CN112795098A - Antibacterial plastic and preparation method thereof - Google Patents
Antibacterial plastic and preparation method thereof Download PDFInfo
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- 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
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- C08K2003/085—Copper
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- C08K2003/2241—Titanium dioxide
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Abstract
The invention discloses an antibacterial plastic and a preparation method thereof, and belongs to the technical field of plastics. The antibacterial plastic is prepared from the following raw materials in parts by weight: 30-40 parts of plastic substrate, 5-10 parts of carbon nanotube fiber, 6-14 parts of montmorillonite, 3-10 parts of plasticizer, 0.5-3 parts of coupling agent, 2-6 parts of dispersing agent, 1-4 parts of nucleating agent, 3-7 parts of stabilizer and 3-10 parts of antibacterial agent. By adding the novel antibacterial agent and the modified nano titanium dioxide, the invention not only maintains the original excellent thermal stability and mechanical property of the antibacterial plastic, but also overcomes the defects of poor antibacterial property and easy aging of the traditional plastic, and has the advantages of simple operation, no pollution, low cost and the like.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to an antibacterial plastic and a preparation method thereof.
Background
The antibacterial plastic is a novel environment-friendly material with special functions developed in recent years, and the antibacterial plastic is made by adding a certain amount of antibacterial agent into the plastic, so that the antibacterial plastic has antibacterial performance, can inhibit and kill microbes such as bacteria, fungi and the like which are in contact with the antibacterial plastic, and does not lose the original conventional performance and processing performance of the antibacterial plastic. The ideal antibacterial plastic has the performances of long-acting, high efficiency, broad spectrum, safety, no toxicity, no irritation and the like, and the type and the processing technology of the antibacterial agent directly determine the service performance of a final product. As a novel functional material, the antibacterial plastic can solve the problem of bacterial infection from the root, thereby improving the health level of people.
The antibacterial plastic mainly takes polypropylene (PP), Polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), Polystyrene (PS) and acrylonitrile-butadiene-styrene copolymer (ABS) as a matrix, has the widest application range, can be widely applied to the fields of industry, construction, agriculture, communication, traffic, medical treatment, environmental protection, daily life and the like, researches and prepares novel antibacterial plastic products with antibacterial property, and has very important significance for improving the living environment of people, reducing the generation of diseases, purifying the environment and the like.
The traditional antibacterial plastic mainly adopts organic antibacterial agents, natural and high-molecular antibacterial agents, and although the organic antibacterial agents have the advantages of strong bactericidal power, wide sources, low price and the like, the antibacterial agents have poor thermal stability, are easy to decompose and have poor durability and certain toxicity in the using process; natural and polymeric antibacterial agents have the advantages of being non-toxic and environmentally friendly, but have poor heat resistance and difficult processing and most polymers have limited thermodynamic compatibility with each other. The inorganic antibacterial agent has long-acting effect, no drug resistance and slow release. The invention provides an antibacterial plastic with long-acting antibacterial effect and good ageing resistance, and overcomes the defects caused by the traditional antibacterial agent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an antibacterial plastic and a preparation method thereof, a 2-step redox method is adopted to synthesize the bimetal composite antibacterial agent, firstly, polydopamine serving as a reducing agent is added into a copper-containing solution to prepare a copper seed crystal solution, so that dopamine-coated copper nanoparticles are obtained, silver ammonia ions are adsorbed on the surface of the nano Cu particles due to the complexation of catechol groups and nitrogen-containing groups in a polydopamine structure to metal ions, the weak reducibility of the polydopamine can reduce the adsorbed metal ions to generate the metal nanoparticles to become catalytic active centers of the subsequent reduction reaction, and the added reducing agent enables the metal nanoparticles to continue to reduce and grow on the formed active centers to form shells, so that the antibacterial agent with a silver-copper core-shell structure coated by silver nanoparticles is formed. The prepared antibacterial agent and the modified nano titanium dioxide can be well dispersed in the antibacterial plastic, so that the mechanical property of the antibacterial plastic is not greatly influenced or can be remarkably improved, and the antibacterial plastic has good antibacterial property and ultraviolet resistance.
The technical scheme adopted by the invention is realized as follows:
the invention provides an antibacterial plastic which comprises the following raw materials in parts by weight: 30-40 parts of plastic substrate, 5-10 parts of carbon nanotube fiber, 6-14 parts of montmorillonite, 3-10 parts of plasticizer, 0.5-3 parts of coupling agent, 2-6 parts of dispersing agent, 1-4 parts of nucleating agent, 3-7 parts of stabilizer and 3-10 parts of antibacterial agent.
The polypropylene is used as a main material, the polypropylene has good chemical resistance, heat resistance, electrical insulation, strength mechanical property, high wear resistance processing property and the like, a small amount of carbon nanotube fiber is added to increase the mechanical property of the plastic, the montmorillonite can effectively improve the impact resistance of the material, and the plasticizer is used for improving the plasticity of the material and the bonding degree among substances by using the coupling agent, so that the processing property is improved; the dispersing agent is used for improving the dispersing performance among various substances, the stabilizing agent can improve the stability of the material, the nucleating agent can effectively change the incomplete crystallization of polypropylene, the crystallization rate is accelerated, the size of the polypropylene crystal is finer, the tensile strength and the mechanical property of the material are improved, the antibacterial agent is used for improving the antibacterial performance of the material, the modified nano titanium dioxide is used for further improving the antibacterial agent of the material, and the service life of the material can be prolonged.
Preferably, the antibacterial plastic is prepared from the following raw materials in parts by weight: 30-40 parts of plastic substrate, 5-10 parts of carbon nanotube fiber, 6-14 parts of montmorillonite, 3-10 parts of plasticizer, 0.5-3 parts of coupling agent, 2-6 parts of dispersing agent, 1-4 parts of nucleating agent, 3-7 parts of stabilizer, 3-10 parts of antibacterial agent and 2-7 parts of modified nano titanium dioxide.
