CN107418103B - Anti-electromagnetic radiation antibacterial film adhered to protective clothing and preparation method thereof - Google Patents
Anti-electromagnetic radiation antibacterial film adhered to protective clothing and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electromagnetic radiation protection, in particular to an anti-electromagnetic radiation antibacterial film adhered to protective clothing and a preparation method thereof, wherein the anti-electromagnetic radiation antibacterial film uses the following raw materials in parts by weight: 25-40 parts of starch, 45-65 parts of polyvinyl chloride, 8-15 parts of wave-absorbing complexing agent and SiO25-10 parts of sol, 1.5-2.5 parts of citric acid, 0.5-1.3 parts of coupling agent, 3-5 parts of plasticizer and 0.2-0.8 part of defoaming agent; the wave-absorbing compound agent is Fe3O4As core, mesoporous SiO2Production of Fe for the Shell3O4‑SiO2After the nanoparticles, Fe is added3O4‑SiO2And compounding with tetrapod-like ZnO, and coating with polypyrrole to obtain the composite microsphere. The preparation method provided by the invention is simple in process and convenient to operate, and the prepared anti-electromagnetic-radiation antibacterial film has excellent anti-electromagnetic-radiation performance, better antibacterial performance, stronger toughness and difficulty in tearing.
Description
Technical Field
The invention relates to the technical field of electromagnetic radiation protection, in particular to an anti-electromagnetic radiation antibacterial film adhered to protective clothing and a preparation method thereof.
Background
Along with the rapid development of the electronic industry and wireless communication technology, the electronic and electrical equipment is more and more widely applied, and meanwhile, the electromagnetic radiation generated in the living environment of people is more and more. Electromagnetic radiation is the physical phenomenon that energy is transmitted in the air in the form of electromagnetic waves at the speed of light, the harm of media at home and abroad to electromagnetic radiation is more and more reported in recent years, and meanwhile, the negative influence on health caused by high-intensity electromagnetic radiation is increasingly paid attention to by the medical community.
A large number of experimental studies and survey observation results show that the effects of electromagnetic radiation on human bodies are as follows: firstly, the heat effect is that more than 70% of human bodies are water, and water molecules rub with each other after being subjected to electromagnetic radiation with certain intensity to cause the temperature of the body to rise, so that the working temperature of internal organs is influenced; secondly, due to non-thermal effect, organs and tissues of a human body have weak electromagnetic fields which are stable and orderly, and once the interference intensity of the external electromagnetic field is overlarge, the weak electromagnetic field in a balanced state is possibly influenced or even damaged; thirdly, after the thermal effect and the non-thermal effect act on the human body, if the influence on the human body is influenced again for a long time by the radiation of the excessive electromagnetic waves before the human body recovers, the influence degree can be accumulated, and permanent accumulation influence can be formed in the long time. Experts introduce that electromagnetic radiation above 2 milligauss can cause diseases of people, the first time the electromagnetic radiation is applied to the skin and mucous membrane tissues of the human body, and symptoms are represented by eyelid swelling, eye congestion, nasal obstruction and nasal discharge, throat discomfort, or repeated urticaria, eczema, pruritus and the like on the skin of the whole body; vitiligo, psoriasis, allergic purpura and the like may appear when the immune function of the human body is affected. It is known that electromagnetic wave radiation is listed as a fourth environmental pollution source after water source, atmosphere and noise by the world health organization, and long-term excessive electromagnetic radiation can cause damage to human reproductive, nervous and immune systems and is a main cause of skin diseases, cardiovascular diseases, diabetes and cancer mutation. The mode of wearing the electromagnetic radiation prevention clothes is often adopted to avoid the harm of electromagnetic radiation to human bodies, and the method is generally applied to special employees.
The radiation protection clothes use the loop formed by metal fiber in the clothes to generate induced current, because the induced current generates the reverse electromagnetic field to shield, namely when the aperture of the metal net is smaller than the wavelength 1/4 of the electromagnetic wave, the electromagnetic wave can not penetrate the metal net. However, metal is used as an electromagnetic shielding material for reflection, reflected radio frequency signals cause secondary pollution to the space environment, the protection effect on electromagnetic radiation is not ideal, and meanwhile, the problem that bacteria are easy to grow exists.
