CN113429676B - Wear-resistant polypropylene boot sleeve with antibacterial function and preparation method thereof - Google Patents
Wear-resistant polypropylene boot sleeve with antibacterial function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a wear-resistant polypropylene boot sleeve with an antibacterial function and a preparation method thereof, wherein the wear-resistant polypropylene boot sleeve with the antibacterial function is made of antibacterial wear-resistant polypropylene plastics and is prepared from the following raw materials: n, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and the balance of polypropylene. The invention overcomes the defects of short service life, poor antibacterial effect, easy abrasion and the like of the traditional boot sleeve.
Description
Technical Field
The invention relates to the technical field of boots, in particular to a wear-resistant polypropylene boot with an antibacterial function and a preparation method thereof.
Background
With the rapid development of the economy of China and the continuous improvement of the living standard of people, people have been generally using protective articles in daily life. The boot cover is a bag body which takes a plastic film as a main raw material, is combined with an elastic band and is provided with an elastic contraction opening. Because of the characteristics of wear resistance, good toughness, softness, convenient use and the like, the coating is widely applied to places with much dust and the like in rainy days. However, in work, the boot sleeve is easy to be wet, worn, slide down and the like when being waterproof and rainy. Once the problems occur, the waterproof rain boots can be polluted, and the probability of cross infection and infection in the hospital of workers can be increased during clinical work.
Therefore, the antibacterial boot cover is particularly important, and the probability of infecting germs of workers can be effectively reduced. The material of the antibacterial boot cover is usually that antibacterial agents are added into polyethylene and polypropylene materials, and the antibacterial boot cover is obtained through a conventional preparation process. However, the abrasion-resistant strength, the tensile strength and the like of the existing antibacterial boot sleeve are general, and after long-time heat, light and oxidation, the abrasion-resistant strength and the tensile strength are continuously reduced, so that the service life of the shoe sleeve is greatly shortened; in addition, in the using process, the material is easy to age and decompose due to the influence of rain, sunlight, ozone and the like for a long time, so that the waterproof performance and the antibacterial performance are also reduced, and the function of the material is influenced. However, with the continuous improvement of the requirements of people, the characteristics of the existing boot sleeve, such as antibiosis, wear resistance and the like, can not meet the requirements of people, and further improvement is needed.
Chinese patent (application number: 201910511393.5) discloses a rain-proof shoe cover material with temperature change function and a shoe cover, which comprise the following raw materials in parts by weight: 20-30 parts of deionized water, 15-20 parts of glycerol, 7-10 parts of titanium dioxide, 10-15 parts of latex, 8-10 parts of chitosan, 11-13 parts of sorbic acid, 15-18 parts of thermochromic powder, 12-15 parts of epoxy resin, 20-25 parts of absolute ethyl alcohol, 12-15 parts of a silane coupling agent and 5-8 parts of a plasticizer. The practical technical problem solved is to improve the antibacterial property and the waterproof property of the rain shoes and increase the practicability of the rain shoes. Then, the wear resistance of the rain-proof shoe cover prepared by the patent is poor, which greatly limits the application in many fields.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a wear-resistant polypropylene boot sleeve with an antibacterial function and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the wear-resistant polypropylene boot sleeve with the antibacterial function is made of antibacterial wear-resistant polypropylene plastics, and the antibacterial wear-resistant polypropylene plastics are prepared from the following raw materials: n, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and the balance of polypropylene.
The wear-resistant polypropylene boot sleeve with the antibacterial function is made of polypropylene, is odorless, non-toxic, wax-like in hand feeling, has excellent low-temperature resistance, good chemical stability, can resist corrosion of most of acid and alkali, is low in water absorption rate, and is the first choice for the boot sleeve material; the N, N' -ethylene bis stearamide is used as a dispersing agent, so that the raw materials of various substances can be effectively dispersed, and the uniformity of the material is improved; the ethylene acrylic acid copolymer is a polymer with thermoplasticity and extremely high adhesion, and the chemical resistance is better; the nano calcium carbonate is used as a filler, so that the rheological property of the polypropylene plastic can be improved, the moldability of the polypropylene plastic is improved, the nano calcium carbonate can be used as a plastic filler, has the functions of toughening and reinforcing, improves the bending strength and the bending elastic modulus of the plastic, the thermal deformation temperature and the dimensional stability, and simultaneously endows the plastic with the thermal hysteresis; dimethyl phthalate and chlorinated paraffin are used as plasticizers for improving the plasticizing performance of plastics; the antioxidant 1076 is used for improving the oxidation resistance of the polypropylene plastic and prolonging the service life; polypropylene wax is used as a dispersing agent and is cooperated with a dispersing agent to improve the uniformity of the material; the organic silicone oil is used as a lubricant for reducing the friction resistance of the friction pair, slowing down the abrasion of the friction pair and prolonging the service life of the plastic; the wear-resistant antibacterial agent is used as a functional additive and is mainly used for improving the antibacterial performance and the wear-resistant performance of the boot sleeve.
Preferably, the antibacterial wear-resistant polypropylene plastic is prepared from the following raw materials: 0.3-1 wt% of N, N' -ethylene bis stearamide, 5-15 wt% of ethylene acrylic acid copolymer, 4-12 wt% of nano calcium carbonate, 1-4 wt% of dimethyl phthalate, 0.1-0.8 wt% of antioxidant 1076, 0.2-1 wt% of polypropylene wax, 0.1-2 wt% of chlorinated paraffin, 0.5-2 wt% of organic silicon oil, 3-8 wt% of wear-resistant antibacterial agent and the balance of polypropylene.