The plastic substrate is any one or a mixture of more than two of polypropylene, polyethylene, polyamide, polyethylene terephthalate and polystyrene.
The plasticizer is any one or a mixture of more than two of styrene-butadiene, methyl methacrylate-butadiene-styrene, acrylonitrile-butadiene-styrene copolymer and chlorosulfonated polyethylene; the coupling agent is any one or a mixture of more than two of isopropyl trioleate acyloxy titanate, isopropyl tri (dodecyl benzenesulfonyl) titanate, bis (acetylacetone) ethoxy isopropoxy titanate and tetraisopropyl di (dioctyl phosphite acyloxy) titanate; the dispersing agent is polyethylene wax, cellulose acetate, methyl amyl alcohol, stearic acid monoglyceride or hexenyl bisstearamide; the nucleating agent is one or a mixture of any two of levorotatory polylactic acid, polyvinyl alcohol and benzotriazole; the stabilizer is one or two of stearate and ethylene oxide.
The antibacterial agent is a silver nano antibacterial agent or a Cu-Ag composite antibacterial agent.
Preferably, the antibacterial agent is a Cu-Ag composite antibacterial agent.
The preparation method of the Cu-Ag composite antibacterial agent comprises the following steps:
(1) mixing 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine, stirring at 80-120 ℃ for 20-50min at the stirring speed of 400-800rpm, keeping stirring, raising the temperature to 160-220 ℃ at the stirring speed of 5-15 ℃/min, continuing stirring for 2-4h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) at normal temperature and under the condition of stirring speed of 450-600rpm, adding 20-40 parts by weight of AgNO with mass fraction of (28-45)% into the seed crystal mixed solution3Heating the oleylamine solution and 5-10 parts by weight of modifier to 70-90 ℃, continuing stirring for 1.5-3 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) adding 10-50 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging at the centrifugal rotation speed of 9000-12000rpm for 10-30min, and drying the obtained solid in a vacuum drying oven at the temperature of 50-70 ℃ for 20-28h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is one or a mixture of more than two of sodium borohydride, ascorbic acid and polydopamine; preferably, the reducing agent is polydopamine.
The modifier is dodecyl triphenyl phosphonium bromide and/or sodium rectorite; preferably, the modifier is dodecyl triphenyl phosphonium bromide and sodium rectorite according to a mass ratio of 1: (1-3).
One of the inventive concepts of the invention is that a specific method is adopted to prepare the Cu-Ag composite antibacterial agent, polydopamine is used as a weak reducing agent and a binder, and a large number of catechol groups and nitrogen-containing groups contained in the structure of the polydopamine make the polydopamine have strong adsorption capacity on metal ions, and the groups are also beneficial to the grafting reaction and the next step of functionalization; the weak reducibility of the polydopamine can reduce metal ions to generate metal nanoparticles, and the metal nanoparticles can be attached to the surfaces of the metal nanoparticles due to strong adsorption force. Specifically, polydopamine and oleylamine are added into a copper solution, under the heating condition, the oleylamine firstly reduces copper nanoparticles to obtain copper nanoparticles, and the polydopamine is adsorbed on the surface of copper ions through catechol groups and nitrogen-containing groups of the polydopamine;
secondly, modifier dodecyl triphenyl phosphonium bromide and/or sodium-based rectorite is added in the process of forming the silver-copper compound, the agglomeration of nano particles is effectively prevented, and the synergistic effect of the modification of the sodium-based rectorite and the dodecyl triphenyl phosphonium bromide is utilized, so that the prepared antibacterial compound has excellent antibacterial effect and can realize long-acting antibacterial. The reason is that the dodecyl triphenyl phosphonium bromide has antibacterial performance, and phosphorus atoms in the molecular structure of the dodecyl triphenyl phosphonium bromide can form coordinate bonds with silver to adsorb the silver, so that the release speed of silver ions is delayed, and the aggregation of the silver ions is prevented. The sodium-based rectorite is aqueous aluminosilicate, is interlayer mineral regularly and alternately stacked by dioctahedral mica layers and dioctahedral montmorillonite layers, has good dispersibility and thermal stability, large specific surface area and strong adsorbability, and exchangeable cations are contained in the montmorillonite layers, and silver ions, copper ions, dodecyl triphenyl phosphonium bromide and dodecyl triphenyl phosphonium bromide adsorbing silver particles can be intercalated into the montmorillonite layers through cation exchange, so that agglomeration is effectively prevented, the antibacterial performance is improved, and a slow release effect is further realized. Specifically, due to the complexation of the catechol group and the nitrogen-containing group in the polydopamine structure on the metal ions, the silver ions are adsorbed on the surface of the nano Cu particles, the weak reducibility of the polydopamine can reduce the adsorbed metal ions to generate metal nanoparticles to become catalytic active centers of the subsequent reduction reaction, and the added reducing agent enables the metal nanoparticles to continue to reduce and grow on the formed active centers to form shells, so that the silver-copper core-shell structure coated with the silver nano antibacterial agent is formed. And dodecyl triphenyl phosphonium bromide in the modifier is adsorbed on the surface of silver particles through forming a coordination bond with the active center of silver, and then intercalated into an rectorite interlayer through cation exchange action to finally form the Cu-Ag composite antibacterial agent.
The sterilization mechanism is as follows: after the silver ions contact with bacteria, the silver ions can be combined with sulfhydryl groups of proteins in cell walls and cell membranes, so that protease of the cells loses activity, inherent components of the cells are damaged, the activity of the cells is damaged, and the bacteria are killed.