Disclosure of Invention
In view of the above, the present invention is directed to an anti-electromagnetic radiation antibacterial film adhered to a protective garment and a preparation method thereof, wherein the preparation method has advantages of simple process and convenient operation, and the prepared anti-electromagnetic radiation antibacterial film has excellent anti-electromagnetic radiation performance, better antibacterial performance, stronger toughness and is not easy to tear.
The invention solves the technical problems by the following technical means:
an anti-electromagnetic radiation antibacterial film adhered to protective clothing comprises the following raw materials in parts by weight:
25-40 parts of starch, 45-65 parts of polyvinyl chloride, 8-15 parts of wave-absorbing complexing agent and SiO25-10 parts of sol, 1.5-2.5 parts of citric acid, 0.5-1.3 parts of coupling agent, 3-5 parts of plasticizer and 0.2-0.8 part of defoaming agent; the wave-absorbing compound agent is Fe3O4As core, mesoporous SiO2Production of Fe for the Shell3O4-SiO2After the nanoparticles, Fe is added3O4-SiO2And compounding with tetrapod-like ZnO, and coating with polypyrrole to obtain the composite microsphere.
The raw materials of the antibacterial film disclosed by the invention use the wave-absorbing complexing agent with a multilayer composite structure, and after the wave-absorbing complexing agent and other raw materials are formed into a film together, the wave-absorbing complexing agent can perform multilayer loss on incoming electromagnetic waves so as to achieve the purpose of radiation protection. Fe3O4Has electromagnetic wave absorption performance, but is easy to agglomerate and oxidize due to the action of magnetic dipole moment of the Fe-Fe alloy, and the invention is applied to the Fe alloy3O4Upper coated SiO2Form with Fe3O4Is SiO with inner core and mesopore2Fe as shell3O4-SiO2Nanoparticles not only capable of preventing Fe3O4Oxidation and increase of Fe3O4The stability of the mesoporous SiO prevents agglomeration, can also enhance the electromagnetic wave absorption performance2The mesoporous structure of the shell can generate certain functions of scattering, reflecting and the like on electromagnetic waves, the process can generate great loss on the electromagnetic waves, and the electromagnetic waves which are not lost are in mesoporous SiO2Under the action of the shell, Fe is smoothly entered3O4The wave absorber is lost. The tetrapod-like ZnO has special three-dimensionTetrapod-like structure and nanoscale needle diameter, when combined with Fe3O4-SiO2When electromagnetic waves are incident to the surface of the composite material, the tetrapod-like ZnO can absorb the electromagnetic waves to reduce reflection, and the vibration energy of the electromagnetic waves is converted into electric energy, heat energy and the like; in addition, the four needle points of the tetrapod-shaped ZnO show special tip nanometer effect, can efficiently kill and eliminate bacteria and decompose toxin secreted by the bacteria, has stronger antibacterial effect, and has stronger and lasting antibacterial activity compared with the traditional antibacterial agent. The polypyrrole has an absorption rate lower than-8 dB in a 3cm wave band and is coated in Fe3O4-SiO2The composite formed by the composite and the tetrapod-like ZnO can further improve the magnetic loss performance of the wave-absorbing composite agent and broaden the absorption frequency band.
Further, said Fe3O4Is a pointed-cone octahedral particle with the average particle size of 45-80 nm synthesized by a hydrothermal method.
Pointed octahedron Fe3O4The particles are a low-reflectivity broadband electromagnetic wave absorbing material, the absorption in a low frequency band (2-13 GHz) mainly comes from magnetic loss and dielectric loss, the absorption in a high frequency band (13-18 GHz) mainly comes from dielectric loss and weak magnetic loss, and the sharp cone shape is favorable for enhancing the electromagnetic loss and electromagnetic matching.
Further, said Fe3O4-SiO2The nanoparticles are of Fe3O4Taking tetraethoxysilane dispersed with nickel nano powder as a precursor as a core, and preparing mesoporous SiO by adopting an improved Stober method2Coated with Fe3O4The mesoporous SiO is2Nickel nano particles are adhered in the pore channels.
The nickel nano particles have higher saturation magnetization and magnetic conductivity, are one of important electromagnetic wave absorption materials, and utilize mesoporous SiO2Good adsorptivity and higher specific surface area characteristic enable nickel nano particles to be adsorbed to mesoporous SiO2On the surface and walls of the pores, with Fe3O4Formation of nickel, Fe3O4And SiO2Composite material capable of further improving electromagnetic shielding of filmThe effect of the radiation.
