CN111875883A - Nano antibacterial antifouling table and chair plastic particles and preparation method thereof - Google Patents
Nano antibacterial antifouling table and chair plastic particles and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional plastics, and particularly relates to nano antibacterial antifouling table and chair plastic particles and a preparation method thereof. Specifically, the method comprises the following steps: firstly, preparing a nano composite antibacterial agent, loading silver ions and zinc ions in nano micropores formed by hydrolyzing sodium methylsilicate into silica gel, treating by using polytetrafluoroethylene emulsion, and obtaining the nano composite antibacterial agent by centrifugal spray drying and a sand mill, wherein the nano composite antibacterial agent has antibacterial property and hydrophobic self-cleaning property; further carrying out compound granulation with polypropylene, high-density polyethylene and the like to obtain nano plastic particles for the antibacterial and antifouling desk and chair; in addition, zinc tungstate is compounded in the nano composite antibacterial agent; the invention better aims at the basic performance requirements of the plastic table and chair, nanometer antibacterial antifouling table and chair plastic particles are prepared by reasonable formula cooperation, and after the antibacterial plastic product is prepared, the nanometer composite antibacterial agent forms antibacterial and self-cleaning antifouling functions in the product; has stable and long-acting antibacterial property.
Description
Technical Field
The invention belongs to the technical field of functional plastics, and particularly relates to nano antibacterial antifouling table and chair plastic particles and a preparation method thereof.
Background
With the development of plastic functionalization, a lot of furniture is widely used by replacing wood materials with plastic materials. Particularly, tables and chairs in public places such as kindergarten tables, chairs and beds are made of plastic materials; the seats of buses, hospitals and the like are made of more plastic materials. Plastic products play a very important role in the daily life of people.
However, the plastic table and chair is easy to breed bacteria due to frequent contact with people in the using process, thereby becoming the source of spreading diseases. Antibacterial plastics are a better means for solving the problem of bacterial pollution of plastic tables and chairs at present. In order to prevent bacteria from adhering to the surface of plastic desks and chairs, antibacterial plastic products are usually prepared by adding an antibacterial agent into plastic, so that the plastic has antibacterial property, and bacteria adhered to the plastic can be killed or the propagation of the bacteria can be inhibited within a certain period of time. The development of antibacterial plastics plays a good demonstration role in protecting human health. Particularly, with the continuous development of antibacterial agents and antibacterial technologies, the antibacterial agent is rapidly applied to various fields of plastic products. Besides the plastic products such as tables and chairs which are easy to pollute are made of antibacterial plastics, the antibacterial plastics are widely used for household air conditioners, refrigerator drawers, automotive interiors and the like.
At present, a complete technical chain is formed aiming at the research of antibacterial plastics, and the types, the antibacterial dispersion and the antibacterial effect of the antibacterial agent are more involved. For example, the current antibacterial agents include inorganic antibacterial agents, organic antibacterial agents, natural antibacterial agents, and synergistic complex antibacterial agents of various antibacterial agents. However, when used in plastic products, the antibacterial effect of the antibacterial agent is not satisfactory. The concrete points are as follows: the inorganic antibacterial agent meets the requirement of high-temperature hot processing of plastics, has good durability, but has limited antibacterial effect; the organic antibacterial agent has obvious antibacterial effect, but has poor heat-resistant processability of plastics, is easy to degrade and decompose at high temperature, and has poor antibacterial durability.
Specifically, when the inorganic antibacterial agent is used for antibacterial plastics, the inorganic antibacterial agent is mostly a metal ion antibacterial agent and consists of a carrier and an antibacterial component. The carrier is mainly titanium dioxide, porous zeolite powder and the like, and the antibacterial active ingredients are silver ions, zinc ions, copper ions and the like. The antibacterial mechanism of the inorganic antibacterial agent is that metal ions are easy to combine with protein, the spatial structure and activity of the protein and enzyme are damaged, and the metabolism of microorganisms is stopped. Therefore, in order to achieve better antibacterial effect, it is desirable that the inorganic antibacterial agent has the best antibacterial effect when contacting bacteria on the surface of the plastic product. However, more often than not, the loaded antimicrobial agent makes it difficult to kill the bacteria attached to the plastic product in a timely manner. In order to provide the antibacterial agent with a lasting antibacterial effect in plastics, at present, an inorganic antibacterial agent such as silver ions is loaded on superfine silicon dioxide or titanium dioxide and added into the plastics, and the inorganic antibacterial agent is mainly physically blended, so that the inorganic antibacterial agent is easy to seep out, and the antibacterial durability is also influenced.
In particular, plastic table and chair products are required to have not only excellent antibacterial properties but also stain resistance. The plastic table and chair product is contacted with the human body for a long time, and dirt such as sweat of the human body is easy to be retained on the surface of the plastic table and chair product, so that bacteria are promoted to breed. Therefore, the antibacterial agent and the antifouling synergistic treatment have important significance for improving the antibacterial and bacteriostatic effects of the plastic table and chair products.