The preparation method of the modified nano titanium dioxide comprises the following steps:
(1) 2 to 7 weight portions of nano TiO2Drying the powder in a constant temperature drying oven at 80-130 deg.C for 8-14h, adding 410 parts by weight of absolute ethyl alcohol, stirring at 400-. Centrifuging at 9000-12000r/min for 20-30min, drying at 50-70 deg.C for 0.5-2h, and grinding to obtain pretreated powder;
(2) adding 8-12 parts by weight of polyacrylonitrile fiber into 15-30 parts by weight of NaSCN aqueous solution with the mass fraction of 40-60%, adding concentrated hydrochloric acid solution at 50-65 ℃ to adjust the pH value to 1-3, reacting for 5-8h, adding 10-20 parts by weight of deionized water, stirring at 600rpm of 300-40 min, performing suction filtration, and freeze-drying at-20-0 ℃ for 20-28h to obtain polyacrylonitrile powder;
(3) taking 1-5 parts by weight of pretreatment powder, 20-40 parts by weight of deionized water in a reaction container, stirring at the room temperature of 400-800rpm for 20-50min, performing ultrasonic treatment at the ultrasonic power of 80-120W and the frequency of 20kHz-45kHz for 20-40min, putting the mixture into a water bath kettle, adding 7-10 parts by weight of polyacrylonitrile powder, raising the water bath temperature to 50-70 ℃, adding 0.2-0.5 part by weight of initiator, reacting for 3-5h, adding 10-20 parts by weight of ethanol for washing, and putting the washed product into a vacuum drying oven at the temperature of 50-70 ℃ for drying for 20-30h to obtain modified nano titanium dioxide;
the initiator is any one of potassium persulfate and diisopropyl peroxydicarbonate.
Preferably, the initiator is diisopropyl peroxydicarbonate.
The second inventive concept of the invention is that modified nano titanium dioxide is added into the plastic, and initiator and polyacrylonitrile are added in the process of preparing the modified nano titanium dioxide, so that the reaction efficiency of the polyacrylonitrile and the nano titanium dioxide can be effectively improved. Specifically, the polyacrylonitrile fiber is hydrolyzed by hydrochloric acid to obtain carboxylated hydrolysis product polyacrylonitrile, and then the polyacrylonitrile and KH-550 modified nano TiO are mixed2Passing the powder through-COOH and-NH2The reaction between the two to obtain the polyacrylonitrile modified nano titanium dioxide, and the initiator is added at the moment, so that-COOH and-NH can be improved2Thereby improving the yield of the product. The prepared polyacrylonitrile-modified nano titanium dioxide not only has good uvioresistant performance, but also can further improve the antibacterial property of the materialCan also improve the modified nano TiO2Compatibility with polypropylene quality.
Because the modified nano TiO titanium dioxide has a non-selective broad-band strong absorption effect on ultraviolet rays, has good stability, is not easy to chemically react with a high polymer material, only a small amount of modified nano titanium dioxide is added, the ultraviolet resistance of the modified nano TiO titanium dioxide has lasting stability, and the modified nano TiO has long-lasting stability2The ultraviolet light-absorbing material has strong absorption performance in the whole ultraviolet band, so that the ultraviolet light-absorbing material has a better effect on improving the aging resistance of a high polymer material.
The invention has the beneficial effects that: compared with the traditional method, the antibacterial agent prepared by the specific method has the advantages of simple steps, no toxicity of the reagent and good binding performance of the plating layer; meanwhile, polydopamine is added, so that the reduction of copper ions can be accelerated, the reaction time is shortened, the binding force between copper and silver can be improved, the addition of a modifier can improve the stabilizer of the antibacterial agent and the dispersibility of the antibacterial agent in plastic, and in addition, modified nano titanium dioxide is added into the antibacterial plastic, so that the prepared antibacterial plastic has the technical effects of high-efficiency antibacterial property, long-acting antibacterial property and ultraviolet resistance.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
in the examples, polypropylene was purchased from the trade of Chang' hei Chuan plastic raw material of Dongguan city, and the trade mark: F5606-GD, CAS: 25085-53-4.
In the examples, carbon nanotube fibers were purchased from the institute of sciences, national institute of sciences, organic chemistry, ltd, model number: TNF1200, diameter: 10 μm, carbon tube strength: 1200 and 1500 MPa.
In the examples, montmorillonite was purchased from Shijiazhuang Guangning mineral products Co., Ltd, and the apparent viscosity: 86(mpa.s), type: 325 mesh.
Examples chlorosulfonated polyethylene, CAS: 68037-39-8.
Examples bis (acetylacetonate) ethoxyisopropoxytitanate, CAS: 445398-76-5.
Example trimethylpentanol, CAS: 16325-63-6.
In the examples, L-polylactic acid was purchased from Jinan Uninary bioengineering, Inc., under the trade designation: a0005, content: 99.5 percent.
Examples ethylene oxide, CAS: 75-21-8.
In the examples, silver nano antibacterial agent was purchased from bio-technology ltd of tokyo koku, concentration: 0.1mg/mL, particle size: 50nm, Commodity number: JK-03-003.
In the examples, the nano titanium dioxide is purchased from Hangzhou Hengge nano science and technology company, and the crystal form is as follows: rutile, content: 99.8%, type: HN-T15, average particle diameter: 15nm, specific surface area: 50m2/g。
Examples dodecyl triphenyl phosphonium bromide, CAS: 15510-55-1.
In the examples, sodium-based rectorite is purchased from Taixiang famous flow rectorite science and technology Limited, Hubei, and the content of the rectorite is as follows: 90 percent.
The oleylamine in the examples was purchased from manba commercial limited, texas, cat # stock: 112-90-3, CAS: 112-90-3.
Example polydopamine was prepared according to example 5 of the chinese invention patent (patent No. 201911147981.1) by the following method:
(1) weighing 0.0948g of DA & HCl, and dissolving in 5mL of Tris-buffer solution to obtain solution A; weighing 0.0990gK2FeO4Dissolved in 5mL of an aqueous ammonia solution (pH 8.5) to obtain a solution B; dropwise adding the solution B into the solution A, magnetically stirring, keeping the rotating speed at 5000r min < -1 >, keeping the reaction temperature at 70 ℃, gradually changing the reaction mixed solution from purple red to black in the reaction process, and stopping stirring after reacting for 40 minutes;
(2) and (3) filtering the reaction mixed solution under reduced pressure, washing the precipitate for 5 times by using distilled water, and freeze-drying the precipitate to constant weight to obtain a polydopamine product, wherein the yield is 94%, and the diameter of the polydopamine nano-particle is about 50 nm.
