CN111218064A - Antistatic and antibacterial multifunctional polymer composite material and preparation method thereof - Google Patents
Antistatic and antibacterial multifunctional polymer composite material and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention relates to the field of high polymer materials, and provides an antistatic and antibacterial multifunctional high polymer composite material which comprises a substrate and a functional nano material filler, wherein the substrate is a high polymer material, the functional nano material filler is Ag @ T-ZnOw modified on the surface, the Ag @ T-ZnOw modified on the surface is Ag @ T-ZnOw modified by a silane coupling agent, and the Ag @ T-ZnOw is a functional nano heterojunction composite material of nano silver and tetrapod-shaped zinc oxide. The surface-modified Ag @ T-ZnOw and polymer composite material has good antistatic and antibacterial capabilities. The invention also provides a preparation method of the composite material, the inorganic material Ag @ T-ZnOw modified by the silane coupling agent and the high polymer material are mixed in an open mill or an internal mixing way, and the composite material can be prepared. And (4) preparing a sample wafer through compression molding and testing the performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antistatic and antibacterial multifunctional high polymer composite material and a preparation method thereof.
Background
The high molecular polymer is widely applied to various fields such as industry, medical treatment and the like as a common material due to low price, easy processing and forming and excellent comprehensive performance. However, most of polymer materials are insulators, have very high surface resistivity and volume resistivity, and are prone to accumulate static charges on the surface of the materials and are difficult to disappear under the action of collision, friction, electrostatic induction and the like. Due to the existence of static electricity, the application of high polymer materials in an environment requiring antistatic is limited. Meanwhile, the high polymer material does not have effective antibacterial property, so that bacteria are easy to breed, and the high polymer material can generate great harm in long-term use, thereby bringing inconvenience to daily life and being limited in application in the fields of medical treatment and the like.
Although some polymer materials with antistatic and antibacterial properties exist in the market at present, metal silver with conductive and antibacterial properties is generally compounded with the polymer materials, but the antistatic and antibacterial effects are still not ideal.
Disclosure of Invention
In view of the above, the present invention provides an antistatic, antibacterial multifunctional polymer composite and a preparation method thereof, and the polymer composite provided by the present invention has high antibacterial and antistatic properties.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an antistatic and antibacterial multifunctional polymer composite material, which comprises a substrate and a functional nano material filler, wherein the substrate is a polymer material, the functional nano material filler is Ag @ T-ZnOw modified on the surface, the Ag @ T-ZnOw modified on the surface is Ag @ T-ZnOw modified by a silane coupling agent, and the Ag @ T-ZnOw is a functional nano heterojunction composite material of nano silver and tetrapod-like zinc oxide.
Preferably, the mass content of the surface-modified Ag @ T-ZnOw is 5-15%.
preferably, the silane coupling agent includes one or more of methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β methoxyethoxy) silane.
The invention provides a preparation method of the antistatic and antibacterial multifunctional polymer composite material, which comprises the following steps:
carrying out photochemical synthesis reaction on silver nitrate and tetrapod-shaped zinc oxide in a polyalcohol water solution to obtain a functional nano heterojunction material Ag @ T-ZnOw;
mixing a silane coupling agent, ethanol and water, and adjusting to be acidic to obtain a mixed solution;
mixing the Ag @ T-ZnOw with the mixed solution, and reacting to obtain surface-modified Ag @ T-ZnOw;
and mixing the surface-modified Ag @ T-ZnOw and a matrix high polymer material to prepare the antistatic and antibacterial multifunctional high polymer composite material.
Preferably, the temperature of the photochemical synthesis reaction is 30-80 ℃ and the time is 4-8 hours.
Preferably, the aqueous polyol solution is an aqueous polyethylene glycol solution.
Preferably, the concentration of the polyalcohol aqueous solution is (0.04-0.08) mol/L.
Preferably, the volume ratio of the ethanol to the water is (80-99) to (1-20).