Further, the ZnO is tetrapod-like ZnO whisker prepared by thermally evaporating zinc oxide sheets, and the Fe is3O4-SiO2The nano particles are uniformly adhered to the surface of the zinc oxide whisker to prepare ZnO-Fe3O4-SiO2。
Four needle point parts with nanometer effect of the four needle zinc oxide do not agglomerate, can be more uniformly dispersed in the film raw material, and can also strengthen, toughen and strengthen the wear resistance of the film. ZnO-Fe3O4-SiO2The film can not only enhance the anti-electromagnetic radiation effect of the film, but also play an antibacterial role.
Further, the coupling agent is a titanate coupling agent, the plasticizer is dioctyl phthalate, and the defoaming agent is one of tributyl polyphosphate, lauryl phenylacetate and polydimethylsiloxane.
In addition, the invention also discloses a preparation method of the anti-electromagnetic radiation, which comprises the following steps: respectively weighing the raw materials in corresponding weight parts for standby application, putting starch into a high-speed mixer, adding polyvinyl chloride and distilled water, stirring for 4.5-5.5 h at 90-96 ℃, cooling to 55-65 ℃, adding citric acid, stirring for 2-3 h, cooling to room temperature, adding plasticizer, coupling agent and defoaming agent, stirring uniformly, heating to 60-70 ℃, adding wave-absorbing complexing agent and SiO2Stirring the sol at a rotating speed of 600-850 r/min for 1.5-3.0 h, cooling to room temperature, standing at 2-5 ℃ for 10-16 h to obtain a membrane solution, coating the membrane solution on a casting machine with a surface temperature of 50-55 ℃ to form a membrane, removing the membrane, and drying in vacuum at 55-60 ℃ to obtain the anti-electromagnetic radiation antibacterial membrane.
Further, the wave-absorbing complexing agent is prepared as follows: adding 5.0g of ZnO-Fe into 0.1mol/L hydrochloric acid solution per liter3O4-SiO2Stirring with 35g of sodium dodecyl benzene sulfonate, adding 60-75 mL of pyrrole, continuously stirring and uniformly mixing, adding 5g of ammonium persulfate under an ice bath condition, reacting for 15h, performing suction filtration, washing filter residues with ethanol and deionized water, performing vacuum drying at 55-60 ℃ for 24h, taking out, and grinding to obtain the wave-absorbing composite agent.
Further, the ZnO-Fe3O4-SiO2The preparation of (a) was as follows: ultrasonically dispersing graphene oxide prepared by a Hunmers method in deionized water to obtain suspension, and taking Fe3O4-SiO2Dispersing the nano particles in the suspension by ultrasonic waves, adding tetrapod-like ZnO, stirring to obtain dispersion, transferring the dispersion into a polytetrafluoroethylene inner container of a reaction kettle, reacting for 2 hours at 120-135 ℃, performing centrifugal separation, and drying to obtain ZnO-Fe3O4-SiO2. The present invention uses graphene oxide as Fe3O4-SiO2Dispersing agent of nano particles to realize Fe3O4-SiO2The nano particles are uniformly and stably loaded on the surface of the tetrapod-like ZnO crystal whisker.
Further, said Fe3O4-SiO2The nanoparticles were prepared as follows: dispersing 5g Fe per liter of deionized water3O4Adding 80mL of 5mol/L HCl and 200mL of 5mol/L sodium citrate solution into the nano particles, stirring for 1.5h, and carrying out magnetic separation to obtain modified Fe3O4Nanoparticles of modified Fe3O4Ultrasonically dispersing in ethanol solution containing 20 w% ammonia water, dropwise adding 5mL of tetraethoxysilane dispersed with nickel nano powder, stirring for 24h, and magnetically separating and washing with water and ethanol to obtain single-layer SiO2Coated with Fe3O4Dispersing composite particles in a mixed solution of 1L of ethanol, 1.5L of deionized water and 50mL of 25 w% ammonia water, adding 10g of hexadecyl trimethyl ammonium bromide for ultrasonic dispersion for 50min, slowly dropwise adding 5mL of tetraethoxysilane dispersed with nickel nano powder, stirring for 15h, magnetically separating and washing with water and ethanol for multiple times, vacuum drying the obtained solid at 60 ℃ for 10h, transferring the dried solid into a tubular furnace, heating to 350 ℃ at the speed of 10 ℃/min under the argon atmosphere, keeping the temperature for 5h, cooling and taking out to obtain Fe3O4-SiO2And (3) nanoparticles.