Example 1
An antibacterial plastic comprises the following components in parts by weight: 35 parts of polypropylene, 8 parts of carbon nano tube fiber, 10 parts of montmorillonite, 4 parts of chlorosulfonated polyethylene, 1 part of bis (acetylacetonato) ethoxy isopropoxy titanate, 3 parts of trimethylpentanol, 2 parts of levorotatory polylactic acid, 4 parts of ethylene oxide and 5 parts of an antibacterial agent.
The antibacterial agent is a Cu-Ag composite antibacterial agent;
the antibacterial agent is a Cu-Ag composite antibacterial agent, and the preparation method comprises the following steps:
(1) mixing 12 parts by weight of copper nitrate, 20 parts by weight of reducing agent and 20 parts by weight of oleylamine, stirring at the temperature of 100 ℃ and 500rpm for 30min, keeping stirring, increasing the temperature to 200 ℃ at the speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is sodium rectorite.
The preparation method of the antibacterial plastic comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, mixing polypropylene, carbon nanotube fiber, montmorillonite, plasticizer, coupling agent, dispersant, nucleating agent and stabilizer in a high-speed mixer at 1500 rpm for 30min, and discharging after uniform mixing to obtain a mixture;
s3, putting the mixed material into a reactor, stirring at a stirring speed of 800rpm and a heating rate of 10 ℃/min while heating to 120 ℃, adding an antibacterial agent, heating to 160 ℃ at the stirring speed of 800rpm and the heating rate of 10 ℃/min, and continuing stirring for 20min to obtain a functional mixed material;
s4, cooling and stirring the functional mixed material in the step S3 at 500rpm until the material temperature is 60 ℃, then adding the material into a double-screw extruder, setting the melting temperature to be 170 ℃ in a feeding section, 200 ℃ in a middle section, 220 ℃ in an extruder head, 150 rpm in the rotating speed of a screw, 40mm in diameter of the screw and 40% in length-diameter ratio of the screw: 1, performing extrusion molding to obtain the antibacterial plastic.
Example 2
Essentially the same as example 1 except that the modifier is dodecyltriphenylphosphonium bromide.
Comparative example 1
Essentially the same as in example 1, except that no modifier was added.
Example 3
Essentially the same as in example 1, except that the reducing agent is sodium borohydride.
Example 4
Essentially the same as in example 1, except that the reducing agent is ascorbic acid.
Example 5
An antibacterial plastic comprises the following components in parts by weight: 35 parts of polypropylene, 8 parts of carbon nano tube fiber, 10 parts of montmorillonite, 4 parts of chlorosulfonated polyethylene, 1 part of bis (acetylacetonato) ethoxy isopropoxy titanate, 3 parts of trimethylpentanol, 2 parts of levorotatory polylactic acid, 4 parts of ethylene oxide and 5 parts of an antibacterial agent.
The antibacterial agent is a Cu-Ag composite antibacterial agent;
the antibacterial agent is a Cu-Ag composite antibacterial agent, and the preparation method comprises the following steps:
(1) mixing 12 parts by weight of copper nitrate, 20 parts by weight of reducing agent and 20 parts by weight of oleylamine, stirring at the temperature of 100 ℃ and 500rpm for 30min, keeping stirring, increasing the temperature to 200 ℃ at the speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Oleylamine solution and 8 weight portionsHeating the modifier to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain a copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is dodecyl triphenyl phosphonium bromide and sodium rectorite according to the mass ratio of 1: 2, or a mixture thereof.
The preparation method of the antibacterial plastic comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, mixing polypropylene, carbon nanotube fiber, montmorillonite, plasticizer, coupling agent, dispersant, nucleating agent and stabilizer in a high-speed mixer at 1500 rpm for 30min, and discharging after uniform mixing to obtain a mixture;
s3, putting the mixed material into a reactor, stirring at a stirring speed of 800rpm and a heating rate of 10 ℃/min while heating to 120 ℃, adding an antibacterial agent, heating to 160 ℃ at the stirring speed of 800rpm and the heating rate of 10 ℃/min, and continuing stirring for 20min to obtain a functional mixed material;
s4, cooling and stirring the functional mixed material in the step S3 at 500rpm until the material temperature is 60 ℃, then adding the material into a double-screw extruder, setting the melting temperature to be 170 ℃ in a feeding section, 200 ℃ in a middle section, 220 ℃ in an extruder head, 150 rpm in the rotating speed of a screw, 40mm in diameter of the screw and 40% in length-diameter ratio of the screw: 1, performing extrusion molding to obtain the antibacterial plastic.
Example 6
An antibacterial plastic comprises the following components in parts by weight: 35 parts of polypropylene, 8 parts of carbon nanotube fiber, 10 parts of montmorillonite, 4 parts of chlorosulfonated polyethylene, 1 part of bis (acetylacetonato) ethoxy isopropoxy titanate, 3 parts of trimethylpentanol, 2 parts of levorotatory polylactic acid, 4 parts of ethylene oxide, 5 parts of an antibacterial agent and 4 parts of anti-modification titanium dioxide.
The antibacterial agent is a Cu-Ag composite antibacterial agent, and the preparation method comprises the following steps:
(1) mixing 12 parts by weight of copper nitrate, 20 parts by weight of reducing agent and 20 parts by weight of oleylamine, stirring at the temperature of 100 ℃ and 500rpm for 30min, keeping stirring, increasing the temperature to 200 ℃ at the speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is dodecyl triphenyl phosphonium bromide and sodium rectorite according to the mass ratio of 1: 2, or a mixture thereof.
