83, adding the mixture B into a hopper of a double-screw extruder, extruding, shearing and granulating by the double-screw extruder, wherein the diameter of a screw is 62mm, the length-diameter ratio of the screw is 39:1, and the temperature of each zone of the screw is as follows: the first zone 160-170 ℃, the second zone 170-180 ℃, the third zone 180-190 ℃, the fourth zone 190-195 ℃, the fifth zone 195-200 ℃ and the sixth zone 200-205 ℃.
Preferably, in step S81, the stirring time is 5 to 10 minutes.
Preferably, in step S82, the stirring time is 10 to 15 minutes.
By adopting the technical scheme, the prepared PP antibacterial material has good antibacterial property and oxidation resistance, does not turn yellow after being boiled, has the advantages of high production efficiency, low cost, suitability for mass production and the like, and is applied to various fields requiring antibacterial property, such as humidifiers and furniture.
In summary, the present application includes at least one of the following beneficial technical effects: the PP antibacterial material obtained by selecting a proper formula and a reasonable proportion and utilizing the composite oxidant and the nano zeolite antibacterial silver-loaded zinc composite antibacterial agent has good antibacterial performance and oxidation resistance, does not turn yellow after being boiled, has the advantages of high production efficiency, low cost, suitability for mass production and the like, and is applied to various fields requiring antibacterial performance, such as humidifiers and furniture. Through 80 ℃ and 18-hour water boiling test of the PP antibacterial material, the test result does not turn yellow; through antibacterial tests, the antibacterial rates of escherichia coli and staphylococcus aureus are both more than 99.9%, and the antibacterial agent has excellent antibacterial performance.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, preparations, which are only for the purpose of illustrating the present application and should not be construed as limiting the scope of the present application, as will be understood by those skilled in the art. The specific conditions in the examples and preparations were not specified, and the examples and preparations were carried out under conventional conditions or conditions recommended by the manufacturer. The reagent or instrument used is not marked by manufacturers, is a conventional product which can be purchased from the market, PP is Dushanzi PP K8003, and antioxidant H161 is an antioxidant H161 of the Bulgeman company.
Example 1
The PP antibacterial material comprises the following raw materials in parts by weight: 97 parts of PP, 0.08 part of antioxidant, 0.08 part of white mineral oil, 0.5 part of dispersing agent and 0.5 part of nano zeolite antibacterial silver-carrying zinc composite antibacterial agent, wherein the Ag mass percent content of the nano zeolite antibacterial silver-carrying zinc composite antibacterial agent is 0.1%, the Zn mass percent content of the nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 0.2%, the particle size of nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 70-90 nanometers, the antioxidant is a composition of 3-aminopropyl triethoxysilane and antioxidant H161 according to the mass percent of 1:6, and the dispersing agent is a composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate according to the mass percent of 1:2:1.
The preparation method of the nano zeolite antibacterial silver-zinc composite antibacterial agent comprises the following steps:
s21, adding 1L of silver nitrate solution with mass solubility of 15g/L into 5L of nano zeolite suspension, mixing and stirring the nano zeolite of the zeolite suspension and deionized water in a mass ratio of 1:1 for 30min, and enabling silver ions and the nano zeolite to react to form silver doped nano zeolite;
s22, adding 1L of zinc nitrate solution with mass solubility of 40g/L into silver-doped nano zeolite suspension, mixing and stirring for 45min to enable iron ions and silver-doped nano zeolite to react to form silver-zinc composite doped nano zeolite;
s23, performing treatments such as precipitation, washing and the like on the prepared silver-zinc composite doped nano zeolite to remove unreacted salts and impurities; s24, drying the washed sample, wherein the drying is vacuum drying, and the technological parameters are as follows: the vacuum degree is 2000Pa, the temperature is 60 ℃ and the time is 1 hour, so that the sample is completely dried;
s25, grinding the dried sample to obtain nano zeolite antibacterial silver-zinc composite antibacterial agent with the particle size of 70-90 nanometers.