Disclosure of Invention
In order to obtain the plastic table and chair with excellent antibacterial and antifouling effects, the invention provides nano antibacterial and antifouling plastic particles for the table and chair; further provides a preparation method for obtaining the plastic particles. The table and chair prepared by the nano antibacterial antifouling table and chair plastic particles through processes of injection molding or mould pressing and the like has a lasting antibacterial effect, can effectively prevent the surface of dirt from being detained, and can keep clean for a long time.
In order to realize the purpose, the following specific technical scheme is adopted:
firstly, the invention provides a preparation method of nano antibacterial antifouling table and chair plastic particles, which is characterized by comprising the following steps of:
s1, adding sodium methylsilicate into water for high-speed dispersion, adding citric acid while high-speed dispersion to adjust the pH value to 3-5, and stirring at high speed to form a gel solution; standing the gel liquid for 1-2h to obtain a gel substance, then washing with deionized water and carrying out vacuum filtration to obtain a semi-dry gel substance;
s2, uniformly stirring the semi-dry gel obtained in the step S1, zinc nitrate hexahydrate, silver nitrate and deionized water, adding polytetrafluoroethylene emulsion, uniformly dispersing, and then performing spray drying to obtain a composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2, zinc tungstate and white oil into slurry, feeding the slurry into a sand mill, grinding the slurry for 2 to 4 hours by taking 0.03mm of zirconium oxide as a grinding medium, and performing centrifugal separation to obtain the nano composite antibacterial agent;
s4, adding the nano composite antibacterial agent obtained in the step S3 into melted 58# paraffin, performing ultrasonic dispersion, then uniformly dispersing the nano composite antibacterial agent, polypropylene, high-density polyethylene, inorganic filler, dispersing agent, antistatic agent, flame retardant, antioxidant and pigment in a high-speed mixer, feeding the mixture into a double-screw extruder for extrusion, performing hot die face granulation, performing air cooling and screening by a vibrating screen to obtain the nano antibacterial antifouling table and chair plastic particles.
Preferably, the speed of high-speed dispersion in S1 is controlled at 800-1200 rpm; because the sodium methyl silicate is alkaline and difficult to dissolve in water, the sodium methyl silicate is dispersed in the water by high-speed stirring, and the system is continuously adjusted to be acidic by utilizing the acidic citric acid, so that the sodium methyl silicate is hydrolyzed into silicon dioxide gel.
Preferably, the semi-dry gel in S2 has abundant nano-micropores and adsorbability, and is used as a carrier for adsorbing and loading zinc nitrate hexahydrate and silver nitrate, and polytetrafluoroethylene emulsion is further added for spray drying, so that zinc ions and silver ions in the obtained composite antibacterial agent are fully dispersed in the nano-micropores; meanwhile, the polytetrafluoroethylene emulsion is used as a hydrophobic self-cleaning material, an adhesive material is fully coated and bonded in the micropores and on the surfaces of the gel particles, and the desorption of zinc ions and silver ions is prevented.
Further preferably, the addition amounts of the semi-dry gel, zinc nitrate hexahydrate, silver nitrate, deionized water and polytetrafluoroethylene emulsion in S2 are as follows: 10-15 parts of semi-dry gel, 3-5 parts of zinc nitrate hexahydrate, 1-3 parts of silver nitrate, 30-50 parts of deionized water and 3-6 parts of polytetrafluoroethylene emulsion. The polytetrafluoroethylene emulsion is emulsion with solid content of 40 wt%, and has excellent adhesion, hydrophobic self-cleaning performance and capacity of preventing contamination of plastic product.
Preferably, the spray drying in S2 is performed by using a centrifugal spray dryer, dispersing and spraying the dispersion liquid in a mist form under the centrifugal action by rotating at a high speed of 25000rpm, entering a drying chamber, contacting with hot air for rapid drying, and collecting by a cyclone separator to obtain the composite antibacterial agent.
Preferably, in S3, the composite antibacterial agent, the zinc tungstate and the white oil are prepared into slurry according to the mass ratio of 4-8:1-2: 40-60; although zinc ions and silver ions are loaded and fixed on the composite antibacterial agent, the particles are thick, and 0.03mm of zirconium oxide is used as a grinding medium, and a sand mill is used for sanding under the assistance of white oil, so that the particles reach the nanometer level, and the antibacterial effect is promoted; the white oil after the sand grinding separation can be recycled, a small amount of white oil is dispersed in the nano antibacterial agent, and the white oil is a common plastic lubricant and cannot influence later use. Further preferably, the sand mill is a double-power centrifugal nano sand mill (the experimental machine is NT-V10S model of Dongguan Eng mechanical Co., Ltd.).
Preferably, the raw materials in S4 are prepared according to the parts by weight, wherein, the nano composite antibacterial agent is 3-5 parts, the No. 58 paraffin is 3-5 parts, the polypropylene is 60-70 parts, the high density polyethylene is 10-15 parts, the inorganic filler is 5-8 parts, the dispersing agent is 0.5-1 part, the antistatic agent is 0.1-0.2 part, the flame retardant is 1-2 parts, the antioxidant is 0.05-0.1 part, and the pigment is 0.1-5 parts.