The preparation method of the modified nano titanium dioxide comprises the following steps:
(1) 5 parts by weight of nano TiO2Drying in a constant temperature drying oven at 100 deg.C for 10h, adding 5 weight parts of anhydrous ethanol, stirring at 600rpm for 30min, adding 0.3 weight part of KH-550, and reacting at 65 deg.C for 1 h. Centrifuging at 10000rpm for 30min, drying at 60 deg.C for 1h, and grinding to obtain pretreated powder;
(2) adding 10 parts by weight of polyacrylonitrile fibers into 20 parts by weight of NaSCN aqueous solution with the mass fraction of 50%, adding 12mol/L concentrated hydrochloric acid solution at the temperature of 60 ℃ to adjust the pH value to 1, reacting for 6 hours, adding 10 parts by weight of deionized water, stirring at 400rpm for 30min, performing suction filtration, and performing freeze drying at the temperature of minus 20 ℃ for 24 hours to obtain polyacrylonitrile powder;
(3) taking 3 parts by weight of pretreatment powder, 25 parts by weight of deionized water in a reaction container, stirring at room temperature of 600rpm for 30min, performing ultrasonic treatment at the ultrasonic power of 100W and the frequency of 25kHz for 30min, putting the mixture into a water bath, adding 9 parts by weight of polyacrylonitrile powder, raising the water bath temperature to 60 ℃, adding 0.3 part by weight of initiator, reacting for 4h, adding 10 parts by weight of absolute ethyl alcohol, washing, and drying the washed product in a vacuum drying oven at 60 ℃ for 24h to obtain modified nano titanium dioxide; the initiator is potassium persulfate.
The preparation method of the antibacterial plastic comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, mixing polypropylene, carbon nanotube fiber, montmorillonite, plasticizer, coupling agent, dispersant, nucleating agent and stabilizer in a high-speed mixer at 1500 rpm for 30min, and discharging after uniform mixing to obtain a mixture;
s3, putting the mixed material into a reactor, stirring at a stirring speed of 800rpm and a heating rate of 10 ℃/min while heating to 120 ℃, adding an antibacterial agent and modified nano titanium dioxide, heating to 160 ℃ at the stirring speed of 800rpm and the heating rate of 10 ℃/min, and stirring for 20min to obtain a functional mixed material;
s4, cooling and stirring the functional mixed material in the step S3 at 500rpm until the material temperature is 60 ℃, then adding the material into a double-screw extruder, setting the melting temperature to be 170 ℃ in a feeding section, 200 ℃ in a middle section, 220 ℃ in an extruder head, 150 rpm in the rotating speed of a screw, 40mm in diameter of the screw and 40% in length-diameter ratio of the screw: 1, performing extrusion molding to obtain the antibacterial plastic.
Example 7
An antibacterial plastic comprises the following components in parts by weight: 35 parts of polypropylene, 8 parts of carbon nanotube fiber, 10 parts of montmorillonite, 4 parts of chlorosulfonated polyethylene, 1 part of bis (acetylacetonato) ethoxy isopropoxy titanate, 3 parts of trimethylpentanol, 2 parts of levorotatory polylactic acid, 4 parts of ethylene oxide, 5 parts of an antibacterial agent and 4 parts of modified nano titanium dioxide.
The antibacterial agent is a Cu-Ag composite antibacterial agent;
the antibacterial agent is a Cu-Ag composite antibacterial agent, and the preparation method comprises the following steps:
(1) mixing 12 parts by weight of copper nitrate, 20 parts by weight of reducing agent and 20 parts by weight of oleylamine, heating at 100 ℃ and stirring at 500rpm for 30min, keeping stirring, increasing the temperature to 200 ℃ at the speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is dodecyl triphenyl phosphonium bromide and sodium rectorite according to the mass ratio of 1: 2, or a mixture thereof.
The preparation method of the modified nano titanium dioxide comprises the following steps:
(1) 5 parts by weight of nano TiO2Drying in a constant temperature drying oven at 100 deg.C for 10h, adding 5 weight parts of anhydrous ethanol, stirring at 600rpm for 30min, adding 0.3 weight part of KH-550, and reacting at 65 deg.C for 1 h. Centrifuging at 10000rpm for 30min, drying at 60 deg.C for 1h, and grinding to obtain pretreated powder;
(2) adding 10 parts by weight of polyacrylonitrile fibers into 20 parts by weight of NaSCN aqueous solution with the mass fraction of 50%, adding 12mol/L concentrated hydrochloric acid solution at the temperature of 60 ℃ to adjust the pH value to 1, reacting for 6 hours, adding 10 parts by weight of deionized water, stirring at 400rpm for 30min, performing suction filtration, and performing freeze drying at the temperature of minus 20 ℃ for 24 hours to obtain polyacrylonitrile powder;
(3) taking 3 parts by weight of pretreatment powder, 25 parts by weight of deionized water in a reaction container, stirring for 30min at room temperature of 600prm, performing ultrasonic treatment for 30min under the ultrasonic power of 100W and the frequency of 25kHz, putting the mixture into a water bath kettle, adding 9 parts by weight of polyacrylonitrile powder, heating the water bath temperature to 60 ℃, adding 0.3 part by weight of initiator, reacting for 4h, adding 10 parts by weight of absolute ethyl alcohol for washing, and putting the washed product into a vacuum drying oven at 60 ℃ for drying for 24h to obtain modified nano titanium dioxide; the initiator is diisopropyl peroxydicarbonate.
The preparation method of the antibacterial plastic comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, mixing polypropylene, carbon nanotube fiber, montmorillonite, plasticizer, coupling agent, dispersant, nucleating agent and stabilizer in a high-speed mixer at 1500 rpm for 30min, and discharging after uniform mixing to obtain a mixture;
s3, putting the mixed material into a reactor, stirring at a stirring speed of 800rpm and a heating rate of 10 ℃/min while heating to 120 ℃, adding an antibacterial agent and modified nano titanium dioxide, heating to 160 ℃ at the stirring speed of 800rpm and the heating rate of 10 ℃/min, and continuing stirring for 20min to obtain a functional mixed material;
s4, cooling and stirring the functional mixed material in the step S3 at 500rpm until the material temperature is 60 ℃, then adding the material into a double-screw extruder, setting the melting temperature to be 170 ℃ in a feeding section, 200 ℃ in a middle section, 220 ℃ in an extruder head, 150 rpm in the rotating speed of a screw, 40mm in diameter of the screw and 40% in length-diameter ratio of the screw: 1, performing extrusion molding to obtain the antibacterial plastic.