Example 2
The PP antibacterial material comprises the following raw materials in parts by weight: 98.5 parts of PP, 0.12 part of antioxidant, 0.12 part of white mineral oil, 0.8 part of dispersing agent and 0.8 part of nano zeolite antibacterial silver-carrying zinc composite antibacterial agent, wherein the Ag mass percent content of the nano zeolite antibacterial silver-carrying zinc composite antibacterial agent is 0.2%, the Zn mass percent content of the nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 0.3%, the particle size of nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 70-90 nanometers, the antioxidant is a composition of 3-aminopropyl triethoxysilane and antioxidant H161 according to the mass percent of 1:8, and the dispersing agent is a composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate according to the mass percent of 1:4:3.
The preparation method of the nano zeolite antibacterial silver-zinc composite antibacterial agent comprises the following steps:
s21, adding 1L of silver nitrate solution with mass solubility of 15g/L into 5L of nano zeolite suspension, mixing and stirring the nano zeolite of the zeolite suspension and deionized water in a mass ratio of 1:1 for 50min, and enabling silver ions and the nano zeolite to react to form silver doped nano zeolite;
s22, adding 1L of zinc nitrate solution with mass solubility of 40g/L into silver-doped nano zeolite suspension, mixing and stirring for 60min to enable iron ions and silver-doped nano zeolite to react to form silver-zinc composite doped nano zeolite;
s23, performing treatments such as precipitation, washing and the like on the prepared silver-zinc composite doped nano zeolite to remove unreacted salts and impurities; s24, drying the washed sample, wherein the drying is vacuum drying, and the technological parameters are as follows: the vacuum degree is 3000Pa, the temperature is 70 ℃ and the time is 2 hours, so that the sample is completely dried;
s25, grinding the dried sample to obtain nano zeolite antibacterial silver-zinc composite antibacterial agent with the particle size of 70-90 nanometers.
Example 3
The PP antibacterial material comprises the following raw materials in parts by weight: 98 parts of PP, 0.1 part of antioxidant, 0.1 part of white mineral oil, 0.65 part of dispersing agent and 0.65 part of nano zeolite antibacterial silver-carrying zinc composite antibacterial agent, wherein the Ag mass percent content of the nano zeolite antibacterial silver-carrying zinc composite antibacterial agent is 0.15%, the Zn mass percent content of the nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 0.25%, the particle size of nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 70-90 nanometers, the antioxidant is a composition of 3-aminopropyl triethoxysilane and antioxidant H161 according to the mass percent of 1:7, and the dispersing agent is a composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate according to the mass percent of 1:3:2.
The preparation method of the nano zeolite antibacterial silver-zinc composite antibacterial agent comprises the following steps:
s21, adding 1L of silver nitrate solution with mass solubility of 15g/L into 5L of nano zeolite suspension, mixing and stirring the nano zeolite of the zeolite suspension and deionized water in a mass ratio of 1:1 for 40min to enable silver ions and the nano zeolite to react to form silver doped nano zeolite;
s22, adding 1L of zinc nitrate solution with mass solubility of 40g/L into silver-doped nano zeolite suspension, mixing and stirring for 53min, and enabling iron ions and silver-doped nano zeolite to react to form silver-zinc composite doped nano zeolite;
s23, performing treatments such as precipitation, washing and the like on the prepared silver-zinc composite doped nano zeolite to remove unreacted salts and impurities; s24, drying the washed sample, wherein the drying is vacuum drying, and the technological parameters are as follows: the vacuum degree is 2500Pa, the temperature is 65 ℃ and the time is 1.5 hours, so that the sample is completely dried;
s25, grinding the dried sample to obtain nano zeolite antibacterial silver-zinc composite antibacterial agent with the particle size of 70-90 nanometers.
Comparative example 1
The same as in example 3, except that: the antioxidant is 0.1 part of 3-aminopropyl triethoxysilane.
Comparative example 2
The same as in example 3, except that: the antioxidant is antioxidant H161.1 weight portions.
Comparative example 3
The same as in example 3, except that: the dispersant is 0.65 part of polyvinyl alcohol.
Comparative example 4
The same as in example 3, except that: the dispersing agent is polyvinylpyrrolidone 0.65 part.
Comparative example 5
The same as in example 3, except that: the dispersant is polymethyl methacrylate 0.65 parts.