The preparation raw materials of the anti-electromagnetic radiation antibacterial film of the invention use the wave-absorbing compound agent with a multilayer composite structure, and the wave-absorbing compound agent endows the antibacterial film with antibacterial efficacy through the special tip nanometer effect of the tetrapod-like zinc oxide whiskersAnd the antibacterial film has stronger toughness, so that the antibacterial film is not easy to grow bacteria and is not easy to tear; on the other hand, the mesoporous SiO with nickel nano particles adhered in the pore passage2Coated with Fe3O4The core-shell composite microspheres improve the anti-electromagnetic radiation effect of the film and can prevent Fe3O4Oxidation and increase of Fe3O4Stability of (2); in addition, the polypyrrole on the outermost layer of the wave-absorbing complexing agent can further improve the magnetic loss performance of the wave-absorbing complexing agent and broaden the absorption frequency band. The anti-electromagnetic radiation antibacterial film disclosed by the invention can be used for carrying out layer-by-layer induced absorption conversion on electromagnetic waves, so that the purpose of thoroughly losing the electromagnetic waves is achieved, the electromagnetic radiation is prevented from harming human health, the film can be adhered to the radiation-proof clothes through glue, and the anti-electromagnetic radiation function of the film can be realized in various different environments.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
the invention relates to an anti-electromagnetic radiation antibacterial film adhered to protective clothing, which uses the following raw materials in parts by weight: 25-40 parts of starch, 45-65 parts of polyvinyl chloride, 8-15 parts of wave-absorbing complexing agent and SiO25-10 parts of sol, 1.5-2.5 parts of citric acid, 0.5-1.3 parts of coupling agent, 3-5 parts of plasticizer and 0.2-0.8 part of defoaming agent. Wherein the wave-absorbing compound agent is Fe3O4As core, mesoporous SiO2Production of Fe for the Shell3O4-SiO2Nanoparticles of Fe and mixing3O4-SiO2And compounding with tetrapod-like ZnO, and coating with polypyrrole to obtain the composite microsphere. In which Fe3O4Is pointed-cone octahedral particles with the average particle size of 45-80 nm, Fe, synthesized by a hydrothermal method3O4-SiO2The nanoparticles are of Fe3O4Taking tetraethoxysilane dispersed with nickel nano powder as a precursor as a core, and preparing mesoporous SiO by adopting an improved Stober method2Coated with Fe3O4The core-shell composite microsphere of (1), and mesoporous SiO2Nickel nano particles are adhered in the pore channels, ZnO is tetrapod-like ZnO crystal whisker and Fe which are prepared by thermally evaporating zinc oxide sheets3O4-SiO2The nano particles are uniformly adhered to the surface of the zinc oxide whisker to prepare ZnO-Fe3O4-SiO2。
The wave-absorbing composite agent used in the invention has a multilayer composite structure and is formed by coating various raw materials layer by layer, and the preparation of the wave-absorbing composite agent is explained by specific examples below.
The first embodiment is as follows: fe3O4Preparation of
Preparation of Fe by hydrothermal method3O4: weighing polyethylene glycol, adding into deionized water to obtain 5mol/L viscous liquid, and weighing 0.3mol ferrous sulfate (FeSO)4·7H2O) and 0.15mol of sodium thiosulfate (NaS)2O3·5H2O), putting the materials into a liner of a polytetrafluoroethylene reaction kettle, adding 0.88L of viscous liquid, stirring uniformly, quickly pouring 0.12L of sodium hydroxide solution with the concentration of 5mol/L, stirring, and generating a precursor Fe (OH) on the surface2Continuously stirring and uniformly mixing, carrying out ultrasonic oscillation for 20min under the conditions of the frequency of 30kHz and the power of 350W, reacting for 8-11 h at 180 ℃ in a reaction kettle, naturally cooling to room temperature, taking out the reactant, carrying out magnetic separation and washing for multiple times by using deionized water, and carrying out vacuum drying for 10h at 65-70 ℃ to obtain Fe3O4And (3) granules. For Fe3O4Scanning of the particles by scanning Electron microscope showed Fe prepared in this example3O4The particles are dispersed octahedral cones, the surfaces of the crystals are flat, each surface is approximate to a regular triangle, and the average particle size distribution of the crystals is measured to be 45-80 nm.