The silver-zinc composite antibacterial agent is used as a main antibacterial agent of the wear-resistant polypropylene boot sleeve with the antibacterial function, but the silver-zinc antibacterial agent used in organic plastics has poor dispersion performance and poor compatibility with other organic matters of a polypropylene plastic matrix, so that the original antibacterial performance is greatly reduced.
Specifically, a silver-zinc compound is prepared into a nano composite antibacterial agent through a hydrothermal method, and then the nano composite antibacterial agent reacts with a coupling agent to obtain a coupling modified silver-zinc nano composite antibacterial agent, silver ions are embedded into crystal lattices of zinc in the nano composite antibacterial agent through high-temperature sintering and mainly exist in a crystal lattice defect form, the electronic structure of the nano composite antibacterial agent is formed by conduction bands formed by valence band and empty tracks, the zinc and the silver ions in the nano composite antibacterial agent have good bactericidal effects, and the silver ions attached to the zinc crystal lattices can promote the photocatalytic activity of the zinc and the silver ions mutually to generate free radicals with extremely strong activity, so that the breeding and growth of bacteria are avoided.
The preparation method of the wear-resistant antibacterial agent comprises the following steps:
s1, placing the zinc gluconate aqueous solution into a reaction container, dropwise adding an ammonium bicarbonate aqueous solution for reaction, then adding a silver nitrate aqueous solution, continuing the reaction, centrifuging to obtain a precursor, and placing the precursor into a muffle furnace for calcination to obtain the nano-composite antibacterial agent;
s2, taking the nano composite antibacterial agent in the step S1, adding isopropanol, performing ultrasonic treatment, adding a coupling agent, and reacting to obtain the wear-resistant antibacterial agent.
The silicon dioxide can improve the wear resistance and the smoothness of the surface of the material, is beneficial to drawing into wires when being added into the material of polypropylene plastics, simultaneously enables the surface of the material to be more compact and finer and the friction coefficient to be smaller, and greatly enhances the wear resistance of the material by the high strength of the nano particles; but the antibacterial agent added with the silicon dioxide can reduce the original performance of the antibacterial agent to a certain extent, so that the invention selects the graphene oxide with very high antibacterial performance and strength and the silicon dioxide loaded with nano silver-zinc composite antibacterial to compound.
Preferably, the preparation method of the wear-resistant antibacterial agent is as follows: s1, placing the zinc gluconate aqueous solution into a reaction container, dropwise adding an ammonium bicarbonate aqueous solution for reaction, then adding a silver nitrate aqueous solution, continuing the reaction, centrifuging to obtain a precursor, and placing the precursor into a muffle furnace for calcination to obtain the nano-composite antibacterial agent;
s2, taking the nano composite antibacterial agent in the step S1, adding isopropanol, performing ultrasonic treatment, adding a coupling agent, and reacting to obtain a modified nano composite antibacterial agent;
s3, mixing absolute ethyl alcohol and tetraethyl orthosilicate, adding the modified nano composite antibacterial agent and ammonia water, continuing stirring, filtering and drying to obtain the wear-resistant antibacterial agent.
Graphene is a two-dimensional layered novel carbon material, the thickness of single-layer graphene is only 0.35nm, the graphene is the thinnest two-dimensional material known in the world, and the graphene has abundant and peculiar physicochemical characteristics, such as heat conduction, high specific surface area, outstanding flame retardance and mechanical properties, extraordinary electron transfer performance and certain antibacterial activity, and can damage cell membranes of bacteria, cause the outflow of intracellular substances and kill the bacteria, so that the mechanical property can be improved and the bacteria can be prevented when the graphene is added into a composite material. Therefore, the invention aims to prepare a multifunctional material with high strength, antibacterial property and wear resistance. Not only endows the boot sleeve with multifunctional application, but also prolongs the service life of the boot sleeve, thereby having wide application prospect and market demand.
Specifically, (1) a silver-zinc compound is prepared into a nano composite antibacterial agent by a hydrothermal method and then reacts with a coupling agent to obtain a coupling modified silver-zinc nano composite antibacterial agent, and the addition of the coupling agent can uniformly and stably disperse silica particles in a finishing liquid below the nano composite antibacterial agent, and can effectively increase the affinity between inorganic substance silica and the nano composite antibacterial agent so as to be firmly attached together after the nano composite antibacterial agent is compounded; (2) mixing a silicon source and the silane-modified nano-composite antibacterial agent, and connecting silicon dioxide through a silane coupling agent on the surface of the nano-composite antibacterial agent to obtain a silicon dioxide-coated antibacterial agent; (3) the graphene oxide and the silicon dioxide coated antibacterial agent are connected by adding the modifying agent, the stability of the graphene oxide in polypropylene plastic can be improved by adding the modifying agent, the occurrence of agglomeration is reduced, and the wear-resistant and antibacterial enhancement effects of the graphene oxide on the wear-resistant polypropylene boot sleeve with the antibacterial function are fully exerted.