Preferably, the ratio of the mass of the Ag @ T-ZnOw to the volume of the mixed solution is (15-25) g/250 mL.
Preferably, the mass ratio of the silane coupling agent to Ag @ T-ZnOw is 1-4%.
The invention provides an antistatic and antibacterial multifunctional polymer composite material, which comprises a substrate and a functional nano material filler, wherein the substrate is a polymer material, the functional nano material filler is Ag @ T-ZnOw modified on the surface, the Ag @ T-ZnOw modified on the surface is Ag @ T-ZnOw modified by a silane coupling agent, and the Ag @ T-ZnOw is a functional nano heterojunction composite material of nano silver and tetrapod-like zinc oxide. The multifunctional polymer composite material provided by the invention can be easily established in a polymer material systemThe four-needle zinc oxide which forms a conductive path in a dimensional network and the nano silver with high antibacterial and conductive properties are compounded in a heterojunction mode to obtain a composite material Ag @ T-ZnOw with better conductive and antibacterial properties; wherein, the formation of the heterojunction improves the dispersibility of Ag on T-ZnOw and combines the advantages of Ag and T-ZnOw; and then the surface of the composite material Ag @ T-ZnOw is modified by a silane coupling agent, so that the hydrophobicity of the Ag @ T-ZnOw composite material is improved, the compatibility of the composite material Ag @ T-ZnOw and a matrix high polymer material is improved, and the antibacterial property and the antistatic property of the high polymer composite material are improved. The results of the examples show that when polypropylene is used as the polymer material, the surface resistivity of the antistatic and antibacterial multifunctional polymer composite material provided by the invention is reduced to 5.5 × 1010Omega, the antibacterial rate of the multifunctional polymer composite material to escherichia coli is improved to 99.9% from 16.0% and the antibacterial rate to staphylococcus aureus is improved to 99.9% from 21.1% compared with that of a pure polypropylene material by 6 orders of magnitude.
The invention also provides a preparation method of the antistatic and antibacterial multifunctional polymer composite material, which comprises the following steps: carrying out photochemical synthesis reaction on silver nitrate and tetrapod-shaped zinc oxide in a polyalcohol water solution to obtain a functional nano heterojunction material Ag @ T-ZnOw; mixing a silane coupling agent, ethanol and water, and adjusting to be acidic to obtain a mixed solution; mixing the Ag @ T-ZnOw with the mixed solution, and reacting to obtain surface-modified Ag @ T-ZnOw; and mixing the surface-modified Ag @ T-ZnOw and a matrix high polymer material to prepare the antistatic and antibacterial multifunctional high polymer composite material. The composite material can be prepared by mixing the Ag @ T-ZnOw subjected to surface modification by the silane coupling agent and a high polymer material, and the preparation method is simple and easy to operate.
Drawings
FIG. 1 is a TEM image of Ag @ T-ZnOw composite prepared in example 1 of the present invention.
Detailed Description
The invention provides an antistatic and antibacterial multifunctional polymer composite material, which comprises a substrate and a functional nano material filler, wherein the substrate is a polymer material, the functional nano material filler is Ag @ T-ZnOw modified on the surface, the Ag @ T-ZnOw modified on the surface is Ag @ T-ZnOw modified by a silane coupling agent, and the Ag @ T-ZnOw is a functional nano heterojunction composite material of nano silver and tetrapod-like zinc oxide.
The antistatic and antibacterial multifunctional polymer composite material provided by the invention comprises a substrate, wherein the substrate is a polymer material. The invention does not limit the base polymer material, and can be any polymer material commonly used in the field. In the present invention, the polymer material exists as a main body of the material.
The antistatic and antibacterial multifunctional polymer composite material provided by the invention comprises a functional nano material filler. In the invention, the functional nano material filler is preferably Ag @ T-ZnOw with surface modification. In the present invention, the modifying agent is preferably a silane coupling agent. In the invention, the mass content of the surface-modified Ag @ T-ZnOw is preferably 5-15%, more preferably 7-12%, and even more preferably 10 wt%.
in the invention, the silane coupling agent is preferably one or more of methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (β methoxyethoxy) silane, and is more preferably methacryloxypropyltrimethoxysilane.