Preparation example 1
The preparation method of the PP antibacterial material adopts the raw materials in the embodiment 1, and comprises the following steps:
s81, adding 97kg of PP and 0.08kg of white mineral oil into a stirring barrel, and stirring for 5 minutes to obtain a mixture A; s82, adding 0.011kg of 3-aminopropyl triethoxysilane, 0.69kg of antioxidant H161, 0.125kg of polyvinyl alcohol, 0.25kg of polyvinylpyrrolidone, 0.125kg of polymethyl methacrylate and 0.5kg of nano zeolite antibacterial silver-loaded zinc composite antibacterial agent into the mixture A, and stirring for 10 minutes to obtain a mixture B;
s83, adding the mixture B into a hopper of a double-screw extruder, extruding, shearing and granulating by the double-screw extruder, wherein the diameter of a screw is 62mm, the length-diameter ratio of the screw is 39:1, and the temperature of each zone of the screw is as follows: the first zone 160 ℃, the second zone 170 ℃, the third zone 180 ℃, the fourth zone 190 ℃, the fifth zone 195 ℃ and the sixth zone 200 ℃.
Preparation example 2
The preparation method of the PP antibacterial material adopts the raw materials in the embodiment 2, and comprises the following steps:
s81, adding 98.5kg of PP98.12 kg of white mineral oil and 0.12kg of white mineral oil into a stirring barrel, and stirring for 10 minutes to obtain a mixture A;
s82, adding 0.013kg of 3-aminopropyl triethoxysilane, 0.107kg of antioxidant H161, 0.1kg of polyvinyl alcohol, 0.4kg of polyvinylpyrrolidone, 0.3kg of polymethyl methacrylate and 0.8kg of nano zeolite antibacterial silver-loaded zinc composite antibacterial agent into the mixture A, and stirring for 10 minutes to obtain a mixture B;
s83, adding the mixture B into a hopper of a double-screw extruder, extruding, shearing and granulating by the double-screw extruder, wherein the diameter of a screw is 62mm, the length-diameter ratio of the screw is 39:1, and the temperature of each zone of the screw is as follows: the first zone 170 ℃, the second zone 180 ℃, the third zone 190 ℃, the fourth zone 195 ℃, the fifth zone 200 ℃, the sixth zone 205 ℃.
Preparation example 3
The preparation method of the PP antibacterial material adopts the raw materials in the embodiment 3, and comprises the following steps:
s81, adding 98kg of PP and 0.10kg of white mineral oil into a stirring barrel, and stirring for 8 minutes to obtain a mixture A; s82, adding 0.0125kg of 3-aminopropyl triethoxysilane, 0.0875kg of antioxidant H161, 0.108kg of polyvinyl alcohol, 0.326kg of polyvinylpyrrolidone, 0.216kg of polymethyl methacrylate and 0.65kg of nano zeolite antibacterial silver-loaded zinc composite antibacterial agent into the mixture A, and stirring for 10 minutes to obtain a mixture B;
s83, adding the mixture B into a hopper of a double-screw extruder, extruding, shearing and granulating by the double-screw extruder, wherein the diameter of a screw is 62mm, the length-diameter ratio of the screw is 39:1, and the temperature of each zone of the screw is as follows: first zone 165 ℃, second zone 175 ℃, third zone 185 ℃, fourth zone 193 ℃, fifth zone 198 ℃, sixth zone 203 ℃.
Preparation example 4
The same as in preparation example 3, except that the material of comparative example 1 was used, and 0.1kg of 3-aminopropyl triethoxysilane was used as the antioxidant.
Preparation example 5
The same as in preparation example 3, except that the material of comparative example 2 was used, and the antioxidant was 0.kg of antioxidant H161.
Preparation example 6
The same as in preparation example 3, except that the material of comparative example 3 was used, the dispersing agent was 0.65kg of polyvinyl alcohol.
Preparation example 7
The same as in preparation example 3, except that the material of comparative example 4 was used, and the dispersing agent was polyvinylpyrrolidone 0.65kg.
Preparation example 8
The same as in preparation example 3, except that the material of comparative example 5 was used, and the dispersant was polymethyl methacrylate 0.65kg.
Performance test
The antibacterial materials prepared in preparation examples 1 to 8 were sampled and tested, respectively, and the test results are shown in table 1.