Further, the preparation method of the wear-resistant antibacterial agent comprises the following steps:
s1, placing 10-30 parts by weight of 0.5-2mol/L zinc gluconate aqueous solution into a reaction container, dropwise adding 30-50 parts by weight of 0.5-2mol/L ammonium bicarbonate aqueous solution under stirring at 15-30 ℃ and 600-1000rpm, wherein the dropwise adding speed is 0.5-1.2mL/min, continuing to react for 1-3h after the dropwise adding is finished, then adding 5-15 parts by weight of 0.1-0.2mol/L silver nitrate aqueous solution, continuing to react for 0.5-2h, centrifuging, washing precipitates with water to obtain a precursor, placing the precursor into a muffle furnace, gradually heating from room temperature to 400-600 ℃, heating at the speed of 3-8 ℃/min, calcining for 2-5h under the nitrogen atmosphere, and cooling to obtain the nano composite antibacterial agent;
s2, taking 8-15 parts by weight of the nano composite antibacterial agent, adding 200 parts by weight of isopropanol with 100-200 parts by weight, adjusting the pH to 4-5 by using 0.5-2mol/L hydrochloric acid, carrying out ultrasonic treatment at the ultrasonic power of 180-300W and the ultrasonic frequency of 30-60kHz for 15-40min, adding 0.05-0.2 part by weight of coupling agent, reacting for 1-3h under the stirring of 40-60 ℃ and 800-1200rpm, carrying out suction filtration, and drying for 8-50h at 60-80 ℃ to obtain the modified nano composite antibacterial agent;
s3, mixing 70-100 parts by weight of absolute ethyl alcohol and 5-12 parts by weight of tetraethyl orthosilicate, adding 5-10 parts by weight of modified nano composite antibacterial agent and 1-4 parts by weight of 10-30 wt% of ammonia water at 30-50 ℃ and 500rpm, continuing stirring for 3-6h, filtering, washing with absolute ethyl alcohol, and drying at 60-80 ℃ for 8-20h to obtain the silica-coated antibacterial agent;
s4, dispersing 5-12 parts by weight of the silicon dioxide coated antibacterial agent in 80-120 parts by weight of 50-80 wt% ethanol water solution, performing ultrasonic treatment at ultrasonic power of 150-200W and ultrasonic frequency of 20-50kHz for 20-40min, adding 2-5 parts by weight of graphene oxide and 0.1-0.6 part by weight of modifier, reacting at 60-80 ℃ for 4-8h, centrifuging, washing with absolute ethyl alcohol, and drying at 60-90 ℃ for 8-20h to obtain the wear-resistant antibacterial agent.
The coupling agent is a silane coupling agent.
The modifier is 1H,1H,2H, 2H-perfluorododecyl triethoxysilane and/or 3- (methacryloyloxy) propyl trimethoxysilane; preferably, the modifier is prepared from 1H,1H,2H, 2H-perfluorododecyl triethoxysilane and 3- (methacryloyloxy) propyl trimethoxysilane in a mass ratio of (1-3): (1-5).
The modifier adopts 1H,1H,2H, 2H-perfluorododecyl triethoxysilane and 3- (methacryloyloxy) propyl trimethoxysilane to have a synergistic effect, F atoms in the 1H,1H,2H, 2H-perfluorododecyl triethoxysilane have stronger affinity with graphene oxide, and 3- (methacryloyloxy) propyl trimethoxysilane and silicon dioxide have stronger affinity, and the two exert advantages respectively, so that the graphene oxide and the silicon dioxide coated antibacterial agent are effectively connected, and finally the wear-resistant antibacterial agent with wear resistance, antibacterial performance and other performances is obtained.
The preparation method of the antibacterial wear-resistant polypropylene plastic comprises the following steps:
putting N, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and polypropylene into a mixer, stirring for 30-50min at the speed of 1000-: the rotation speed of the host is 100-: 20-30rpm, the reference temperatures of the screw heating four sections are respectively as follows: the temperature of the first zone is 160-.
A wear-resistant polypropylene boot sleeve with an antibacterial function is prepared by the following steps: extruding and blowing the antibacterial wear-resistant polypropylene plastic into a film by using a plastic film blowing machine to obtain a film; the film is made into a wear-resistant polypropylene boot cover with an antibacterial function according to a conventional process. Wherein the four-section temperature of the rear section of the material barrel of the film blowing machine is respectively 160-165 ℃, 175-180 ℃, 180-185 ℃ and 190-195 ℃, the four-section temperature of the front section of the material barrel is respectively 180-185 ℃, 195-200 ℃, 200-205 ℃ and 210-215 ℃, the two-section temperature of the head is respectively 215-220 ℃, 220-225 ℃, the blowing ratio is 1-2, the screw rotation speed is 45-50rpm and the traction speed is 30-32 m/min.
The invention has the beneficial effects that:
1. the wear-resistant antibacterial agent prepared by the invention has multiple functions, has excellent antibacterial performance and wear resistance, and also has excellent mechanical properties, and can effectively overcome the defects of poor antibacterial performance, poor wear resistance and the like of the traditional boot sleeve.
2. The wear-resistant polypropylene boot sleeve with the antibacterial function, which is prepared by the invention, has good antibacterial and wear-resistant performances, can effectively prolong the service life of the boot sleeve, can effectively protect toes, prevent puncture and the like, is simple in process operation, low in production cost, good in processability, wear resistance and antibacterial performance, wide in application prospect and large in market demand.
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:
the polypropylene in the examples was purchased from san east chang gao new materials ltd, model: CY-148572.