In the invention, the Ag @ T-ZnOw is a functional nano heterojunction composite material of nano silver and tetrapod-shaped zinc oxide. In the invention, the tetrapod-like zinc oxide can establish a three-dimensional net shape in a high polymer material system to form a conductive path, and is compounded with nano silver with high antibacterial and conductive properties in a heterojunction form to obtain the functional nano material Ag @ T-ZnOw with better conductive and antibacterial properties.
In the invention, the mass ratio of the nano silver to the tetrapod-like zinc oxide is preferably 1 to 5%, more preferably 2 to 4%, and still more preferably 3%.
The antistatic and antibacterial multifunctional polymer composite material provided by the invention comprises a substrate and a functional nano material filler, wherein the substrate is a polymer material, the functional nano material filler is Ag @ T-ZnOw modified on the surface, the Ag @ T-ZnOw modified on the surface is Ag @ T-ZnOw modified by a silane coupling agent, and the Ag @ T-ZnOw is a functional nano heterojunction composite material of nano silver and tetrapod-like zinc oxide. According to the multifunctional polymer composite material provided by the invention, the tetrapod-like zinc oxide which is easy to establish a three-dimensional net shape in a polymer material system to form a conductive path and the nano silver with high antibacterial and conductive properties are compounded in a heterojunction form to obtain the composite material Ag @ T-ZnOw with better conductive and antibacterial properties; wherein, the formation of the heterojunction improves the dispersibility of Ag on T-ZnOw and combines the advantages of Ag and T-ZnOw; and then the surface of the composite material Ag @ T-ZnOw is modified by a silane coupling agent, so that the hydrophobicity of the Ag @ T-ZnOw composite material is improved, the compatibility of the composite material Ag @ T-ZnOw and a matrix high polymer material is improved, and the antibacterial capacity and the antistatic capacity of the high polymer composite material are improved.
The invention also provides a preparation method of the antistatic and antibacterial multifunctional polymer composite material, which comprises the following steps:
carrying out photochemical synthesis reaction on silver nitrate and tetrapod-shaped zinc oxide in a polyalcohol water solution to obtain a functional nano heterojunction material Ag @ T-ZnOw;
mixing a silane coupling agent, ethanol and water, and adjusting to be acidic to obtain a mixed solution;
mixing the Ag @ T-ZnOw with the mixed solution, and reacting to obtain surface-modified Ag @ T-ZnOw;
and mixing the surface-modified Ag @ T-ZnOw and a matrix high polymer material to prepare the antistatic and antibacterial multifunctional high polymer composite material.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
In the present invention, the operation is carried out at room temperature unless otherwise specified.
The invention carries out photochemical synthesis reaction on silver nitrate and tetrapod-shaped zinc oxide in a polyalcohol aqueous solution to obtain the functional nano heterojunction material Ag @ T-ZnOw.
The tetrapod-like zinc oxide is not specially specified in the invention and is a conventional commercial product in the field.
In the present invention, the number average molecular weight of the polyol in the aqueous polyol solution is preferably 4000 to 8000. In the present invention, the concentration of the aqueous polyol solution is preferably (0.04 to 0.08) mol/L, more preferably (0.05 to 0.07) mol/L, and still more preferably 0.06 mol/L. In the present invention, the aqueous polyol solution is preferably an aqueous polyethylene glycol solution. In the present invention, the aqueous polyol solution serves as a solvent and a reducing agent.
In the invention, the volume ratio of the mass of the silver nitrate to the volume of the polyethylene glycol is preferably (0.5-2) g/650mL, more preferably 0.5-1.5 g/650mL, and even more preferably 1g/650 mL. In the present invention, the mass ratio of the silver nitrate to the tetrapod-like zinc oxide is preferably 3 to 7%, more preferably 4 to 6%, and still more preferably 5%.