Melt index: melt index, mass (300 ℃,1.2 kg) tested according to ASTM D1238;
tensile strength: testing according to ASTM/D638;
flexural strength: testing according to ASTM/D790;
notched Izod impact Strength: testing according to ASTM/D256;
elongation at break: testing according to ASTM D638;
flexural modulus: testing according to ASTM D790;
and (3) water boiling test: the method comprises the following steps of: preparing a test sample: preparing a PP antibacterial material sample meeting the requirements; heating water: heating water to 80 degrees, and then keeping the water temperature stable; soaking a sample: completely immersing the prepared PP antibacterial material sample in hot water to ensure that the sample is completely covered in the water; test time: continuously soaking the sample for 18 hours; observing the sample: observing the state of the sample every 2 hours, including the conditions of color change, deformation and the like; ending the test: ending the test after 18 hours, and observing the condition of the final sample;
TABLE 1
From Table 1, the PP antibacterial materials prepared in preparation examples 1 to 3 are good in various performance indexes, and particularly do not turn yellow after 18 hours of water boiling test. The obtained PP antibacterial material has good oxidation resistance and yellowing resistance, and also has excellent toughness and plasticity, and is applied to humidifiers and furniture.
From the comparative analysis of preparation example 3 and preparation example 4 and preparation example 5 in table 1, the composition of 3-aminopropyl triethoxysilane as an antioxidant and antioxidant H161 is more excellent in yellowing resistance than 3-aminopropyl triethoxysilane or antioxidant H161 as a single component thereof, because 3-aminopropyl triethoxysilane and antioxidant H161 have synergistic effect, the reaction of free radicals and oxygen in the PP antibacterial material is effectively inhibited, the aging speed of the material is delayed, the structure of the material is stabilized, the oxidation reaction is inhibited, the performance stability and the aging resistance of the material are maintained, and the phenomena of color change, surface yellowing, embrittlement and the like of the PP material are prevented.
From the comparative analysis of preparation example 3 and preparation examples 6-8 in Table 1, the dispersing agent is a composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate according to the mass percentage of 1:4:3, and the yellowing resistance is more excellent than that of the single-component polyvinyl alcohol, polyvinylpyrrolidone or polymethyl methacrylate, because the composition of the polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate has synergistic effect, the dispersibility and stability of the material are enhanced, and the mixed use of the polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate can better control the dispersion state and particle size distribution of the material, and the boiling resistance, heat resistance and antibacterial property of the material are improved.
Antibacterial test
The PP antibacterial materials prepared in preparation examples 1 to 8 were sampled and injection-molded into plates, and the plates were sent to the microbiological analysis inspection center in Guangdong province for antibacterial test according to JIS Z2801:2000 standard, and the test results are shown in Table 2.
TABLE 2
From Table 2, it can be seen that the antibacterial ratio of Staphylococcus aureus and Escherichia coli of the PP antibacterial materials prepared in preparation examples 1 to 3 is more than 99.91%, and excellent antibacterial effect is obtained.
From Table 2, it can be seen that the antibacterial ratio of Staphylococcus aureus and Escherichia coli of the PP antibacterial material prepared in preparation example 3 is higher than that of the PP antibacterial materials prepared in preparation examples 4 and 5, because in preparation examples 4 and 5, the antioxidant is a combination of 3-aminopropyl triethoxysilane and antioxidant H161, which is more conducive to improving the antibacterial efficacy of the nano zeolite antibacterial silver-zinc composite antibacterial agent than 3-aminopropyl triethoxysilane or antioxidant H161 which is a single component thereof.
From Table 2, it can be seen that the antibacterial ratio of Staphylococcus aureus and Escherichia coli of the PP antibacterial material prepared in preparation example 3 is higher than that of the PP antibacterial materials prepared in preparation examples 6 to 8, because in preparation examples 6 to 8, the dispersing agent is a composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate in a mass ratio of 1:4:3, which is more helpful to improve the antibacterial effect of the nano zeolite antibacterial silver-loaded zinc composite antibacterial agent than the single-component polyvinyl alcohol, polyvinylpyrrolidone or polymethyl methacrylate. The composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate can better control the dispersion state and particle size distribution of the material, and improve the water resistance, heat resistance and antibacterial property of the material. Can effectively disperse nano zeolite antibacterial silver-loaded zinc composite antibacterial agent particles, prevent aggregation and precipitation of the nano zeolite antibacterial silver-loaded zinc composite antibacterial agent particles, and improve the antibacterial function of the product.