In the examples, the ethylene acrylic acid copolymer was purchased from Yingcang plastification Co., Ltd, Yuyao, trade name: 3003.
in the examples, the nano calcium carbonate is purchased from Hebei red land mineral products Co., Ltd, model number: CD-108, fineness: 6250 mesh.
In the examples, polypropylene wax was purchased from jinan yuyi commercial limited, model number: JX-301, molecular weight: 1500-5000.
In the examples, chlorinated paraffin was purchased from Shandong Chuangying chemical Co., Ltd, Cat No.: 13.
in the examples, silicone oils were purchased from denna, refreshing materials ltd, model: 201.
example 1H, 2H-perfluorododecyl triethoxysilane, CAS No.: 146090-84-8.
Example 3- (methacryloyloxy) propyltrimethoxysilane, CAS No.: 2530-85-0.
In the examples, graphene oxide is commercially available, and is available from Shanghai micro application materials technology, Inc., state: powder, number of layers: 1-10, thickness: 1nm, monolayer diameter: 0.2-10um, the strippability rate is more than or equal to 95 percent, and the carbon content is as follows: 45.7%, oxygen content: 51.6 percent.
Example 1
A wear-resistant polypropylene boot sleeve with an antibacterial function is made of antibacterial wear-resistant polypropylene plastics;
the antibacterial wear-resistant polypropylene plastic is prepared from the following raw materials: 0.6 wt% of N, N' -ethylene bis stearamide, 10 wt% of ethylene acrylic acid copolymer, 5 wt% of nano calcium carbonate, 2 wt% of dimethyl phthalate, 0.5 wt% of antioxidant 1076, 0.8 wt% of polypropylene wax, 1 wt% of chlorinated paraffin, 1 wt% of organic silicone oil, 5 wt% of wear-resistant antibacterial agent and the balance of polypropylene;
the preparation method of the wear-resistant antibacterial agent comprises the following steps:
s1, placing 20 parts by weight of 1mol/L zinc gluconate aqueous solution into a reaction container, dropwise adding 40 parts by weight of 1mol/L ammonium bicarbonate aqueous solution under stirring at 20 ℃ and 800rpm, wherein the dropwise adding speed is 1mL/min, continuing to react for 2 hours after the dropwise adding is finished, then adding 10 parts by weight of 0.168mol/L silver nitrate aqueous solution, continuing to react for 1 hour, centrifuging, washing precipitates with water to obtain a precursor, placing the precursor into a muffle furnace, gradually heating from room temperature to 500 ℃, heating at a speed of 4 ℃/min, calcining for 3 hours in a nitrogen atmosphere, and cooling to obtain the nano composite antibacterial agent;
s2 taking 10 parts by weight of the nano composite antibacterial agent, adding 150 parts by weight of isopropanol, adjusting the pH to 4.5 by using 1mol/L hydrochloric acid, carrying out ultrasonic treatment at an ultrasonic power of 200W and an ultrasonic frequency of 45kHz for 20min, adding 0.1 part by weight of 3-aminopropyltriethoxysilane, reacting for 1.5h under the stirring of 50 ℃ and 1000rpm, carrying out suction filtration, and drying for 12h at 70 ℃ to obtain the wear-resistant antibacterial agent.
The preparation method of the antibacterial wear-resistant polypropylene plastic comprises the following steps: putting N, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and polypropylene into a mixer, stirring at 1200rpm for 30min, melting and blending the mixed materials at 140 ℃ for 20min to obtain a blend, adding the blend into a double-screw extruder, and extruding and granulating, wherein the specific parameters are as follows: host rotation speed 100rpm, feed rate: 20rpm, the reference temperatures of the four screw heating sections are respectively as follows: the temperature of the first zone is 160 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 220 ℃, the retention time is 1.5min, and the pressure is 14Mpa, so that the antibacterial wear-resistant polypropylene plastic is obtained.
A preparation method of a wear-resistant polypropylene boot sleeve with an antibacterial function comprises the following steps: extruding and blowing the antibacterial wear-resistant polypropylene plastic into a film by using a plastic film blowing machine, wherein the temperatures of the four sections of the rear section of a charging barrel of the film blowing machine are respectively 160 ℃, 180 ℃ and 190 ℃, the temperatures of the four sections of the front section of the charging barrel are respectively 180 ℃, 200 ℃ and 210 ℃, the temperatures of the two sections of a head are respectively 220 ℃ and 220 ℃, the blowing ratio is 1.5, the rotating speed of a screw is 45rpm, and the traction speed is 32m/min, so as to obtain the film; the film is made into a wear-resistant polypropylene boot cover with an antibacterial function according to a conventional process.