Because the nano composite antibacterial agent is less in use amount and difficult to disperse, and is directly mixed with bulk raw materials to influence the mixing effect and the dispersity, the nano composite antibacterial agent is pre-dispersed in the No. 58 paraffin melted into liquid through ultrasonic dispersion, so that the nano composite antibacterial agent is favorably dispersed in the bulk raw materials.
Further preferably, the high-speed mixer in S4 is a conventional device for premixing plastics, the temperature of the high-speed mixer is set to be 80-100 ℃, and the rotating speed is controlled to be 600-800 rpm.
Further preferably, the polypropylene in S4 is selected from the polypropylene with the trade name of K7726H; the high-density polyethylene is selected to be HDPE 8050; the inorganic filler is at least one of talcum powder, mica powder and wollastonite powder; the dispersing agent is one of polyethylene wax and ethylene bis stearamide; the antistatic agent is one of glyceryl monostearate and vegetable glyceride; the flame retardant is one or more of antimony trioxide, magnesium hydroxide and aluminum hydroxide; the antioxidant is one of an antioxidant 1010, an antioxidant 168 and an antioxidant DSTP; the pigment is a special pigment or color master batch for plastics according to the color requirements of specific products, and is not specially limited.
Further preferably, the twin-screw extruder in S4 is a co-rotating twin-screw extruder, the twin-screw extruder is provided with five sections of temperature control, and the temperature control from feeding to discharging is as follows: the first section is 130-.
Further preferably, the twin-screw extruder described in S4 is a co-rotating twin-screw extruder having a screw length-diameter ratio L/D of 45.
Furthermore, the invention provides the nano antibacterial antifouling plastic particles for tables and chairs prepared by the method. In view of the risk that residual bacteria in plastic table and chair products easily cause cross infection, the invention prepares the antibacterial plastic particles specially used for the plastic table and chair, and the prominent expression of the antibacterial plastic particles is as follows: firstly, preparing a nano composite antibacterial agent, loading silver ions and zinc ions in nano micropores formed by hydrolyzing sodium methylsilicate into silica gel, treating the nano composite antibacterial agent by using polytetrafluoroethylene emulsion, and obtaining the nano composite antibacterial agent by centrifugal spray drying and a sand mill, wherein the nano composite antibacterial agent has antibacterial property and hydrophobic self-cleaning property, and after being used for preparing an antibacterial plastic product, the nano composite antibacterial agent forms antibacterial and self-cleaning antifouling functions in the product; furthermore, zinc tungstate is compounded in the nano-composite antibacterial agent, and zinc tungstate is a semiconductor and contains zinc ions, so that the zinc ions of the zinc tungstate are antibacterial on one hand, and the photocatalysis effect of the zinc tungstate can be further antibacterial and bactericidal on the other hand. In addition, the invention better aims at the basic performance requirements of plastic tables and chairs, prepares the nano antibacterial antifouling table and chair plastic particles through reasonable formula cooperation, can be directly used for preparing the tables and chairs by injection molding, and has stable and long-acting antibacterial property.
The nanometer antibacterial antifouling plastic particles for tables and chairs and the preparation method have the outstanding characteristics and obvious advantages that:
(1) according to the invention, silver ions and zinc ions are loaded in nano micropores formed by hydrolyzing sodium methylsilicate into silica gel, polytetrafluoroethylene emulsion is used for treatment, and the nano composite antibacterial agent is obtained through centrifugal spray drying and a sand mill, has antibacterial and hydrophobic self-cleaning properties, and is beneficial to preventing bacteria from breeding on the surface of a plastic table and chair and improving antibacterial property due to the synergistic effect.
(2) According to the invention, zinc tungstate is compounded in the nano-composite antibacterial agent, and the zinc ion antibacterial and photocatalytic sterilization of the zinc tungstate are utilized, so that the antibacterial effect is synergistically improved.
(3) The formula of the nano antibacterial antifouling table and chair plastic particles is cooperated, the particles can be directly injected to prepare the plastic table and chair, the use is convenient, and the obtained plastic table and chair has long-acting antibacterial and antifouling functions.
(4) The preparation method has easily controlled process, and the key is that the nano composite antibacterial agent is obtained by centrifugal spraying and sand grinding, so that the nano composite antibacterial agent has less occupied land due to separation, spray drying and sand grinding, and the burden of production enterprises is not increased; the other devices are common devices for plastic extrusion processing. Therefore, the technology is easy to quickly load, and the large-scale stable production is realized. 1. The invention relates to a method for preparing a high-performance composite material.
Drawings
The beneficial effects of the invention are further explained in the following with the attached drawings:
FIG. 1 is a schematic diagram of a process for preparing nano plastic particles for anti-bacterial and anti-fouling tables and chairs according to the invention.
FIG. 2 shows plastic particles of a nanometer antibacterial and antifouling table and chair prepared by the method of example 1, which are white and smooth in particle color and can be used for preparing an antibacterial table and chair for direct lodging.