The order of mixing the silver nitrate, the tetrapod-like zinc oxide, and the aqueous solution of the polyalcohol is not particularly limited, and the raw materials may be mixed. In the present invention, it is preferable to mix the silver nitrate with the aqueous polyol solution first and then with the T-ZnOw. The mixing method of the silver nitrate and the aqueous solution of the polyalcohol is not particularly limited in the present invention, and a mixing method known to those skilled in the art may be used. In the present invention, the mixing of the silver nitrate and the aqueous polyol solution is preferably performed under stirring. In a specific embodiment of the invention, the stirring time is preferably 15 minutes. In the present invention, the mixing of the mixed solution of silver nitrate and polyalcohol and T-ZnOw is preferably performed under stirring conditions. In a specific embodiment of the invention, the stirring time is preferably 1 h. In the present invention, the mixing of the silver nitrate, the tetrapod-like zinc oxide, and the aqueous polyol solution is preferably performed under a condition of being shielded from light.
After the silver nitrate, the tetrapod-shaped zinc oxide and the polyalcohol water solution are mixed, the suspension obtained by mixing is subjected to photochemical synthesis reaction to obtain the functional nano heterojunction material Ag @ T-ZnOw. In the invention, the temperature of the photochemical synthesis reaction is preferably 30-80 ℃, more preferably 40-70 ℃, and more preferably 50 ℃; the photochemical synthesis reaction time is preferably 2 to 8 hours, more preferably 3 to 5 hours, and even more preferably 4 hours. The apparatus for the photochemical synthesis reaction according to the present invention is not particularly limited, and any apparatus for photochemical synthesis reaction known to those skilled in the art may be used. In a specific embodiment of the present invention, the photochemical reaction is preferably carried out under a photocatalytic device-ultraviolet light. In the invention, the wavelength of the ultraviolet lamp is preferably 100-365 nm, and the power is preferably 15-25W.
After the photochemical synthesis reaction is finished, products of the photochemical synthesis reaction are preferably separated, washed and dried in sequence to obtain the functional nano heterojunction material Ag @ T-ZnOw.
In the present invention, the separation method is not particularly limited, and solid-liquid separation can be performed by using a technical scheme well known to those skilled in the art. In the present invention, the separation is preferably suction filtration. In the present invention, the washing is preferably washing with water and ethanol in this order. The present invention does not have any special regulation on the number of times of washing, and can clean unreacted impurities. In a specific embodiment of the invention, it is preferred that water and ethanol are washed 3 times each. In the present invention, the drying is preferably vacuum drying, the temperature of the drying is preferably 50 ℃, and the time of the drying is preferably 12 hours.
According to the invention, a silane coupling agent, ethanol and water are mixed and adjusted to be acidic, so as to obtain a mixed solution. In the present invention, the ethanol is preferably anhydrous ethanol; the water is preferably deionized water.
In the invention, the volume ratio of the ethanol to the water is preferably (80-99): (1-20), and more preferably 95: 5.
The invention has no special requirement on the operation of mixing the silane coupling agent, the ethanol and the water, and the three substances are uniformly mixed. In the embodiment of the present invention, the mixing of the silane coupling agent, ethanol and water is preferably performed by adding the coupling agent to an absolute ethanol-water mixed solution.
In the invention, after the silane coupling agent, ethanol and water are mixed, the pH value of the system is preferably adjusted to 3-5. The reagent for adjusting is not particularly required in the invention, and the conventional acidic reagent in the field can be adopted. In an embodiment of the invention, the modulating agent is preferably acetic acid.
After the functional nano heterojunction material Ag @ T-ZnOw and the mixed solution are obtained, the Ag @ T-ZnOw and the mixed solution are mixed and react to obtain the surface modified Ag @ T-ZnOw.