Example 2
A wear-resistant polypropylene boot sleeve with an antibacterial function is made of antibacterial wear-resistant polypropylene plastics;
the antibacterial wear-resistant polypropylene plastic is prepared from the following raw materials: 0.6 wt% of N, N' -ethylene bis stearamide, 10 wt% of ethylene acrylic acid copolymer, 5 wt% of nano calcium carbonate, 2 wt% of dimethyl phthalate, 0.5 wt% of antioxidant 1076, 0.8 wt% of polypropylene wax, 1 wt% of chlorinated paraffin, 1 wt% of organic silicone oil, 5 wt% of wear-resistant antibacterial agent and the balance of polypropylene;
the preparation method of the wear-resistant antibacterial agent comprises the following steps: placing 20 parts by weight of 1mol/L zinc gluconate aqueous solution into a reaction container, dropwise adding 40 parts by weight of 1mol/L ammonium bicarbonate aqueous solution under stirring at 20 ℃ and 800rpm, wherein the dropwise adding speed is 1mL/min, continuing to react for 2 hours after the dropwise adding is finished, then adding 10 parts by weight of 0.168mol/L silver nitrate aqueous solution, continuing to react for 1 hour, centrifuging, washing the precipitate with water to obtain a precursor, placing the precursor into a muffle furnace, gradually heating from room temperature to 500 ℃, heating at a speed of 4 ℃/min, calcining for 3 hours under a nitrogen atmosphere, and cooling to obtain the wear-resistant antibacterial agent.
The preparation method of the antibacterial wear-resistant polypropylene plastic comprises the following steps: putting N, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and polypropylene into a mixer, stirring at 1200rpm for 30min, melting and blending the mixed materials at 140 ℃ for 20min to obtain a blend, adding the blend into a double-screw extruder, and extruding and granulating, wherein the specific parameters are as follows: host rotation speed 100rpm, feed rate: 20rpm, the reference temperatures of the four screw heating sections are respectively as follows: the temperature of the first zone is 160 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 220 ℃, the retention time is 1.5min, and the pressure is 14Mpa, so that the antibacterial wear-resistant polypropylene plastic is obtained.
A preparation method of a wear-resistant polypropylene boot sleeve with an antibacterial function comprises the following steps: extruding and blowing the antibacterial wear-resistant polypropylene plastic into a film by using a plastic film blowing machine, wherein the temperatures of the four sections of the rear section of a charging barrel of the film blowing machine are respectively 160 ℃, 180 ℃ and 190 ℃, the temperatures of the four sections of the front section of the charging barrel are respectively 180 ℃, 200 ℃ and 210 ℃, the temperatures of the two sections of a head are respectively 220 ℃ and 220 ℃, the blowing ratio is 1.5, the rotating speed of a screw is 45rpm, and the traction speed is 32m/min, so as to obtain the film; the film is made into a wear-resistant polypropylene boot cover with an antibacterial function according to a conventional process.
Example 3
A wear-resistant polypropylene boot sleeve with an antibacterial function is made of antibacterial wear-resistant polypropylene plastics;
the antibacterial wear-resistant polypropylene plastic is prepared from the following raw materials: 0.6 wt% of N, N' -ethylene bis stearamide, 10 wt% of ethylene acrylic acid copolymer, 5 wt% of nano calcium carbonate, 2 wt% of dimethyl phthalate, 0.5 wt% of antioxidant 1076, 0.8 wt% of polypropylene wax, 1 wt% of chlorinated paraffin, 1 wt% of organic silicone oil, 5 wt% of wear-resistant antibacterial agent and the balance of polypropylene;
the preparation method of the wear-resistant antibacterial agent comprises the following steps:
s1, placing 20 parts by weight of 1mol/L zinc gluconate aqueous solution into a reaction container, dropwise adding 40 parts by weight of 1mol/L ammonium bicarbonate aqueous solution under stirring at 20 ℃ and 800rpm, wherein the dropwise adding speed is 1mL/min, continuing to react for 2 hours after the dropwise adding is finished, then adding 10 parts by weight of 0.168mol/L silver nitrate aqueous solution, continuing to react for 1 hour, centrifuging, washing precipitates with water to obtain a precursor, placing the precursor into a muffle furnace, gradually heating from room temperature to 500 ℃, heating at a speed of 4 ℃/min, calcining for 3 hours in a nitrogen atmosphere, and cooling to obtain the nano composite antibacterial agent;
s2, taking 10 parts by weight of the nano composite antibacterial agent, adding 150 parts by weight of isopropanol, adjusting the pH to 4.5 by using 1mol/L hydrochloric acid, carrying out ultrasonic treatment at an ultrasonic frequency of 45kHz and an ultrasonic power of 200W for 20min, adding 0.1 part by weight of 3-aminopropyltriethoxysilane, reacting for 1.5h under the stirring of 50 ℃ and 1000rpm, carrying out suction filtration, and drying for 12h at 70 ℃ to obtain a modified nano composite antibacterial agent;
s3 mixing 80 parts by weight of absolute ethyl alcohol and 8 parts by weight of tetraethyl orthosilicate, adding 8 parts by weight of the modified nano composite antibacterial agent and 2 parts by weight of 20 wt% ammonia water at 40 ℃ and 400rpm, continuing stirring for 4h, filtering, washing with absolute ethyl alcohol, and drying at 70 ℃ for 12h to obtain the wear-resistant antibacterial agent.
The preparation method of the antibacterial wear-resistant polypropylene plastic comprises the following steps: putting N, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and polypropylene into a mixer, stirring at 1200rpm for 30min, melting and blending the mixed materials at 140 ℃ for 20min to obtain a blend, adding the blend into a double-screw extruder, and extruding and granulating, wherein the specific parameters are as follows: host rotation speed 100rpm, feed rate: 20rpm, the reference temperatures of the four screw heating sections are respectively as follows: the temperature of the first zone is 160 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 220 ℃, the retention time is 1.5min, and the pressure is 14Mpa, so that the antibacterial wear-resistant polypropylene plastic is obtained.