Detailed Description
The following examples are intended to further illustrate the present invention, but not to limit the scope of the claims of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. On the premise of not influencing the use, the conventional raw materials can be obtained by commercial purchase, for example, the pigment can be toner or color master batch which is prepared by manufacturers according to the color requirement.
Example 1
S1, adding sodium methyl silicate into water, dispersing the sodium methyl silicate in the water through high-speed dispersion at 800rpm, gradually adding citric acid while dispersing at high speed, continuously testing by using test paper until the pH value is 4, and continuously stirring for 15min to form a gel solution; standing the gel liquid for 2h to obtain a gel substance, then washing with deionized water and carrying out vacuum filtration to remove most of water adsorbed by the gel to obtain a semi-dry gel substance;
s2, mixing and stirring uniformly 10kg of the semi-dry gel obtained in the step S1, 3kg of zinc nitrate hexahydrate, 1kg of silver nitrate and 30kg of deionized water, then adding 3kg of polytetrafluoroethylene emulsion with the solid content of 40% (wt), sending the mixture into a centrifugal spray dryer after uniform dispersion, dispersing and spraying the dispersion in a mist form under the centrifugal action by high-speed rotation at 25000rpm, entering a drying chamber to contact with hot air for quick drying, and collecting the mixture through a cyclone separator to obtain the composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2, zinc tungstate and white oil into slurry according to the mass ratio of 8:1:40, taking 10kg of slurry, grinding the slurry for 2 hours in an NT-V10S type double-power centrifugal nano sand mill (equipment of Dongguan Engting Diamond mechanical Co., Ltd.) by taking 0.03mm of zirconium oxide as a grinding medium, and performing centrifugal separation to obtain the nano composite antibacterial agent;
s4, adding 5 parts by weight of fused 58# paraffin wax into 3 parts by weight of the nano composite antibacterial agent obtained in the step S3, performing ultrasonic dispersion for 10min, and then uniformly dispersing the mixture with 70 parts by weight of polypropylene K7726H, 15 parts by weight of high density polyethylene HDPE8050, 5 parts by weight of talcum powder with the particle size of 10 mu m, 0.5 part by weight of polyethylene wax serving as a dispersing agent, 0.2 part by weight of glycerol monostearate serving as an antistatic agent, 2 parts by weight of magnesium hydroxide serving as a flame retardant, 0.05 part by weight of antioxidant 1010 and 0.2 part by weight of titanium dioxide color masterbatch in a high-speed mixer, wherein the temperature of the high-speed mixer is set to be 100 ℃, and the rotating speed is controlled; then feeding the mixture into a 65-type co-rotating double-screw extruder with the length-diameter ratio of 45, wherein the double-screw extruder is provided with five-section temperature control, and the feeding and the discharging are respectively as follows: the first section is 150 ℃, the second section is 170 ℃, the third section is 190 ℃, the fourth section is 180 ℃ and the fifth section is 160 ℃; the nanometer antibacterial antifouling table and chair plastic particles are obtained through extrusion, grain cutting on a hot die surface, air cooling and screening by a vibrating screen. As shown in fig. 2. The nano antibacterial antifouling table and chair plastic particles prepared by the method in the embodiment 1 are white and smooth in particle color, and can be directly used for lodging to prepare antibacterial table and chairs.
Example 2
S1, adding sodium methyl silicate into water, dispersing at a high speed of 1200rpm to make the sodium methyl silicate difficult to disperse in the water, gradually adding citric acid while dispersing at a high speed, continuously testing by using a test paper until the pH value is 5, and continuously stirring for 15min to form a gel solution; standing the gel liquid for 2h to obtain a gel substance, then washing with deionized water and carrying out vacuum filtration to remove most of water adsorbed by the gel to obtain a semi-dry gel substance;
s2, mixing and stirring uniformly 15kg of the semi-dry gel obtained in the step S1, 5kg of zinc nitrate hexahydrate, 2kg of silver nitrate and 50kg of deionized water, then adding 3kg of polytetrafluoroethylene emulsion with the solid content of 40% (wt), sending the mixture into a centrifugal spray dryer after uniform dispersion, dispersing and spraying dispersion liquid in a mist form under the centrifugal action through high-speed rotation at 25000rpm, entering a drying chamber to contact with hot air for quick drying, and collecting the mixture through a cyclone separator to obtain the composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2, zinc tungstate and white oil into slurry according to the mass ratio of 6:2:60, taking 10kg of slurry, grinding the slurry for 2 hours in an NT-V10S type double-power centrifugal nano sand mill (equipment of Dongguan Engting Diamond mechanical Co., Ltd.) by taking 0.03mm of zirconium oxide as a grinding medium, and performing centrifugal separation to obtain the nano composite antibacterial agent;
s4, adding 3-5 parts by weight of the nano composite antibacterial agent obtained in the step S3 into 3-5 parts by weight of melted 58# paraffin wax, performing ultrasonic dispersion for 10min, and then uniformly dispersing the mixture with 70 parts by weight of polypropylene K7726H, 15 parts by weight of high density polyethylene HDPE8050, 5 parts by weight of mica powder with the particle size of 10 mu m, 0.5 part by weight of dispersing agent ethylene-based bis-stearamide, 0.2 part by weight of antistatic agent vegetable glyceride, 1 part by weight of flame retardant antimony trioxide, 0.1 part by weight of antioxidant DSTP and 0.1 part by weight of cobalt blue pigment in a high-speed mixer, wherein the temperature of the high-speed mixer is set as 80 ℃, and the rotating speed is controlled at 600 rpm; sending into a 65-type co-rotating double-screw extruder with a length-diameter ratio of 45, wherein the double-screw extruder is provided with five-section temperature control, and the feeding to the discharging respectively comprises: the first section is 130 ℃, the second section is 170 ℃, the third section is 200 ℃, the fourth section is 180 ℃ and the fifth section is 165 ℃; the nanometer antibacterial antifouling table and chair plastic particles are obtained through extrusion, grain cutting on a hot die surface, air cooling and screening by a vibrating screen.