In the invention, the ratio of the mass of the Ag @ T-ZnOw to the volume of the mixed solution is preferably (15-25) g/250mL, and more preferably (16-21) g/250 mL. In the invention, the mass ratio of the silane coupling agent to Ag @ T-ZnOw is preferably 1-4%, and more preferably 2%.
In the invention, the operation of mixing the Ag @ T-ZnOw and the mixed solution has no special requirement, and the Ag @ T-ZnOw and the mixed solution are uniformly mixed. In the invention, the mixing temperature is preferably 50-70 ℃, and more preferably 60 ℃. In the invention, in the mixing operation, Ag @ T-ZnOw is connected with an organophilic group part of the silane coupling agent, and the organophilic group part of the silane coupling agent is exposed outside, so that the hydrophobicity of the Ag @ T-ZnOw is improved.
After the reaction is finished, the invention preferably separates, washes and dries the product obtained by the reaction in sequence to obtain the surface modified Ag @ T-ZnOw.
The separation mode is not specially specified, and the solid-liquid separation can be realized by adopting the technical scheme commonly used in the field. In the present invention, the separation is preferably suction filtration. In the present invention, the washing is preferably performed by sequentially using water and ethanol. The present invention does not have any special regulation on the number of times of washing, and can clean unreacted impurities. In a specific embodiment of the present invention, the number of washing is preferably 3 times for each of water and ethanol. The drying mode is not specially specified, and water and ethanol on the Ag @ T-ZnOw are removed by adopting the conventional drying mode in the field. In the embodiment of the present invention, the drying is preferably vacuum drying, the temperature of the drying is preferably 50 ℃, and the time is preferably 12 h.
After the surface modified Ag @ T-ZnOw is obtained, the invention prepares the antistatic and antibacterial multifunctional polymer composite material by mixing the surface modified Ag @ T-ZnOw and a polymer material. In the invention, the mass ratio of the surface modified Ag @ T-ZnOw to the antistatic and antibacterial multifunctional polymer composite material is preferably 5-15%, and more preferably 10%.
The invention has no special regulation on the mixing mode, and adopts the conventional mixing mode of high polymer materials in the field to ensure that the structural characteristics of the T-ZnOw can not be damaged when the T-ZnOw is blended and compounded with a high polymer base material. In the present invention, the kneading is preferably conducted by open mixing or internal mixing, and more preferably conducted by open mixing.
In the invention, the mixing temperature is preferably 160-170 ℃, and more preferably 165 ℃; the kneading time is preferably 5 to 15 minutes, and more preferably 10 minutes. In the present invention, the kneading apparatus is preferably a two-roll mill. In the invention, the gap between the front roller and the rear roller of the two-roller open mill is preferably 1.2-1.5 mm. In the invention, the ratio of the rotation speed of the front roller and the rotation speed of the rear roller of the open mill is preferably 1 (1.34-1.36), and more preferably 1.35. In the embodiment of the invention, the rotating speed of the front roller of the open mill is preferably 15r/min, and the rotating speed of the rear roller of the open mill is preferably 20.25 r/min.
After the antistatic and antibacterial multifunctional polymer composite material is obtained, a corresponding test sample is obtained preferably by compression molding.
In the present invention, the molding method is not particularly limited, and the kneaded material may be molded into a sheet form. In the present invention, the mold temperature for the press molding is preferably 25 ℃ to 40 ℃, more preferably 35 ℃. In the invention, the mould pressing temperature is preferably 180-220 ℃, and further preferably 200 ℃; the time for the die pressing is preferably 5-15 minutes, and more preferably 10 minutes; the pressure of the die pressing is preferably 9-11 MPa, and more preferably 10 MPa.
In the present invention, the cooling method is preferably natural cooling. In the present invention, the end temperature of the cooling is preferably room temperature.
According to the preparation method provided by the invention, the functional heterojunction material Ag @ T-ZnOw modified by the silane coupling agent and the high polymer material are subjected to open mixing or banburying mixing to obtain the antistatic and antibacterial multifunctional high polymer composite material, and the preparation method is simple and easy to operate.