A preparation method of a wear-resistant polypropylene boot sleeve with an antibacterial function comprises the following steps: extruding and blowing the antibacterial wear-resistant polypropylene plastic into a film by using a plastic film blowing machine, wherein the temperatures of the four sections of the rear section of a charging barrel of the film blowing machine are respectively 160 ℃, 180 ℃ and 190 ℃, the temperatures of the four sections of the front section of the charging barrel are respectively 180 ℃, 200 ℃ and 210 ℃, the temperatures of the two sections of a head are respectively 220 ℃ and 220 ℃, the blowing ratio is 1.5, the rotating speed of a screw is 45rpm, and the traction speed is 32m/min, so as to obtain the film; the film is made into a wear-resistant polypropylene boot cover with an antibacterial function according to a conventional process.
Example 4
A wear-resistant polypropylene boot sleeve with an antibacterial function is made of antibacterial wear-resistant polypropylene plastics;
the antibacterial wear-resistant polypropylene plastic is prepared from the following raw materials: 0.6 wt% of N, N' -ethylene bis stearamide, 10 wt% of ethylene acrylic acid copolymer, 5 wt% of nano calcium carbonate, 2 wt% of dimethyl phthalate, 0.5 wt% of antioxidant 1076, 0.8 wt% of polypropylene wax, 1 wt% of chlorinated paraffin, 1 wt% of organic silicone oil, 5 wt% of wear-resistant antibacterial agent and the balance of polypropylene;
the preparation method of the wear-resistant antibacterial agent comprises the following steps:
s1, placing 20 parts by weight of 1mol/L zinc gluconate aqueous solution into a reaction container, dropwise adding 40 parts by weight of 1mol/L ammonium bicarbonate aqueous solution under stirring at 20 ℃ and 800rpm, wherein the dropwise adding speed is 1mL/min, continuing to react for 2 hours after the dropwise adding is finished, then adding 10 parts by weight of 0.168mol/L silver nitrate aqueous solution, continuing to react for 1 hour, centrifuging, washing precipitates with water to obtain a precursor, placing the precursor into a muffle furnace, gradually heating from room temperature to 500 ℃, heating at a speed of 4 ℃/min, calcining for 3 hours in a nitrogen atmosphere, and cooling to obtain the nano composite antibacterial agent;
s2, taking 10 parts by weight of the nano composite antibacterial agent, adding 150 parts by weight of isopropanol, adjusting the pH to 4.5 by using 1mol/L hydrochloric acid, carrying out ultrasonic treatment at an ultrasonic frequency of 45kHz and an ultrasonic power of 200W for 20min, adding 0.1 part by weight of 3-aminopropyltriethoxysilane, reacting for 1.5h under the stirring of 50 ℃ and 1000rpm, carrying out suction filtration, and drying for 12h at 70 ℃ to obtain a modified nano composite antibacterial agent;
s3, mixing 80 parts by weight of absolute ethyl alcohol and 8 parts by weight of tetraethyl orthosilicate, adding 8 parts by weight of the modified nano composite antibacterial agent and 2 parts by weight of 20 wt% ammonia water at 40 ℃ and 400rpm, continuing stirring for 4 hours, filtering, washing with absolute ethyl alcohol, and drying at 70 ℃ for 12 hours to obtain a silicon dioxide coated antibacterial agent;
s4, dispersing 10 parts by weight of the silicon dioxide coated antibacterial agent into 100 parts by weight of 60 wt% ethanol aqueous solution, performing ultrasonic treatment for 30min at ultrasonic frequency of 25kHz and ultrasonic power of 180W, then adding 3 parts by weight of graphene oxide and 0.3 part by weight of modifier, reacting for 6h at 70 ℃, centrifuging, washing with absolute ethyl alcohol, and drying at 80 ℃ for 12h to obtain the wear-resistant antibacterial agent.
The modifier is 1H,1H,2H, 2H-perfluoro dodecyl triethoxysilane.
The preparation method of the antibacterial wear-resistant polypropylene plastic comprises the following steps: putting N, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and polypropylene into a mixer, stirring at 1200rpm for 30min, melting and blending the mixed materials at 140 ℃ for 20min to obtain a blend, adding the blend into a double-screw extruder, and extruding and granulating, wherein the specific parameters are as follows: host rotation speed 100rpm, feed rate: 20rpm, the reference temperatures of the four screw heating sections are respectively as follows: the temperature of the first zone is 160 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 220 ℃, the retention time is 1.5min, and the pressure is 14Mpa, so that the antibacterial wear-resistant polypropylene plastic is obtained.
A preparation method of a wear-resistant polypropylene boot sleeve with an antibacterial function comprises the following steps: extruding and blowing the antibacterial wear-resistant polypropylene plastic into a film by using a plastic film blowing machine, wherein the temperatures of the four sections of the rear section of a charging barrel of the film blowing machine are respectively 160 ℃, 180 ℃ and 190 ℃, the temperatures of the four sections of the front section of the charging barrel are respectively 180 ℃, 200 ℃ and 210 ℃, the temperatures of the two sections of a head are respectively 220 ℃ and 220 ℃, the blowing ratio is 1.5, the rotating speed of a screw is 45rpm, and the traction speed is 32m/min, so as to obtain the film; the film is made into a wear-resistant polypropylene boot cover with an antibacterial function according to a conventional process.