Example two: fe3O4-SiO2Preparation of
5g of Fe prepared in example one was dispersed in deionized water per liter3O4Adding 80mL of 5mol/L HCl and 200mL of 5mol/L trisodium citrate solution into the nano particles, stirring for 1.5h, and carrying out magnetic separation to obtain modified Fe3O4Nanoparticles, sodium citrate adsorbed on Fe3O4The surface of the nano-particle is changed into Fe3O4Surface potential of (1) of (2) is favorable for Fe3O4The nano particles overcome the magnetic dipole moment to modify Fe3O4Ultrasonically dispersing the mixture into an ethanol solution containing 20 w% ammonia water, stirring and dropwise adding 5mL of tetraethoxysilane dispersed with nickel nano powder, dispersing the nickel nano powder with the mass concentration of 5% in the tetraethoxysilane, continuing stirring for 24 hours after the tetraethoxysilane is dropwise added, and magnetically separating and washing the mixture by using water and ethanol until the solution is neutral to obtain a single-layer SiO2Coated with Fe3O4Dispersing composite particles in a mixed solution of 1L of ethanol, 1.5L of deionized water and 50mL of 25-25 w% ammonia water, adding 10g of hexadecyl trimethyl ammonium bromide for ultrasonic dispersion for 50min, slowly dropwise adding 5mL of tetraethoxysilane dispersed with nickel nano powder, continuously stirring for 15h, then magnetically separating and washing with water and ethanol for several times, vacuum drying the obtained solid at 60 ℃ for 10h, transferring the dried solid into a tubular furnace, heating to 350 ℃ at the speed of 10 ℃/min under the argon atmosphere, keeping the temperature for 5h, cooling and taking out to obtain Fe3O4-SiO2And (3) nanoparticles.
Example three: ZnO-Fe3O4-SiO2Preparation of
Preparing graphene oxide by adopting a Hunmers method, and ultrasonically dispersing the graphene oxide in deionized water to prepare a suspension with the mass concentration of 1.2 mg/mL; putting zinc particles into a tablet press to be pressed into slices, then putting the slices into an alumina crucible, putting the alumina crucible into a hearth, heating to 450 ℃ at the speed of 8 ℃/min, keeping the temperature for 2h at constant temperature, heating to 950 ℃ at the speed of 5 ℃/min, keeping the temperature for 1h, cooling along with the furnace, and grinding to obtain tetrapod-like ZnO powder particles; taking Fe prepared in example two3O4-SiO2Adding the nano particles into the suspension, performing ultrasonic dispersion for 30min under the conditions of frequency of 25kHz and power of 100W, and then adding 2 times of Fe3O4-SiO2Stirring the mass tetrapod-like ZnO powder particles for 1h at the rotating speed of 450-600 r/min to obtain dispersion, transferring the dispersion into a polytetrafluoroethylene inner container of a reaction kettle, reacting for 2h at the temperature of 120-135 ℃, centrifuging, and drying to obtain ZnO-Fe3O4-SiO2。
Example four: preparation of wave-absorbing compound agent
Adding 5.0g of ZnO-Fe into 0.1mol/L hydrochloric acid solution per liter3O4-SiO2Stirring the mixture and 35g of sodium dodecyl benzene sulfonate for 1.5-2.0 h, adding 60mL of pyrrole, continuously stirring for 1.0h, adding 5g of ammonium persulfate under an ice bath condition to react for 15h, performing suction filtration, washing filter residues with ethanol and deionized water until the filtrate is colorless, performing vacuum drying at 55-60 ℃ for 24h, taking out and grinding to obtain a product, namely ZnO-Fe3O4-SiO2The wave-absorbing compound is a microsphere structure with a core and a polypyrrole shell coated outside the core, namely the wave-absorbing compound.
Example five: preparation of wave-absorbing compound agent
Adding 5.0g of ZnO-Fe into 0.1mol/L hydrochloric acid solution per liter3O4-SiO2Stirring the mixture and 35g of sodium dodecyl benzene sulfonate for 1.5-2.0 h, adding 70mL of pyrrole, continuously stirring for 2.0h, adding 5g of ammonium persulfate under an ice bath condition to react for 15h, performing suction filtration, washing filter residues with ethanol and deionized water until the filtrate is colorless, performing vacuum drying at 55-60 ℃ for 24h, taking out and grinding to obtain a product, namely ZnO-Fe3O4-SiO2The wave-absorbing compound is a microsphere structure with a core and a polypyrrole shell coated outside the core, namely the wave-absorbing compound.