The antistatic and antibacterial multifunctional polymer composite and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Preparation of Ag @ T-ZnOw functional nano heterojunction composite material
650ml of polyethylene glycol aqueous solution (0.06mol/L) is weighed and placed in a beaker, and 1g of AgNO is added in turn3Stirring for 15 minutes at room temperature, stirring for 20g T-ZnOw for 1 hour under the condition of keeping out of the sun to prepare cement ash or powder blue suspension, placing the prepared suspension in a self-made photocatalysis device-ultraviolet light, reacting for 4 hours at 50 ℃, after the reaction is finished, carrying out suction filtration on silver gray suspension to obtain solid, washing the solid for 3 times by water and ethanol respectively, and placing the washing product in a drying box for drying for 12 hours at 50 ℃ to obtain the Ag @ T-ZnOw functional nano heterojunction composite material.
Surface modification of Ag @ T-ZnOw composite material
Weighing 250mL of absolute ethyl alcohol-water (volume ratio is 95:5) mixed solvent, placing the mixed solvent in a beaker, adding methacryloxypropyl trimethoxy silane, wherein the mass of the methacryloxypropyl trimethoxy silane is 2% of the mass of the Ag @ T-ZnOw, adjusting the pH of the solution to 3-5 by using acetic acid (analytically pure), then adding the Ag @ T-ZnOw, stirring at the constant temperature of 60 ℃ for 1.5h to obtain uniform mixed solution, carrying out suction filtration on the obtained mixed solution to obtain solid, sequentially washing the solid by using water and ethyl alcohol for 3 times, and then transferring the solid to a drying box for drying at the temperature of 50 ℃ for 12h to obtain the Ag @ T-ZnOw functional nano heterojunction composite material with the modified surface.
FIG. 1 is a TEM image of the functional nano-heterojunction Ag @ T-ZnOw composite material prepared in this example. As can be seen from fig. 1, nano silver is uniformly deposited on the surface of the tetrapod-like zinc oxide.
Preparation of antistatic, antibacterial multifunctional polymer composite material
Weighing polypropylene, placing the polypropylene in a drying box, drying at 50 ℃ for 12h, placing the dried polypropylene in an open mill, sequentially adding ten drops of liquid paraffin and surface-modified Ag @ T-ZnOw, wherein the mass of the surface-modified Ag @ T-ZnOw is 10% of the total mass of the Ag @ T-ZnOw and the dried polypropylene, uniformly stirring, mixing at 165 ℃ with a front roller moving speed of 15r/min and a front roller moving speed and a rear roller moving speed ratio of 1:1.35, continuously adjusting a front roller gap and a rear roller gap, keeping the two roller gaps at 1.2-1.5 mm, and mixing for 10 minutes to obtain the antistatic and antibacterial multifunctional polymer composite material. Pressing for 10 minutes at the temperature of 200 ℃ and the pressure of 10Mpa in a tablet press, pressing into a sheet, and naturally cooling to room temperature to obtain a test sample.
Example 2
The other operations were the same as in example 1 except that the mass of the surface-modified Ag @ T-ZnOw was 12% of the total mass of the surface-modified Ag @ T-ZnOw and the polypropylene after drying.
Example 3
The other operations were the same as in example 1 except that the mass of the surface-modified Ag @ T-ZnOw was 15% of the total mass of the surface-modified Ag @ T-ZnOw and the polypropylene after drying.
Comparative example 1
The other operations were the same as those in example 1 except that only the dried polypropylene was added and the addition of the surface-modified Ag @ T-ZnOw was omitted.
Comparative example 2
The other operations were the same as in comparative example 1 except that polypropylene after drying and Ag @ T-ZnOw without surface modification were added, and the mass of the Ag @ T-ZnOw without surface modification was 5% of the total mass of the Ag @ T-ZnOw without surface modification and the polypropylene after drying.