Example 5
Essentially the same as example 4, except that the abrasion resistant antimicrobial agent was prepared as follows:
s1, placing 20 parts by weight of 1mol/L zinc gluconate aqueous solution into a reaction container, dropwise adding 40 parts by weight of 1mol/L ammonium bicarbonate aqueous solution under stirring at 20 ℃ and 800rpm, wherein the dropwise adding speed is 1mL/min, continuing to react for 2 hours after the dropwise adding is finished, then adding 10 parts by weight of 0.168mol/L silver nitrate aqueous solution, continuing to react for 1 hour, centrifuging, washing precipitates with water to obtain a precursor, placing the precursor into a muffle furnace, gradually heating from room temperature to 500 ℃, heating at a speed of 4 ℃/min, calcining for 3 hours in a nitrogen atmosphere, and cooling to obtain the nano composite antibacterial agent;
s2, taking 10 parts by weight of the nano composite antibacterial agent, adding 150 parts by weight of isopropanol, adjusting the pH to 4.5 by using 1mol/L hydrochloric acid, carrying out ultrasonic treatment at an ultrasonic frequency of 45kHz and an ultrasonic power of 200W for 20min, adding 0.1 part by weight of 3-aminopropyltriethoxysilane, reacting for 1.5h under the stirring of 50 ℃ and 1000rpm, carrying out suction filtration, and drying for 12h at 70 ℃ to obtain a modified nano composite antibacterial agent;
s3, dispersing 10 parts by weight of the modified nano composite antibacterial agent in 100 parts by weight of 60 wt% ethanol aqueous solution, performing ultrasonic treatment for 30min at ultrasonic frequency of 25kHz and ultrasonic power of 180W, adding 3 parts by weight of graphene oxide and 0.3 part by weight of modifier, reacting for 6h at 70 ℃, centrifuging, washing with absolute ethyl alcohol, and drying at 80 ℃ for 12h to obtain the wear-resistant antibacterial agent.
The modifier is 1H,1H,2H, 2H-perfluoro dodecyl triethoxysilane.
Example 6
Essentially the same as example 4 except that the modifier was 3- (methacryloyloxy) propyltrimethoxysilane.
Example 7
The process is substantially the same as in example 4 except that the modifier is 1H,1H,2H, 2H-perfluorododecatriethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane in a mass ratio of 1: 2.
Test example 1
And (3) testing antibacterial performance: refer to appendix A in GB21551.2-2010 Special requirements for antibacterial, sterilizing, and purifying functional antibacterial materials for household and similar appliances: antibacterial performance test method 1 (film pasting method) agent effect evaluation antibacterial performance test is performed on the wear-resistant polypropylene boot sleeve with antibacterial function prepared in embodiments 1-4 of the present invention; test bacteria: staphylococcus aureus ATCC6538p, tested 5 times in parallel, averaged, and the results are shown in table 1.
TABLE 1 antibacterial Property test results
| Staphylococcus aureus antibacterial ratio (%) | |
| Example 1 | 96.7 |
| Example 2 | 93.6 |
| Example 3 | 94.0 |
| Example 4 | 99.6 |
From the results, the wear-resistant polypropylene boot sleeve with the antibacterial function has good antibacterial performance, and the antibacterial effect is improved after modification, because the dispersing performance and the compatibility of the nano composite antibacterial agent in polypropylene plastic are improved after modification, and the stability of the nano composite antibacterial agent in the polypropylene plastic is further improved; the reason why the antibacterial performance is reduced after the silicon dioxide is added is that although the dispersion performance of the nano composite antibacterial agent in the polypropylene plastic is improved, the silicon dioxide has no antibacterial performance, and when the wear-resistant antibacterial agent with the same quality is added, the quality of the nano composite antibacterial agent is reduced, so that the antibacterial performance is reduced; the antibacterial performance of the graphene oxide which is sold in the market is not the same as that of the graphene oxide which is prepared by a specific method; in the embodiment 3, the antibacterial performance is improved after the graphene oxide is added, the graphene oxide has good antibacterial performance, and the dispersion performance and compatibility of the whole wear-resistant antibacterial agent in the matrix are improved after the graphene oxide is added, so that the antibacterial performance is relatively stable.
Test example 2
And (3) wear resistance test: the wear-resistant polypropylene boots with antibacterial function prepared in examples 1-7 of the present invention were tested by referring to the national standard GB/T6672-2001, Measure of thickness of plastic film and sheet, average test 5 groups, and the smaller the value of the average value, the better the wear resistance, and the measurement results are shown in Table 2.
Table 2 abrasion resistance test results
From the results in table 2, it can be seen that the wear resistance of the wear-resistant polypropylene boot cover with antibacterial function can be obviously improved after the silicon dioxide is added, the silicon dioxide can improve the wear resistance, the silicon dioxide is added into the polypropylene plastic material to facilitate drawing into filaments, meanwhile, the silicon dioxide can make the surface of the material more compact and finer, the friction coefficient is reduced, and the high strength of the nano particles greatly enhances the wear resistance of the material. Meanwhile, in the embodiment 5, the graphene oxide and the silicon dioxide coated antibacterial agent are connected by adding the modifying agent, the modified addition can improve the stability of the graphene oxide in the polypropylene plastic, reduce the occurrence of agglomeration, and fully play the wear-resistant and antibacterial enhancement effects of the graphene oxide on the wear-resistant polypropylene boot sleeve with the antibacterial function; in addition, 1H,1H,2H, 2H-perfluorododecyl triethoxysilane and 3- (methacryloyloxy) propyl trimethoxysilane are adopted as the modifier, so that the modifier has a synergistic effect, the affinity of the F atom in the 1H,1H,2H, 2H-perfluorododecyl triethoxysilane and graphene oxide is stronger, the affinity of the 3- (methacryloyloxy) propyl trimethoxysilane and silicon dioxide is stronger, the two exert advantages respectively, the graphene oxide and the silicon dioxide coated antibacterial agent are effectively connected, and finally the wear-resistant antibacterial agent with the performances of wear resistance, bacteria resistance and the like is obtained.