Example six: preparation of wave-absorbing compound agent
Adding 5.0g of ZnO-Fe into 0.1mol/L hydrochloric acid solution per liter3O4-SiO2Stirring the mixture and 35g of sodium dodecyl benzene sulfonate for 1.5-2.0 h, adding 75mL of pyrrole, continuously stirring for 2.0h, adding 5g of ammonium persulfate under an ice bath condition to react for 15h, performing suction filtration, washing filter residues with ethanol and deionized water until the filtrate is colorless, performing vacuum drying at 55-60 ℃ for 24h, taking out and grinding to obtain a product, namely ZnO-Fe3O4-SiO2The wave-absorbing compound is a microsphere structure with a core and a polypyrrole shell coated outside the core, namely the wave-absorbing compound.
Example seven: preparation of anti-electromagnetic radiation antibacterial film
Weighing the following raw materials in parts by weight: 25 parts of starch, 45 parts of polyvinyl chloride, 8 parts of wave-absorbing complexing agent prepared in the fourth embodiment and SiO25 parts of sol, 1.5 parts of citric acid, 0.5 part of titanate coupling agent, 3 parts of dioctyl phthalate and 0.2 part of tributyl polyphosphate for standby application, putting starch into a high-speed mixer, and adding polyvinyl chloride and distilled waterAdding distilled water in an amount which is 60 times of the weight of polyvinyl chloride, stirring at 90 ℃ for 4.5-5.5 h, cooling to 55-65 ℃, adding citric acid, stirring for 2-3 h, cooling to room temperature, adding plasticizer, coupling agent and defoaming agent, stirring uniformly, heating to 60 ℃, adding wave-absorbing complexing agent and SiO, adding2Stirring the sol at a rotating speed of 600r/min for 1.5h, cooling to room temperature, standing at 2-5 ℃ for 10-16 h to obtain a membrane solution, coating the membrane solution on a casting machine with a surface temperature of 50-55 ℃ to form a membrane, uncovering the membrane, and drying at 55-60 ℃ in vacuum to obtain the electromagnetic radiation resistant antibacterial membrane.
Example eight: preparation of anti-electromagnetic radiation antibacterial film
Weighing the following raw materials in parts by weight: 40 parts of starch, 65 parts of polyvinyl chloride, 10 parts of wave-absorbing complexing agent prepared in the sixth embodiment and SiO210 parts of sol, 2.0 parts of citric acid, 1.3 parts of titanate coupling agent, 4 parts of dioctyl phthalate and 0.8 part of polydimethylsiloxane for standby application, putting starch into a high-speed mixer, adding polyvinyl chloride and distilled water, wherein the adding amount of the distilled water is 60 times of the mass of the polyvinyl chloride, stirring for 4.5-5.5 h at 96 ℃, cooling to 55-65 ℃, adding citric acid, stirring for 2-3 h, cooling to room temperature, adding plasticizer, coupling agent and defoaming agent, stirring uniformly, heating to 65 ℃, adding wave-absorbing complexing agent and SiO, stirring uniformly, and drying to obtain the final product2Stirring the sol at a rotating speed of 700r/min for 3.0h, cooling to room temperature, standing at 2-5 ℃ for 10-16 h to obtain a membrane solution, coating the membrane solution on a casting machine with a surface temperature of 50-55 ℃ to form a membrane, removing the membrane, and drying at 55-60 ℃ in vacuum to obtain the electromagnetic radiation resistant antibacterial membrane.
Example nine: preparation of anti-electromagnetic radiation antibacterial film
Weighing the following raw materials in parts by weight: 40 parts of starch, 65 parts of polyvinyl chloride, 12 parts of wave-absorbing compound prepared in the fifth embodiment and SiO210 parts of sol, 2.0 parts of citric acid, 1.3 parts of titanate coupling agent, 4 parts of dioctyl phthalate and 0.8 part of lauryl phenylacetate for standby application, putting starch into a high-speed mixer, adding polyvinyl chloride and distilled water, wherein the adding amount of the distilled water is 60 times of the mass of the polyvinyl chloride, stirring for 4.5-5.5 hours at 96 ℃, and reducing the temperatureHeating to 55-65 ℃, adding citric acid, stirring for 2-3 h, cooling to room temperature, adding plasticizer, coupling agent and defoaming agent, stirring uniformly, heating to 68 ℃, adding wave-absorbing complexing agent and SiO2Stirring the sol at the rotating speed of 800r/min for 3.0h, cooling to room temperature, standing at the temperature of 2-5 ℃ for 10-16 h to obtain a membrane liquid, coating the membrane liquid on a casting machine with the surface temperature of 50-55 ℃ to form a membrane, uncovering the membrane, and drying in vacuum at the temperature of 55-60 ℃ to obtain the electromagnetic radiation resistant antibacterial membrane.