Example 3
S1, adding sodium methyl silicate into water, dispersing at a high speed of 800rpm to make the sodium methyl silicate difficult to disperse in the water, gradually adding citric acid while dispersing at a high speed, continuously testing by using a test paper until the pH value is 5, and continuously stirring for 10min to form a gel solution; standing the gel liquid for 1-2h to obtain a gel substance, then washing with deionized water and vacuum filtering to remove most water adsorbed by the gel to obtain a semi-dry gel substance;
s2, mixing and stirring uniformly 12kg of the semi-dry gel obtained in the step S1, 3kg of zinc nitrate hexahydrate, 3kg of silver nitrate and 50kg of deionized water, then adding 3kg of polytetrafluoroethylene emulsion with the solid content of 40% (wt), sending the mixture into a centrifugal spray dryer after uniform dispersion, dispersing and spraying the dispersion in a mist form under the centrifugal action by high-speed rotation at 25000rpm, entering a drying chamber to contact with hot air for quick drying, and collecting the mixture through a cyclone separator to obtain the composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2, zinc tungstate and white oil into slurry according to the mass ratio of 8:2:60, taking 10kg of slurry, grinding the slurry for 4 hours in an NT-V10S type double-power centrifugal nano sand mill (equipment of Dongguan Engting Diamond mechanical Co., Ltd.) by taking 0.03mm of zirconium oxide as a grinding medium, and performing centrifugal separation to obtain the nano composite antibacterial agent;
s4, adding 5 parts by weight of the nano composite antibacterial agent obtained in the step S3 into 5 parts by weight of melted 58# paraffin, performing ultrasonic dispersion for 10min, and then uniformly dispersing the mixture with 65 parts by weight of polypropylene K7726H, 15 parts by weight of high density polyethylene HDPE8050, 8 parts by weight of talcum powder inorganic filler with the particle size of 10 mu m, 0.5 part by weight of dispersing agent ethylene-based bis-stearamide, 0.2 part by weight of antistatic agent glyceryl monostearate, 2 parts by weight of flame retardant aluminum hydroxide, 1680.1 parts by weight of antioxidant and 0.1 part by weight of cobalt blue pigment in a high-speed mixer, wherein the temperature of the high-speed mixer is set as 100 ℃, and the rotating speed is controlled at 600 rpm; sending into a 65-type co-rotating double-screw extruder with a length-diameter ratio of 45, wherein the double-screw extruder is provided with five-section temperature control, and the feeding to the discharging respectively comprises: the first section is 150 ℃, the second section is 180 ℃, the third section is 200 ℃, the fourth section is 170 ℃ and the fifth section is 160 ℃; the nanometer antibacterial antifouling table and chair plastic particles are obtained through extrusion, grain cutting on a hot die surface, air cooling and screening by a vibrating screen.
Comparative example 1
S1, adding sodium methyl silicate into water, dispersing the sodium methyl silicate in the water through high-speed dispersion at 800rpm, gradually adding citric acid while dispersing at high speed, continuously testing by using test paper until the pH value is 4, and continuously stirring for 15min to form a gel solution; standing the gel liquid for 2h to obtain a gel substance, then washing with deionized water and carrying out vacuum filtration to remove most of water adsorbed by the gel to obtain a semi-dry gel substance;
s2, mixing and stirring 10kg of the semi-dry gel obtained in the step S1, 3kg of zinc nitrate hexahydrate, 1kg of silver nitrate and 30kg of deionized water uniformly, sending the mixture into a centrifugal spray dryer, dispersing and spraying dispersion liquid in a mist form under the centrifugal action through high-speed rotation at 25000rpm, entering a drying chamber to contact with hot air for quick drying, and collecting the mixture through a cyclone separator to obtain the composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2, zinc tungstate and white oil into slurry according to the mass ratio of 8:1:40, taking 10kg of slurry, grinding the slurry for 2 hours in an NT-V10S type double-power centrifugal nano sand mill (equipment of Dongguan Engting Diamond mechanical Co., Ltd.) by taking 0.03mm of zirconium oxide as a grinding medium, and performing centrifugal separation to obtain the nano composite antibacterial agent;
s4, adding 5 parts by weight of fused 58# paraffin wax into 3 parts by weight of the nano composite antibacterial agent obtained in the step S3, performing ultrasonic dispersion for 10min, and then uniformly dispersing the mixture with 70 parts by weight of polypropylene K7726H, 15 parts by weight of high density polyethylene HDPE8050, 5 parts by weight of talcum powder with the particle size of 10 mu m, 0.5 part by weight of polyethylene wax serving as a dispersing agent, 0.2 part by weight of glycerol monostearate serving as an antistatic agent, 2 parts by weight of magnesium hydroxide serving as a flame retardant, 0.05 part by weight of antioxidant 1010 and 0.2 part by weight of titanium dioxide color masterbatch in a high-speed mixer, wherein the temperature of the high-speed mixer is set to be 100 ℃, and the rotating speed is controlled; then feeding the mixture into a 65-type co-rotating double-screw extruder with the length-diameter ratio of 45, wherein the double-screw extruder is provided with five-section temperature control, and the feeding and the discharging are respectively as follows: the first section is 150 ℃, the second section is 170 ℃, the third section is 190 ℃, the fourth section is 180 ℃ and the fifth section is 160 ℃; the nanometer antibacterial antifouling table and chair plastic particles are obtained through extrusion, grain cutting on a hot die surface, air cooling and screening by a vibrating screen.