While the present application has been particularly shown and described with reference to the foregoing embodiments and examples, it will be understood by those skilled in the art that various changes may be made and equivalents substituted for elements thereof without departing from the spirit and scope of the application.
Claims (10)
1. The PP antibacterial material is characterized by comprising the following raw materials in parts by weight: 97-98.5 parts of PP, 0.08-0.12 part of antioxidant, 0.08-0.12 part of white mineral oil, 0.5-0.8 part of dispersing agent and 0.5-0.8 part of antibacterial agent, wherein the antibacterial agent is nano zeolite antibacterial silver-carrying zinc composite antibacterial agent, the Ag mass percentage content is 0.1-0.2%, the Zn mass percentage content is 0.2-0.3%, and the particle size of the nano zeolite antibacterial silver-carrying iron composite antibacterial agent is 70-90 nanometers.
2. The PP antibacterial material according to claim 1, wherein the preparation method of the nano zeolite antibacterial silver-loaded zinc composite antibacterial agent comprises the following steps:
s21, adding 1L of silver nitrate solution into 5L of nano zeolite suspension, mixing and stirring to enable silver ions to react with nano zeolite to form silver doped nano zeolite;
s22, adding 1L of zinc nitrate solution into the silver-doped nano zeolite suspension, mixing and stirring to enable iron ions and the silver-doped nano zeolite to react to form silver-zinc composite doped nano zeolite;
s23, performing treatments such as precipitation, washing and the like on the prepared silver-zinc composite doped nano zeolite to remove unreacted salts and impurities;
s24, drying the washed sample to enable the sample to be completely dried;
s25, grinding the dried sample to obtain nano zeolite antibacterial silver-zinc composite antibacterial agent with the particle size of 70-90 nanometers.
3. The PP antibacterial material of claim 2, wherein in step S21, the mass solubility of the silver nitrate solution is 15g/L, the mass ratio of the nano zeolite suspension to deionized water is 1:1, and the mixing and stirring time is 30-50min.
4. The PP antibacterial material of claim 2, wherein in step S22, the mass solubility of the zinc nitrate solution is 40g/L, and the mixing and stirring time is 45-60min.
5. The PP antibacterial material of claim 2, wherein in step S24, the drying process is vacuum drying, and the process parameters are: vacuum degree is 2000-3000Pa, temperature is 60-70deg.C, and time is 1-2 hr.
6. The PP antibacterial material according to claim 1, wherein the antioxidant is a composition with an antioxidant H161 in a mass ratio of 1:6-8.
7. The PP antibacterial material according to claim 1, wherein the dispersing agent is a composition of polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate in a mass percentage of 1:2-4:1-3.
8. A method for preparing a PP antibacterial material, characterized by adopting the raw materials of a PP antibacterial material according to any one of claims 1 to 6, comprising the following steps:
s81, adding 97-98.5 parts of PP and 0.08-0.12 part of white mineral oil into a stirring barrel according to parts by weight, and stirring to obtain a mixture A;
s82, adding 0.08-0.12 part of antioxidant, 0.5-0.8 part of dispersing agent and 0.5-0.8 part of antibacterial agent into the mixture A according to parts by weight, and stirring to obtain a mixture B;
s83, adding the mixture B into a hopper of a double-screw extruder, extruding, shearing and granulating by the double-screw extruder, wherein the diameter of a screw is 62mm, the length-diameter ratio of the screw is 39:1, and the temperature of each zone of the screw is as follows: the first zone 160-170 ℃, the second zone 170-180 ℃, the third zone 180-190 ℃, the fourth zone 190-195 ℃, the fifth zone 195-200 ℃ and the sixth zone 200-205 ℃.
9. The method for producing a PP antibacterial material according to claim 8, wherein in step S81, the stirring time is 5 to 10 minutes.
10. The method of producing a PP antibacterial material according to claim 8, wherein in step S82, the stirring time is 10 to 15 minutes.
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