CN112300526A - Novel wormwood HIPS plastic applied to refrigerator - Google Patents
Novel wormwood HIPS plastic applied to refrigerator Download PDFInfo
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Abstract
The invention provides a novel wormwood HIPS plastic applied to a refrigerator, which is prepared by blending wormwood HIPS master batches and common HIPS slices; the wormwood HIPS master batch comprises the following raw materials: 90-100 parts of HIPS (high impact polystyrene), 5-10 parts of wormwood functional particles, 2-4 parts of modified bentonite, 1-2 parts of stearic acid, 1-2 parts of liquid paraffin, 0.5-1 part of polypropylene grafted maleic anhydride, 2-3 parts of aluminum hydroxide, 0.5-1 part of antioxidant and 0.5-1 part of coupling agent. The preparation method of the wormwood functional particles comprises the following steps: preparing a wormwood extracting solution, pretreating and loading a molecular nest. The invention has the beneficial effects that: the bacteriostasis rate to staphylococcus aureus, colibacillus, candida albicans and other bacteria is 98.5-99.7%; the tensile strength is 39.8-45.1MPa, the bending strength is 52.4-58.3MPa, and the elongation at break is 67-72%.
Description
Technical Field
The invention relates to the field of HIPS (high impact polystyrene) plastics, in particular to a novel wormwood HIPS plastic applied to a refrigerator.
Background
With the enhancement of people's awareness of product safety and hygiene, the scale of the global antibacterial plastic market is continuously expanding. Relevant research reports predict that by 2015, the market scale of industrial application of global antibacterial plastics reaches 14 billion pounds, the product value of consumer products is 10.3 billion pounds, and 20% of global plastic products have antibacterial function.
At present, the popularization rate of antibacterial household appliances in developed countries such as japan is high, and household appliances such as antibacterial refrigerators and antibacterial washing machines are introduced in the early 90 s of the last century, and the current antibacterial household appliances account for over 50% of the market share of household appliances. The antibacterial plastic in Japan covers all plastic varieties, and the dosage of the antibacterial plastic is more than 150 million tons every year, so that the antibacterial plastic is the market with the largest usage amount of the antibacterial agent per capita.
The antibacterial plastics in China are rapidly developed in recent years, and the application field is continuously widened. In 2008, the national technical quality supervision and quarantine bureau promulgates a series of standards for implementing household electrical appliance antibiosis and sterilization. In 2011, the national standards for antibacterial home appliances are promulgated, so that the application of the antibacterial plastic in the home appliance industry is further specified. At present, the domestic demand of the antibacterial plastics is 15 ten thousand tons per year.
The existing antibacterial plastics are novel functional materials which are prepared by adding antibacterial substances into base materials, so that the materials have the capability of inhibiting or killing surface bacteria. The core of the antibacterial plastic is an antibacterial agent. Nowadays, antibacterial agents can be divided into three major systems, namely inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents according to the components. Wherein the natural antibacterial agent is the first antibacterial agent used by human, such as chitin, mustard, castor oil, etc. From past experience, the performance of the natural antibacterial agent is greatly influenced by the environment and is easy to lose efficacy; meanwhile, the natural antibacterial agent has poor thermal stability and is easy to decompose and lose efficacy in the processing process. Therefore, the improvement of the antibacterial performance of the natural antibacterial agent and the improvement of the processing stability thereof have been the key points and difficulties in the research of the antibacterial plastics adopting the natural antibacterial agent.
HIPS plastic, also known as high impact polystyrene, is a thermoplastic material made from elastomer-modified polystyrene, a two-phase system consisting of a rubber phase and a continuous polystyrene phase. HIPS plastics have been developed into important polymer commodities in the world, have a wide range of impact properties and processability, are widely applied to the fields of automobiles, appliances, electric products, furniture, electric appliances, computers and the like, and are increasingly researched and popularized in the field of kitchens due to the oil resistance, water resistance and low temperature resistance of the HIPS plastics.