Comparative example 1 no polytetrafluoroethylene emulsion is added to bond and fix silver ions and zinc ions when the composite antibacterial agent is prepared, on one hand, the durability of the antibacterial property is affected, for example, after the plastic product is boiled for a period of time in hot water, the silver ions, the zinc ions and the like are lost, and the antibacterial property is affected; on the other hand, plastic products are prone to bacterial growth due to the lack of hydrophobic self-cleaning properties of polytetrafluoroethylene.
Comparative example 2
S1, adding sodium methyl silicate into water, dispersing the sodium methyl silicate in the water through high-speed dispersion at 800rpm, gradually adding citric acid while dispersing at high speed, continuously testing by using test paper until the pH value is 4, and continuously stirring for 15min to form a gel solution; standing the gel liquid for 2h to obtain a gel substance, then washing with deionized water and carrying out vacuum filtration to remove most of water adsorbed by the gel to obtain a semi-dry gel substance;
s2, mixing and stirring uniformly 10kg of the semi-dry gel obtained in the step S1, 3kg of zinc nitrate hexahydrate, 1kg of silver nitrate and 30kg of deionized water, then adding 3kg of polytetrafluoroethylene emulsion with the solid content of 40% (wt), sending the mixture into a centrifugal spray dryer after uniform dispersion, dispersing and spraying the dispersion in a mist form under the centrifugal action by high-speed rotation at 25000rpm, entering a drying chamber to contact with hot air for quick drying, and collecting the mixture through a cyclone separator to obtain the composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2 and white oil into slurry according to the mass ratio of 8:40, taking 10kg of slurry, grinding the slurry for 2h in a NT-V10S double-power centrifugal type nano sand mill (equipment of Dongguan Eng Mitsubishi mechanical Co., Ltd.) by taking 0.03mm of zirconium oxide as a grinding medium, and performing centrifugal separation to obtain the nano composite antibacterial agent;
s4, adding 5 parts by weight of fused 58# paraffin wax into 3 parts by weight of the nano composite antibacterial agent obtained in the step S3, performing ultrasonic dispersion for 10min, and then uniformly dispersing the mixture with 70 parts by weight of polypropylene K7726H, 15 parts by weight of high density polyethylene HDPE8050, 5 parts by weight of talcum powder with the particle size of 10 mu m, 0.5 part by weight of polyethylene wax serving as a dispersing agent, 0.2 part by weight of glycerol monostearate serving as an antistatic agent, 2 parts by weight of magnesium hydroxide serving as a flame retardant, 0.05 part by weight of antioxidant 1010 and 0.2 part by weight of titanium dioxide color masterbatch in a high-speed mixer, wherein the temperature of the high-speed mixer is set to be 100 ℃, and the rotating speed is controlled; then feeding the mixture into a 65-type co-rotating double-screw extruder with the length-diameter ratio of 45, wherein the double-screw extruder is provided with five-section temperature control, and the feeding and the discharging are respectively as follows: the first section is 150 ℃, the second section is 170 ℃, the third section is 190 ℃, the fourth section is 180 ℃ and the fifth section is 160 ℃; the nanometer antibacterial antifouling table and chair plastic particles are obtained through extrusion, grain cutting on a hot die surface, air cooling and screening by a vibrating screen.
Comparative example 2 zinc tungstate was not added at the time of sanding refinement, and there was a certain influence on antibacterial performance.