Comparative example 3
The other operations were the same as in comparative example 2 except that the mass of Ag @ T-ZnOw which was not surface-modified was 8% of the total mass of Ag @ T-ZnOw which was not surface-modified and polypropylene after drying.
Comparative example 4
The other operations were the same as in comparative example 2 except that the mass of Ag @ T-ZnOw which was not surface-modified was 10% of the total mass of Ag @ T-ZnOw which was not surface-modified and polypropylene after drying.
Comparative example 5
The other operations were the same as in comparative example 2 except that the mass of Ag @ T-ZnOw which was not surface-modified was 12% of the total mass of the surface-modified Ag @ T-ZnOw and the polypropylene after drying.
Comparative example 6
The other operations were the same as in comparative example 2 except that the mass of Ag @ T-ZnOw which was not surface-modified was 5% of the total mass of Ag @ T-ZnOw which was not surface-modified and polypropylene after drying.
The materials obtained in examples 1 to 3 and comparative examples 1 to 6 were tested for antistatic and antibacterial properties.
The Escherichia coli is ATCC 8739; staphylococcus aureus type ATCC 6538P.
And (4) testing standard: QB/T31402-2015 antibacterial plastic antibacterial performance test method and antibacterial effect, and QB/T1410-2006 solid insulating material volume resistivity and surface resistivity test method.
The test results are shown in table 1:
TABLE 1 materials antimicrobial and surface resistivity testing
As can be seen from the above examples 1-3 and comparative examples 1-6, when the surface-modified Ag @ T-ZnOw is 10% by mass, the surface resistivity of the antistatic and antibacterial multifunctional polymer composite material provided by the invention is reduced to 5.5 × 1010Omega, the antibacterial rate of the multifunctional polymer composite material to escherichia coli is improved to 99.9% from 16.0% and the antibacterial rate to staphylococcus aureus is improved to 99.9% from 21.1% compared with that of a pure polypropylene material by 6 orders of magnitude.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The antistatic and antibacterial multifunctional polymer composite material comprises a substrate and a functional nano material filler, wherein the substrate is a polymer material, the functional nano material filler is Ag @ T-ZnOw modified on the surface, the Ag @ T-ZnOw modified on the surface is Ag @ T-ZnOw modified by a silane coupling agent, and the Ag @ T-ZnOw is a functional nano heterojunction composite material of nano silver and tetrapod-shaped zinc oxide.
2. The antistatic and antibacterial multifunctional polymer composite material as claimed in claim 1, wherein the mass content of the surface-modified Ag @ T-ZnOw is 5-15%.
3. the antistatic, antibacterial multifunctional polymeric composite of claim 1, wherein the silane coupling agent comprises one or more of methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β methoxyethoxy) silane.
4. The method for preparing the antistatic, antibacterial multifunctional polymer composite material according to any one of claims 1 to 3, comprising the steps of:
carrying out photochemical synthesis reaction on silver nitrate and tetrapod-shaped zinc oxide in a polyalcohol water solution to obtain a functional nano heterojunction material Ag @ T-ZnOw;
mixing a silane coupling agent, ethanol and water, and adjusting to be acidic to obtain a mixed solution;
mixing the Ag @ T-ZnOw with the mixed solution, and reacting to obtain surface-modified Ag @ T-ZnOw;
and mixing the surface-modified Ag @ T-ZnOw and a matrix high polymer material to prepare the antistatic and antibacterial multifunctional high polymer composite material.
5. The method according to claim 4, wherein the photochemical synthesis reaction is carried out at a temperature of 30 to 80 ℃ for 4 to 8 hours.
6. The method according to claim 4, wherein the aqueous polyol solution is an aqueous polyethylene glycol solution.
7. The method according to claim 4 or 6, wherein the concentration of the aqueous polyol solution is (0.04 to 0.08) mol/L.
8. The method according to claim 4, wherein the volume ratio of ethanol to water is (80-99): 1-20).
9. The preparation method according to claim 4, wherein the ratio of the mass of Ag @ T-ZnOw to the volume of the mixed solution is (15-25) g/250 mL.