Example ten: preparation of anti-electromagnetic radiation antibacterial film
Weighing the following raw materials in parts by weight: 40 parts of starch, 65 parts of polyvinyl chloride, 15 parts of wave-absorbing complexing agent prepared in the fifth embodiment and SiO210 parts of sol, 2.5 parts of citric acid, 1.3 parts of titanate coupling agent, 5 parts of dioctyl phthalate and 0.8 part of tributyl polyphosphate for standby application, putting starch into a high-speed mixer, adding polyvinyl chloride and distilled water, wherein the adding amount of the distilled water is 60 times of the mass of the polyvinyl chloride, stirring for 4.5-5.5 h at 96 ℃, cooling to 55-65 ℃, adding the citric acid, stirring for 2-3 h, cooling to room temperature, adding plasticizer, coupling agent and defoaming agent, stirring uniformly, heating to 70 ℃, adding wave-absorbing complexing agent and SiO2Stirring the sol at the rotating speed of 850r/min for 3.0h, cooling to room temperature, standing at the temperature of 2-5 ℃ for 10-16 h to obtain a membrane solution, coating the membrane solution on a casting machine with the surface temperature of 50-55 ℃ to form a membrane, uncovering the membrane, and drying in vacuum at the temperature of 55-60 ℃ to obtain the electromagnetic radiation resistant antibacterial membrane.
The performance of the anti-electromagnetic radiation antibacterial films prepared in the seven to ten embodiments is respectively detected, an electromagnetic wave shielding performance tester (XF type) scans the films to test the anti-electromagnetic radiation performance of each point in different frequency bands (scanning frequency bands are 30 to 1000MHz, frequency intervals are 10MHz), and the results are shown in Table 1; the antibacterial films prepared in the examples were tested for the average strength in the transverse direction, the average modulus of elasticity in the transverse direction, the average strength in the machine direction, and the average modulus of elasticity in the machine direction according to GB/T1040.3-2006, and the results are shown in Table 1; finally, the antibacterial effect of the antibacterial film prepared in each example on escherichia coli and staphylococcus aureus was examined, and the results are shown in table 1.
TABLE 1
The data in table 1 show that the anti-electromagnetic-radiation antibacterial film prepared by the invention has an excellent anti-electromagnetic-radiation function, certain strength and toughness, is not easy to tear, has a strong antibacterial effect, and can prevent bacteria from growing on the film. The anti-electromagnetic radiation antibacterial film can be adhered to protective clothing, so that the harm of electromagnetic radiation to the health of human bodies is avoided.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (8)
1. An anti-electromagnetic radiation antibacterial film adhered to a protective garment is characterized by comprising the following raw materials in parts by weight:
25-40 parts of starch, 45-65 parts of polyvinyl chloride, 8-15 parts of wave-absorbing complexing agent and SiO25-10 parts of sol, 1.5-2.5 parts of citric acid, 0.5-1.3 parts of coupling agent, 3-5 parts of plasticizer and 0.2-0.8 part of defoaming agent;
the wave-absorbing compound agent is Fe3O4As core, mesoporous SiO2Production of Fe for the Shell3O4-SiO2After the nanoparticles, Fe is added3O4-SiO2The composite microsphere is compounded with tetrapod-like ZnO and coated with polypyrrole, and the Fe is3O4Is prepared by a hydrothermal methodThe prepared pointed octahedral particles with the average particle size of 45-80 nm.
2. The anti-electromagnetic radiation antimicrobial film adhered to protective clothing of claim 1, wherein said Fe3O4-SiO2The nanoparticles are of Fe3O4Taking tetraethoxysilane dispersed with nickel nano powder as a precursor as a core, and preparing mesoporous SiO by adopting an improved Stober method2Coated with Fe3O4The mesoporous SiO is2Nickel nano particles are adhered in the pore channels.