Comparative example 3
S1, adding sodium methyl silicate into water, dispersing the sodium methyl silicate in the water through high-speed dispersion at 800rpm, gradually adding citric acid while dispersing at high speed, continuously testing by using test paper until the pH value is 4, and continuously stirring for 15min to form a gel solution; standing the gel liquid for 2h to obtain a gel substance, then washing with deionized water and carrying out vacuum filtration to remove most of water adsorbed by the gel to obtain a semi-dry gel substance;
s2, mixing and stirring uniformly 10kg of the semi-dry gel obtained in the step S1, 3kg of zinc nitrate hexahydrate, 1kg of silver nitrate and 30kg of deionized water, then adding 3kg of polytetrafluoroethylene emulsion with the solid content of 40% (wt), sending the mixture into a centrifugal spray dryer after uniform dispersion, dispersing and spraying the dispersion in a mist form under the centrifugal action by high-speed rotation at 25000rpm, entering a drying chamber to contact with hot air for quick drying, and collecting the mixture through a cyclone separator to obtain the composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2, zinc tungstate and white oil into slurry according to the mass ratio of 8:1:40, taking 10kg of slurry, carrying out ball milling for 2 hours in a ball mill, and carrying out centrifugal separation to obtain the composite antibacterial agent;
s4, adding 5 parts by weight of molten 58# paraffin wax into 3 parts by weight of the composite antibacterial agent obtained in the step S3, performing ultrasonic dispersion for 10min, and then uniformly dispersing the mixture with 70 parts by weight of polypropylene K7726H, 15 parts by weight of high-density polyethylene HDPE8050, 5 parts by weight of talcum powder with the particle size of 10 mu m, 0.5 part by weight of polyethylene wax serving as a dispersing agent, 0.2 part by weight of glycerol monostearate serving as an antistatic agent, 2 parts by weight of magnesium hydroxide serving as a flame retardant, 0.05 part by weight of antioxidant 1010 and 0.2 part by weight of titanium dioxide color masterbatch in a high-speed mixer, wherein the temperature of the high-speed mixer is set to be 100 ℃, and the rotating speed is; then feeding the mixture into a 65-type co-rotating double-screw extruder with the length-diameter ratio of 45, wherein the double-screw extruder is provided with five-section temperature control, and the feeding and the discharging are respectively as follows: the first section is 150 ℃, the second section is 170 ℃, the third section is 190 ℃, the fourth section is 180 ℃ and the fifth section is 160 ℃; the nanometer antibacterial antifouling table and chair plastic particles are obtained through extrusion, grain cutting on a hot die surface, air cooling and screening by a vibrating screen.
Comparative example 3 the composite antibacterial agent ground to nanometer level by a sand mill is not adopted, the composite antibacterial agent after ball milling is in micron level, the interface is less when the composite antibacterial agent is used in plastics, and the antibacterial performance of the antibacterial agent with the same addition amount in plastics is obviously different.
The plastic particles obtained in examples 1-3 and comparative examples 1-3 were injection molded to prepare a flatness test template, and the injection molding process was: the temperature of the charging barrel is 200 ℃, the nozzle is 190 ℃, the rotating speed of the screw is 120RPM, a flat test sample is obtained, and the test sample is cut into a standard 50mm multiplied by 50mm plate for the antibacterial property test. And each sample was boiled in an oil-water mixed solution for 15min, and the antibacterial properties before and after boiling were tested.
Referring to QB/T2591 'antibacterial property test method of antibacterial plastics', the antibacterial rate of the antibacterial agent to staphylococcus aureus and escherichia coli is calculated by a film pasting method through blank sample control. Inoculating bacteria on a sample to be detected, enabling the bacteria to uniformly contact the sample by a film pasting method, measuring the number of viable bacteria in the sample after 48 hours of culture, and calculating the antibacterial rate of the sample.
R(％)＝(B－C)/B×100
In the formula:
r-antibacterial rate (%);
b-average number of recovered bacteria (cfu/patch) for placebo;
c-average number of recovered bacteria (cfu/piece) of the antibacterial plastic sample.
The antibacterial ratio is shown in table 1.
Table 1:
| test sample | Antibacterial Rate (%) before boiling treatment | Antibacterial ratio after boiling (%) |
| Example 1 | 96 | 95 |
| Example 2 | 94 | 94 |
| Example 3 | 97 | 96 |
| Comparative example 1 | 96 | 81 |
| Comparative example 2 | 90 | 89 |
| Comparative example 3 | 92 | 91 |
Through tests, the sample prepared from the antibacterial plastic disclosed by the invention has good antibacterial property occasionally, the antibacterial agent is not lost after the sample is boiled in an oil-water mixed solution, and the special self-cleaning property enables grease to be difficult to adhere to the plastic and still keep the good antibacterial property. Comparative example 1 does not use polytetrafluoroethylene to treat the antibacterial agent, resulting in adhesion of grease to the plastic and loss of antibacterial anions and zinc ions, affecting the antibacterial effect.