And (3) testing results: the sterilization rate of escherichia coli is as follows: 99.9%, staphylococcus aureus bactericidal rate: 100%, and the sterilization rate of pseudomonas aeruginosa: 99.6%, candida albicans bactericidal rate: 99.7%, yellow index color difference Δ YI (700 h): 1.01.
comparative example 2
An antibacterial plastic comprises the following components in parts by weight: 35 parts of polypropylene, 8 parts of carbon nanotube fiber, 10 parts of montmorillonite, 4 parts of chlorosulfonated polyethylene, 1 part of bis (acetylacetonato) ethoxy isopropoxy titanate, 3 parts of trimethylpentanol, 2 parts of levorotatory polylactic acid, 4 parts of ethylene oxide, 5 parts of an antibacterial agent and 4 parts of anti-modification titanium dioxide.
The antibacterial agent is a Cu-Ag composite antibacterial agent, and the preparation method comprises the following steps:
(1) mixing 12 parts by weight of copper nitrate, 20 parts by weight of reducing agent and 20 parts by weight of oleylamine, heating at 100 ℃, stirring at 500rpm for 30min, heating to 200 ℃, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is dodecyl triphenyl phosphonium bromide and sodium rectorite according to the mass ratio of 1: 2, or a mixture thereof.
The preparation method of the modified nano titanium dioxide comprises the following steps:
(1) 5 parts by weight of nano TiO2Drying in a constant temperature drying oven at 100 deg.C for 10 hr, adding 5 weight parts of anhydrous ethanol, stirring for 30min, adding 0.3 weight part of KH-550, and reacting at 65 deg.C under stirring for 1 hr. Centrifuging at 10000rpm for 30min, drying at 60 deg.C for 1h, and grinding to obtain pretreated powder;
(2) taking 3 parts by weight of pretreatment powder, 25 parts by weight of deionized water in a reaction container, stirring for 30min at room temperature, performing ultrasonic treatment for 30min under the ultrasonic power of 100W and the frequency of 25kHz, putting the mixture into a water bath kettle, heating the water bath to 60 ℃, adding 0.3 part by weight of initiator, reacting for 4h, adding 10 parts by weight of absolute ethyl alcohol for washing, and putting the washed product into a vacuum drying oven at 60 ℃ for drying for 24h to obtain modified nano titanium dioxide; the initiator is diisopropyl peroxydicarbonate.
The preparation method of the antibacterial plastic comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, mixing polypropylene, carbon nanotube fiber, montmorillonite, plasticizer, coupling agent, dispersant, nucleating agent and stabilizer in a high-speed mixer at 1500 rpm for 30min, and discharging after uniform mixing to obtain a mixture;
s3, putting the mixed material into a reactor, stirring at a stirring speed of 800rpm and a heating rate of 10 ℃/min while heating to 120 ℃, adding an antibacterial agent and modified nano titanium dioxide, heating to 160 ℃ at the stirring speed of 800rpm and the heating rate of 10 ℃/min, and continuing stirring for 20min to obtain a functional mixed material;
s4, cooling and stirring the functional mixed material in the step S3 at 500rpm until the material temperature is 60 ℃, then adding the material into a double-screw extruder, setting the melting temperature to be 170 ℃ in a feeding section, 200 ℃ in a middle section, 220 ℃ in an extruder head, 150 rpm in the rotating speed of a screw, 40mm in diameter of the screw and 40% in length-diameter ratio of the screw: 1, performing extrusion molding to obtain the antibacterial plastic.
Comparative example 3
An antibacterial plastic comprises the following components in parts by weight: 35 parts of polypropylene, 8 parts of carbon nano tube fiber, 10 parts of montmorillonite, 4 parts of chlorosulfonated polyethylene, 1 part of bis (acetylacetonato) ethoxy isopropoxy titanate, 3 parts of trimethylpentanol, 2 parts of levorotatory polylactic acid, 4 parts of ethylene oxide and 5 parts of an antibacterial agent.
The antibacterial agent is a silver nano antibacterial agent;
the preparation method of the antibacterial plastic comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, mixing polypropylene, carbon nanotube fiber, montmorillonite, plasticizer, coupling agent, dispersant, nucleating agent and stabilizer in a high-speed mixer at 1500 rpm for 30min, and discharging after uniform mixing to obtain a mixture;
s3, putting the mixed material into a reactor, stirring at a stirring speed of 800rpm and a heating rate of 10 ℃/min while heating to 120 ℃, adding an antibacterial agent, heating to 160 ℃ at the stirring speed of 800rpm and the heating rate of 10 ℃/min, and continuing stirring for 20min to obtain a functional mixed material;
s4, cooling and stirring the functional mixed material in the step S3 at 500rpm until the material temperature is 60 ℃, then adding the material into a double-screw extruder, setting the melting temperature to be 170 ℃ in a feeding section, 200 ℃ in a middle section, 220 ℃ in an extruder head, 150 rpm in the rotating speed of a screw, 40mm in diameter of the screw and 40% in length-diameter ratio of the screw: 1, performing extrusion molding to obtain the antibacterial plastic.
Test example 1
1. And (3) testing antibacterial performance: the test is carried out by referring to GB/T31402-2015' test method for the surface antibacterial performance of plastic, the test method adopts a film pasting method, the tests all adopt escherichia coli ATYCC 8739, staphylococcus aureus ATCC 6538P, pseudomonas aeruginosa ATCC 15442 and candida albicans ATCC 10231, the parallel tests are carried out for 5 times, and the average value is taken.