3. The anti-electromagnetic radiation antibacterial film adhered to the protective clothing of claim 2, wherein said ZnO is tetrapod-like ZnO whiskers made by thermally evaporating zinc oxide flakes, and said Fe is3O4-SiO2The nano particles are uniformly adhered to the surface of the zinc oxide whisker to prepare ZnO-Fe3O4-SiO2。
4. An anti-electromagnetic radiation antibacterial film adhered to protective clothing as claimed in claim 3, wherein said coupling agent is titanate coupling agent, said plasticizer is dioctyl phthalate, and said defoaming agent is one of tributyl polyphosphate, lauryl phenylacetate and polydimethylsiloxane.
5. The method for preparing the anti-electromagnetic radiation antibacterial film adhered to the protective clothing according to any one of claims 1 to 4, wherein the method comprises the following steps: respectively weighing the raw materials in corresponding weight parts for standby application, putting starch into a high-speed mixer, adding polyvinyl chloride and distilled water, stirring for 4.5-5.5 h at 90-96 ℃, cooling to 55-65 ℃, adding citric acid, stirring for 2-3 h, cooling to room temperature, adding plasticizer, coupling agent and defoaming agent, stirring uniformly, heating to 60-70 ℃, adding wave-absorbing complexing agent and SiO2Stirring the sol at 600-850 r/min for 1.5-3.0 h, cooling to room temperature at 2-5 deg.CStanding for 10-16 h to obtain a membrane liquid, coating the membrane liquid on a casting machine with the surface temperature of 50-55 ℃ to form a membrane, uncovering the membrane, and drying in vacuum at 55-60 ℃ to obtain the anti-electromagnetic-radiation antibacterial membrane.
6. The method for preparing the anti-electromagnetic radiation antibacterial film adhered to the protective clothing according to claim 5, wherein the wave-absorbing complexing agent is prepared as follows: adding ZnO-Fe into 0.1mol/L hydrochloric acid solution3O4-SiO2Stirring with sodium dodecyl benzene sulfonate, adding pyrrole, continuously stirring and uniformly mixing, adding ammonium persulfate under an ice bath condition, reacting for 15 hours, performing suction filtration, washing filter residues with ethanol and deionized water, performing vacuum drying at 55-60 ℃ for 24 hours, taking out, and grinding to obtain the wave-absorbing compound agent.
7. The method for preparing the anti-electromagnetic radiation antibacterial film adhered to the protective clothing of claim 6, wherein the ZnO-Fe3O4-SiO2The preparation of (a) was as follows: ultrasonically dispersing graphene oxide prepared by a Hunmers method in deionized water to obtain suspension, and taking Fe3O4-SiO2Dispersing the nano particles in the suspension by ultrasonic waves, adding tetrapod-like ZnO, stirring to obtain dispersion, transferring the dispersion into a polytetrafluoroethylene inner container of a reaction kettle, reacting for 2 hours at 120-135 ℃, performing centrifugal separation, and drying to obtain ZnO-Fe3O4-SiO2。
8. The method of claim 7, wherein the Fe is selected from the group consisting of Fe, Cr, Fe, and Fe3O4-SiO2The nanoparticles were prepared as follows: dispersing Fe in deionized water3O4Adding 5mol/L hydrochloric acid solution and 5mol/L sodium citrate solution into the nano particles, stirring for 1.5h, and carrying out magnetic separation to obtain modified Fe3O4Nanoparticles of modified Fe3O4Ultrasonically dispersing in ethanol solution containing 20 w% ammonia water, and dropwise adding nickel nanopowder dispersed positive electrodeStirring ethyl silicate for 24h, and magnetically separating and washing with water and ethanol to obtain single-layer SiO2Coated with Fe3O4Dispersing composite particles in a mixed solution of ethanol, deionized water and 25 w% ammonia water, adding hexadecyl trimethyl ammonium bromide for ultrasonic dispersion for 50min, slowly dropwise adding tetraethoxysilane dispersed with nickel nano powder, stirring for 15h, magnetically separating and washing with water and ethanol for multiple times, vacuum-drying the obtained solid at 60 ℃ for 10h, transferring the dried solid into a tubular furnace, heating to 350 ℃ at the speed of 10 ℃/min under the argon atmosphere, keeping the temperature for 5h, cooling and taking out to obtain Fe3O4-SiO2And (3) nanoparticles.
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