Claims (10)
1. A preparation method of nano antibacterial antifouling table and chair plastic particles is characterized by comprising the following steps:
s1, adding sodium methylsilicate into water for high-speed dispersion, adding citric acid while high-speed dispersion to adjust the pH value to 3-5, and stirring at high speed to form a gel solution; standing the gel liquid for 1-2h to obtain a gel substance, then washing with deionized water and carrying out vacuum filtration to obtain a semi-dry gel substance;
s2, uniformly stirring the semi-dry gel obtained in the step S1, zinc nitrate hexahydrate, silver nitrate and deionized water, adding polytetrafluoroethylene emulsion, uniformly dispersing, and then performing spray drying to obtain a composite antibacterial agent;
s3, preparing the composite antibacterial agent obtained in the step S2, zinc tungstate and white oil into slurry, feeding the slurry into a sand mill, grinding the slurry for 2 to 4 hours by taking 0.03mm of zirconium oxide as a grinding medium, and performing centrifugal separation to obtain the nano composite antibacterial agent;
s4, adding the nano composite antibacterial agent obtained in the step S3 into melted 58# paraffin, performing ultrasonic dispersion, then uniformly dispersing the nano composite antibacterial agent, polypropylene, high-density polyethylene, inorganic filler, dispersing agent, antistatic agent, flame retardant, antioxidant and pigment in a high-speed mixer, feeding the mixture into a double-screw extruder for extrusion, performing hot die face granulation, performing air cooling and screening by a vibrating screen to obtain the nano antibacterial antifouling table and chair plastic particles.
2. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: the speed of high-speed dispersion in S1 was controlled at 800-1200 rpm.
3. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: the addition amounts of the semi-dry gel, zinc nitrate hexahydrate, silver nitrate, deionized water and polytetrafluoroethylene emulsion in the S2 are as follows: 10-15 parts of semi-dry gel, 3-5 parts of zinc nitrate hexahydrate, 1-3 parts of silver nitrate, 30-50 parts of deionized water and 3-6 parts of polytetrafluoroethylene emulsion.
4. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: the polytetrafluoroethylene emulsion in S2 is an emulsion with a solid content of 40% (wt).
5. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: and S2, performing spray drying by using a centrifugal spray dryer, dispersing and spraying the dispersion liquid in a mist form under the centrifugal action by high-speed rotation at 25000rpm, allowing the dispersion liquid to enter a drying chamber to contact with hot air for rapid drying, and collecting the dried dispersion liquid by using a cyclone separator to obtain the composite antibacterial agent.
6. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: s3, preparing the composite antibacterial agent, the zinc tungstate and the white oil into slurry according to the mass ratio of 4-8:1-2: 40-60.
7. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: the raw materials in the S4 are prepared according to the parts by weight, wherein, 3-5 parts of nano composite antibacterial agent, 3-5 parts of 58# paraffin, 60-70 parts of polypropylene, 10-15 parts of high density polyethylene, 5-8 parts of inorganic filler, 0.5-1 part of dispersant, 0.1-0.2 part of antistatic agent, 1-2 parts of flame retardant, 0.05-0.1 part of antioxidant and 0.1-5 parts of pigment.
8. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: in S4, the polypropylene is selected from K7726H; the high-density polyethylene is selected to be HDPE 8050; the inorganic filler is at least one of talcum powder, mica powder and wollastonite powder; the dispersing agent is one of polyethylene wax and ethylene bis stearamide; the antistatic agent is one of glyceryl monostearate and vegetable glyceride; the flame retardant is one or more of antimony trioxide, magnesium hydroxide and aluminum hydroxide; the antioxidant is selected from one of antioxidant 1010, antioxidant 168 and antioxidant DSTP.
9. The preparation method of the nano antibacterial antifouling plastic particles for tables and chairs according to claim 1 is characterized by comprising the following steps: the extrusion of the double-screw extruder in S4 is a co-rotating double-screw extruder, the double-screw extruder is provided with five-section temperature control, and the feeding and discharging are respectively as follows: the first section is 130-150 ℃, the second section is 170-180 ℃, the third section is 190-200 ℃, the fourth section is 170-180 ℃ and the fifth section is 160-165 ℃; the double-screw extruder adopts a co-rotating double-screw extruder with the length-diameter ratio L/D of a screw rod of 45.
10. A nano antibacterial antifouling plastic particle for tables and chairs, which is characterized by being prepared by the method of any one of claims 1 to 9.
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| CN112980088A (en) * | 2021-02-25 | 2021-06-18 | 深圳市台钜电工有限公司 | High-durability data line protective sleeve and preparation process thereof |
| CN113929997A (en) * | 2021-09-02 | 2022-01-14 | 华南理工大学 | Environment-friendly inorganic composite nano antibacterial and mildew-proof polymer master batch and preparation method and application thereof |
| WO2022021908A1 (en) * | 2020-07-25 | 2022-02-03 | 陈志益 | Nano antibacterial and antifouling plastic particles for tables and chairs and preparation method |
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| CN115232473A (en) * | 2022-08-24 | 2022-10-25 | 重庆晟淦新材料科技有限公司 | Antibacterial and corrosion-resistant PPS composite material and preparation method thereof |
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Denomination of invention: A nano antibacterial antifouling table and chair plastic particle and its preparation method Effective date of registration: 20221226 Granted publication date: 20211119 Pledgee: Agricultural Bank of China Limited Taizhou Economic Development Zone sub branch Pledgor: ZHEJIANG SENCHUAN FURNITURE Co.,Ltd. Registration number: Y2022330003708 |