Claims (4)
1. The wear-resistant polypropylene boot sleeve with the antibacterial function is made of antibacterial wear-resistant polypropylene plastic, and is characterized in that the antibacterial wear-resistant polypropylene plastic is prepared from the following raw materials: 0.3-1 wt% of N, N' -ethylene bis stearamide, 5-15 wt% of ethylene acrylic acid copolymer, 4-12 wt% of nano calcium carbonate, 1-4 wt% of dimethyl phthalate, 0.1-0.8 wt% of antioxidant 1076, 0.2-1 wt% of polypropylene wax, 0.1-2 wt% of chlorinated paraffin, 0.5-2 wt% of organic silicon oil, 3-8 wt% of wear-resistant antibacterial agent and the balance of polypropylene;
the preparation method of the wear-resistant antibacterial agent comprises the following steps:
s1, placing 10-30 parts by weight of 0.5-2mol/L zinc gluconate aqueous solution into a reaction container, dropwise adding 30-50 parts by weight of 0.5-2mol/L ammonium bicarbonate aqueous solution under stirring at 15-30 ℃ and 600-1000rpm, wherein the dropwise adding speed is 0.5-1.2mL/min, continuing to react for 1-3h after the dropwise adding is finished, then adding 5-15 parts by weight of 0.1-0.2mol/L silver nitrate aqueous solution, continuing to react for 0.5-2h, centrifuging, washing precipitates with water to obtain a precursor, placing the precursor into a muffle furnace, gradually heating from room temperature to 400-600 ℃, heating at the speed of 3-8 ℃/min, calcining for 2-5h under the nitrogen atmosphere, and cooling to obtain the nano composite antibacterial agent;
s2, taking 8-15 parts by weight of the nano composite antibacterial agent, adding 200 parts by weight of isopropanol with 100-200 parts by weight, adjusting the pH to 4-5 by using 0.5-2mol/L hydrochloric acid, carrying out ultrasonic treatment at the ultrasonic power of 180-300W and the ultrasonic frequency of 30-60kHz for 15-40min, adding 0.05-0.2 part by weight of coupling agent, reacting for 1-3h under the stirring of 40-60 ℃ and 800-1200rpm, carrying out suction filtration, and drying for 8-50h at 60-80 ℃ to obtain the modified nano composite antibacterial agent;
s3, mixing 70-100 parts by weight of absolute ethyl alcohol and 5-12 parts by weight of tetraethyl orthosilicate, adding 5-10 parts by weight of modified nano composite antibacterial agent and 1-4 parts by weight of 10-30 wt% of ammonia water at 30-50 ℃ and 500rpm, continuing stirring for 3-6h, filtering, washing with absolute ethyl alcohol, and drying at 60-80 ℃ for 8-20h to obtain the silica-coated antibacterial agent;
s4, dispersing 5-12 parts by weight of the silicon dioxide coated antibacterial agent into 80-120 parts by weight of 50-80 wt% ethanol water solution, performing ultrasonic treatment at the ultrasonic power of 150-200W and the ultrasonic frequency of 20-50kHz for 20-40min, adding 2-5 parts by weight of graphene oxide and 0.1-0.6 part by weight of modifier, reacting at 60-80 ℃ for 4-8h, centrifuging, washing with absolute ethyl alcohol, and drying at 60-90 ℃ for 8-20h to obtain the wear-resistant antibacterial agent;
the modifier is 1H,1H,2H, 2H-perfluorododecyl triethoxysilane and/or 3- (methacryloyloxy) propyl trimethoxysilane.
2. The abrasion-resistant polypropylene bootie having an antibacterial function according to claim 1, wherein the coupling agent is a silane coupling agent.
3. The wear-resistant polypropylene boot cover with antibacterial function as claimed in claim 1, wherein the preparation method of the antibacterial wear-resistant polypropylene plastic is as follows: putting N, N' -ethylene bis stearamide, ethylene acrylic acid copolymer, nano calcium carbonate, dimethyl phthalate, antioxidant 1076, polypropylene wax, chlorinated paraffin, organic silicon oil, wear-resistant antibacterial agent and polypropylene into a mixer, stirring uniformly, then carrying out melt blending to obtain a blend, adding the blend into a double-screw extruder, and carrying out extrusion granulation to obtain the antibacterial wear-resistant polypropylene plastic.
4. The method for manufacturing a wear-resistant polypropylene boot cover with an antibacterial function according to any one of claims 1 or 3, wherein the antibacterial wear-resistant polypropylene plastic is extrusion-blown by a plastic film blowing machine to obtain a thin film; the film is made into the wear-resistant polypropylene boots with the antibacterial function according to the conventional process.
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