10. The production method according to claim 4, wherein the mass ratio of the silane coupling agent to Ag @ T-ZnOw is 1 to 4%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010191010.3A CN111218064B (en) | 2020-03-18 | 2020-03-18 | Antistatic and antibacterial multifunctional polymer composite material and preparation method thereof |
| AU2020103516A AU2020103516A4 (en) | 2020-03-18 | 2020-11-18 | Antistatic, antibacterial, and multifunctional polymer composite material, and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280195A (en) * | 2020-10-12 | 2021-01-29 | 中国电力科学研究院有限公司 | Nano-sheet ZnO @ Ag/insulating composite material and preparation method thereof |
| CN113788498A (en) * | 2021-09-09 | 2021-12-14 | 同曦集团有限公司 | Material with visible light catalytic air purification and antibacterial functions and preparation method thereof |
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| CN112980050B (en) * | 2021-04-28 | 2022-09-06 | 宁夏大学 | Heterojunction composite material and preparation method thereof, antibacterial and antistatic high polymer material and preparation method and application thereof |
| CN115162008B (en) * | 2022-07-15 | 2024-01-12 | 吉祥三宝高科纺织有限公司 | Durable antibacterial hydrophilic polylactic acid fiber and preparation method thereof |
| CN115109468B (en) * | 2022-08-03 | 2023-09-08 | 浙江工业大学 | Multifunctional water-based damping paint and preparation method thereof |
| CN115850544B (en) * | 2022-12-21 | 2023-10-20 | 浙江工业大学 | Ag@PMMA nanocomposite, preparation method thereof and preparation method of PVDF-based dielectric composite |
| CN115820117B (en) * | 2023-01-10 | 2023-08-01 | 福州大学 | Antibacterial super-hydrophobic composite coating and preparation method thereof |
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| CN104162681A (en) * | 2014-07-30 | 2014-11-26 | 青岛科技大学 | Preparation method for silver-zinc oxide nano-composite structure |
| CN109735105A (en) * | 2018-12-27 | 2019-05-10 | 张家港大塚化学有限公司 | High-intensitive wear-resisting polyetherimide composite wood of antistatic antibiotic and preparation method thereof |
| CN109845743A (en) * | 2019-01-29 | 2019-06-07 | 深圳市永宏半导体生物科技有限公司 | Complex antimicrobials and preparation method thereof are applied with it |
| CN110591184A (en) * | 2019-09-18 | 2019-12-20 | 泉州师范学院 | Styrene polymer antibacterial material and preparation method thereof |
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| CN104162681A (en) * | 2014-07-30 | 2014-11-26 | 青岛科技大学 | Preparation method for silver-zinc oxide nano-composite structure |
| CN109735105A (en) * | 2018-12-27 | 2019-05-10 | 张家港大塚化学有限公司 | High-intensitive wear-resisting polyetherimide composite wood of antistatic antibiotic and preparation method thereof |
| CN109845743A (en) * | 2019-01-29 | 2019-06-07 | 深圳市永宏半导体生物科技有限公司 | Complex antimicrobials and preparation method thereof are applied with it |
| CN110591184A (en) * | 2019-09-18 | 2019-12-20 | 泉州师范学院 | Styrene polymer antibacterial material and preparation method thereof |
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| CN112280195A (en) * | 2020-10-12 | 2021-01-29 | 中国电力科学研究院有限公司 | Nano-sheet ZnO @ Ag/insulating composite material and preparation method thereof |
| CN113788498A (en) * | 2021-09-09 | 2021-12-14 | 同曦集团有限公司 | Material with visible light catalytic air purification and antibacterial functions and preparation method thereof |
| CN113788498B (en) * | 2021-09-09 | 2023-09-29 | 同曦集团有限公司 | Material with visible light catalytic air purification and antibacterial functions and preparation method thereof |
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| CN111218064B (en) | 2022-08-02 |
| AU2020103516A4 (en) | 2021-01-28 |
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