Comparing example 1 with comparative example 2, it can be seen that the bactericidal effect of the commercially available silver nano antibacterial agent is far lower than that of the copper-silver nano composite antibacterial agent prepared by the special method, because the technical effect of the copper nano and silver nano composite antibacterial synergy is firmly grasped by the invention; comparing examples 2-5 with comparative example 1, it can be seen that the antibacterial effect of the composite antibacterial agent prepared without adding a modifier is not ideal, and the different antibacterial rates of the reducing agent are different, because sodium borohydride and ascorbic acid are only used for reducing copper ions, silver nanoparticles are not adsorbed on the surface of copper ions through adhesion to form silver-coated copper nanocomposites, and only simple copper and silver nanoparticles are superposed, so that the antibacterial effect is reduced; the reducing property of the sodium borohydride is larger than that of the ascorbic acid, so that the yield of the obtained product is increased, and the antibacterial effect is better. Meanwhile, the antibacterial effect is further improved after the modifier is added for compounding, because the dodecyl triphenyl phosphonium bromide belongs to a cationic surfactant and has antibacterial performance, and phosphorus atoms in the molecular structure of the dodecyl triphenyl phosphonium bromide can form coordinate bonds with silver to adsorb the silver ions, so that the release speed of the silver ions is delayed, and the aggregation of the silver ions is prevented. The sodium-based rectorite is aqueous aluminosilicate, is interlayer mineral regularly and alternately stacked by dioctahedral mica layers and dioctahedral montmorillonite layers, has good dispersibility and thermal stability, large specific surface area and strong adsorbability, and exchangeable cations are contained in the montmorillonite layers, and silver ions, copper ions, dodecyl triphenyl phosphonium bromide and dodecyl triphenyl phosphonium bromide adsorbing silver particles can be intercalated into the montmorillonite layers through cation exchange, so that agglomeration is effectively prevented, the antibacterial performance is improved, and a slow release effect is further realized.
Further comparing example 5 with example 6, it is found that the antibacterial property is slightly improved after adding the modified nano titanium dioxide, because the nano titanium dioxide has not only the ultraviolet resistance but also a certain antibacterial property, but the antibacterial effect is much lower than that of the copper-silver nano composite antibacterial agent when adding the same equivalent of antibacterial agent, so the antibacterial effect is slightly improved but the amplitude is very small when adding the modified nano titanium dioxide.
Test example 2
1. And (3) testing ultraviolet resistance: reference GB/T16422.2-2014 Plastic laboratory light Source Exposure test method part 2: method a in the xenon arc lamp "was tested on exposure using a daylight filter.
Placing the sample in a xenon lamp exposure photoaging test box for irradiation accelerated aging, and testing the temperature: 23 ℃, relative humidity: 40 percent, and measuring the yellow index according to HG/T3862-2006 Plastic yellow index test method to obtain the yellowing index delta YI. At least 4 specimens per material sample were exposed and averaged.
| Sample (I) | Yellow index color difference Delta YI (700h) |
| Example 5 | 6.21 |
| Example 6 | 1.52 |
| Example 7 | 1.01 |
| Comparative example 2 | 2.58 |
It can be seen from comparison of examples 5 and 6 that the ultraviolet resistance of the modified nano titanium dioxide (example 6) is significantly improved because the modified nano titanium dioxide is mainly used for blocking ultraviolet rays in a long wave region and mainly used for absorbing ultraviolet rays in short and medium wave regions, thereby widening the ultraviolet absorption range, and meanwhile, the particle size of the modified nano titanium dioxide prepared by the invention is less than 100nm, and people in the art are familiar with that the particle size of nano titanium oxide is less than 100nm, so that the modified nano titanium dioxide has good ultraviolet scattering and absorbing capabilities. Further comparing examples 6 and 7 with comparative example 2, the UV resistance of nano-modified titanium dioxide obtained without adding polyacrylonitrile was not very good because polyacrylonitrile and KH-550 modified nano-TiO2Passing the powder through-COOH and-NH2The polyacrylonitrile-COOH and KH-550 modified nano TiO can be improved by adding the initiator2Of (2) is-NH2The binding reaction force between the two is necessary to improve the yield of the product, so the process of the polyacrylonitrile in the second step is necessary. The kind of the initiator has great influence on the preparation of the modified nano-titanium dioxide, the ultraviolet resistance effect of adding the initiator diisopropyl peroxydicarbonate (embodiment 7) is better than the technical effect of adding the potassium persulfate (embodiment 6), because the activity of the diisopropyl peroxydicarbonate is stronger than that of the potassium persulfate, the polyacrylonitrile and the KH-550 modified nano-TiO can be more effectively promoted2Passing the powder through-COOH and-NH2From a reaction betweenThe yield of the product is improved, and the uvioresistant performance is also improved.
Claims (10)
1. The antibacterial plastic is characterized by comprising the following raw materials in parts by weight: 30-40 parts of plastic substrate, 5-10 parts of carbon nanotube fiber, 6-14 parts of montmorillonite, 3-10 parts of plasticizer, 0.5-3 parts of coupling agent, 2-6 parts of dispersing agent, 1-4 parts of nucleating agent, 3-7 parts of stabilizer and 3-10 parts of antibacterial agent.
2. The antibacterial plastic as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 30-40 parts of plastic substrate, 5-10 parts of carbon nanotube fiber, 6-14 parts of montmorillonite, 3-10 parts of plasticizer, 0.5-3 parts of coupling agent, 2-6 parts of dispersing agent, 1-4 parts of nucleating agent, 3-7 parts of stabilizer, 3-10 parts of antibacterial agent and 2-7 parts of modified nano titanium dioxide.
3. The antibacterial plastic according to claim 2, wherein the plastic substrate is any one or a mixture of two or more of polypropylene, polyethylene, polyamide, polyethylene terephthalate and polystyrene.
4. The antibacterial plastic of claim 2, wherein the plasticizer is any one or a mixture of two or more of styrene-butadiene, methyl methacrylate-butadiene-styrene, acrylonitrile-butadiene-styrene copolymer, and chlorosulfonated polyethylene; the coupling agent is any one or a mixture of more than two of isopropyl trioleate acyloxy titanate, isopropyl tri (dodecyl benzenesulfonyl) titanate, bis (acetylacetone) ethoxy isopropoxy titanate and tetraisopropyl di (dioctyl phosphite acyloxy) titanate; the dispersing agent is polyethylene wax, cellulose acetate, methyl amyl alcohol, stearic acid monoglyceride or hexenyl bisstearamide; the nucleating agent is one or a mixture of any two of levorotatory polylactic acid, polyvinyl alcohol and benzotriazole; the stabilizer is one or two of stearate and ethylene oxide.
5. The antibacterial plastic of claim 2, wherein the antibacterial agent is a silver nano antibacterial agent or a Cu-Ag composite antibacterial agent.
6. The antibacterial plastic of claim 5, wherein the antibacterial agent is a Cu-Ag composite antibacterial agent, and the preparation method comprises the following steps:
(1) mixing 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine, heating and stirring at 80-120 ℃ for 20-50min, heating to 220 ℃ for 160-;
(2) at normal temperature and under the condition of stirring speed of 450-600rpm, adding 20-40 parts by weight of AgNO with mass fraction of (28-45)% into the seed crystal mixed solution3Heating the oleylamine solution and 5-10 parts by weight of modifier to 70-90 ℃, continuing stirring for 1.5-3 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) adding 10-50 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging at the centrifugal rotation speed of 9000-12000rpm for 10-30min, and drying the obtained solid in a vacuum drying oven at the temperature of 50-70 ℃ for 20-28h to obtain the Cu-Ag composite antibacterial agent.
7. The antibacterial plastic of claim 6, wherein the reducing agent is one or a mixture of more than two of sodium borohydride, ascorbic acid and polydopamine.
8. The antimicrobial plastic of claim 6, wherein the modifier is dodecyltriphenylphosphonium bromide and/or sodium-based rectorite.
9. The antibacterial plastic of claim 2, wherein the preparation method of the modified nano titanium dioxide comprises the following steps:
(1) 2 to 7 weight portions of nano TiO2Drying the powder in a constant temperature drying oven at 80-130 deg.C for 8-14h, adding 4-10 weight parts of anhydrous ethanol, stirring at 800rpm for 20-50min at 400-. Centrifuging at 9000-12000r/min for 20-30min, drying at 50-70 deg.C for 0.5-2h, and grinding to obtain pretreated powder;
(2) adding 8-12 parts by weight of polyacrylonitrile fiber into 15-30 parts by weight of NaSCN aqueous solution with the mass fraction of 40-60%, adding concentrated hydrochloric acid solution at 50-65 ℃ to adjust the pH value to 1-3, reacting for 5-8h, adding 10-20 parts by weight of deionized water, stirring at 600rpm of 300-40 min, performing suction filtration, and freeze-drying at-20-0 ℃ for 20-28h to obtain polyacrylonitrile powder;
(3) taking 1-5 parts by weight of pretreatment powder, 20-40 parts by weight of deionized water in a reaction container, stirring at the room temperature of 400-800rpm for 20-50min, performing ultrasonic treatment at the ultrasonic power of 80-120W and the frequency of 20kHz-45kHz for 20-40min, putting the mixture into a water bath kettle, adding 7-10 parts by weight of polyacrylonitrile powder, raising the water bath temperature to 50-70 ℃, adding 0.2-0.5 part by weight of initiator, reacting for 3-5h, adding 10-20 parts by weight of ethanol for washing, and putting the washed product into a vacuum drying oven at the temperature of 50-70 ℃ for drying for 20-30h to obtain modified nano titanium dioxide; the initiator is any one of potassium persulfate and diisopropyl peroxydicarbonate.
10. A process for the preparation of an antimicrobial plastic according to any of claims 1 to 9, characterized in that it comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, taking the plastic substrate, the carbon nano tube fiber, the montmorillonite, the plasticizer, the coupling agent, the dispersing agent, the nucleating agent and the stabilizing agent, stirring in a high-speed stirrer at 1400-1600rpm for 20-30min, and discharging after uniform to obtain a mixed material;
s3, putting the mixed material into a reactor, stirring at a stirring speed of 500-;
s4, cooling and stirring the functional mixed material in the step S3 at the speed of 400-: 1, performing extrusion molding to obtain the antibacterial plastic.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113388210A (en) * | 2021-06-22 | 2021-09-14 | 安徽驭风风电设备有限公司 | Wind power generation fan blade forming die and forming process thereof |
| CN113429676A (en) * | 2021-07-20 | 2021-09-24 | 仙桃市鼎业劳保用品有限公司 | Wear-resistant polypropylene boot sleeve with antibacterial function and preparation method thereof |
| CN115109349A (en) * | 2022-07-26 | 2022-09-27 | 浙江硕华生命科学研究股份有限公司 | Sedimentation test tube and sedimentation test tube composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113388210A (en) * | 2021-06-22 | 2021-09-14 | 安徽驭风风电设备有限公司 | Wind power generation fan blade forming die and forming process thereof |
| CN113429676A (en) * | 2021-07-20 | 2021-09-24 | 仙桃市鼎业劳保用品有限公司 | Wear-resistant polypropylene boot sleeve with antibacterial function and preparation method thereof |
| CN113429676B (en) * | 2021-07-20 | 2022-03-25 | 仙桃市鼎业劳保用品有限公司 | Wear-resistant polypropylene boot sleeve with antibacterial function and preparation method thereof |
| CN115109349A (en) * | 2022-07-26 | 2022-09-27 | 浙江硕华生命科学研究股份有限公司 | Sedimentation test tube and sedimentation test tube composite material |
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