The applicant finds that when the HIPS plastic prepared by adding natural antibacterial ingredients is applied to a refrigerator as an inner container of the refrigerator, the antibacterial ingredients on the outer surface of the HIPS plastic lose effectiveness quickly due to the environmental conditions of low temperature, humidity and easy oil contamination in the refrigerator in the daily use process; meanwhile, due to the comprehensive influence of the environment, the migration rate of the antibacterial components existing in the HIPS plastic to the surface is unstable, so that the long-term comprehensive antibacterial performance of the HIPS plastic surface is poor.
Further, in the research and development process of the novel wormwood HIPS plastic, the applicant also finds that after antibacterial substances such as wormwood extracts or wormwood functional particles are added into the HIPS plastic, the antibacterial substances are poor in distribution in the ABS plastic, not only are the antibacterial effects not ideal, but also the physical properties of the HIPS plastic are affected.
Chinese patent CN110857356A discloses an antibacterial plastic for automotive upholstery and a preparation method thereof, wherein effective components are extracted from Bishu, Chinese juniper and houttuynia cordata and are added into HIPS plastic as raw materials to endow the HIPS plastic with certain antibacterial performance. The disadvantages of the patent are that: the antibacterial plastic disclosed by the invention has a poor antibacterial effect in a long-term low-temperature environment, and when the antibacterial plastic is applied to a refrigerator as an inner container, the antibacterial component on the outer surface of HIPS plastic loses effectiveness quickly due to the environmental conditions of low temperature, humidity and easiness in oil contamination in the refrigerator; the migration rate of the antibacterial components existing in the HIPS plastic to the surface is unstable, and the long-term comprehensive antibacterial performance is poor.
Chinese patent CN103059496A discloses an antibacterial HIPS plastic, which is endowed with an antibacterial function by adding a composite antibacterial agent comprising cedar wood oil, chitosan, montmorillonite, nano silver oxide, polyhexamethylene guanidine phosphate and N- (trichloromethylthio) phthalimide into a HIPS plastic raw material. The disadvantages of the patent are that: when the antibacterial HIPS plastic is applied to a refrigerator as an inner container of the refrigerator, in the daily use process, the antibacterial component on the outer surface of the HIPS plastic is relatively quick to lose efficacy under the environmental conditions of low temperature, humidity and easy oil contamination in the refrigerator; meanwhile, the added antibacterial substance has poor distribution in ABS plastics, and the physical properties of HIPS plastics are seriously influenced.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a novel wormwood HIPS plastic applied to a refrigerator, so as to achieve the following purposes:
(1) the problems that the antibacterial components applied to the surface of HIPS (high impact polystyrene) plastic of a refrigerator lose effectiveness quickly, the migration rate of the antibacterial components in the plastic to the surface is unstable, and the long-term comprehensive antibacterial performance is poor are solved;
(2) the problem of poor distribution of the antibacterial substances added into the HIPS plastic in the plastic is solved;
(3) the problem that the physical properties of the plastic are influenced by the antibacterial substance added into the HIPS plastic is solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a novel wormwood HIPS plastic applied to a refrigerator is prepared by blending wormwood HIPS master batches and common HIPS slices;
the addition amount of the wormwood HIPS master batch is 1-9% of the total mass of the HIPS plastic;
the wormwood HIPS master batch comprises the following raw materials in parts by weight: 90-100 parts of HIPS (high impact polystyrene), 5-10 parts of wormwood functional particles, 2-4 parts of modified bentonite, 1-2 parts of stearic acid, 1-2 parts of liquid paraffin, 0.5-1 part of polypropylene grafted maleic anhydride, 2-3 parts of aluminum hydroxide, 0.5-1 part of antioxidant and 0.5-1 part of coupling agent;
the preparation method of the wormwood functional particles comprises the following steps: preparing a wormwood extracting solution, pretreating, loading and coating a molecular nest;
pretreating the molecular nest, namely putting the molecular nest into a concentrated sulfuric acid/concentrated nitric acid mixture with the volume 5 times that of the molecular nest, heating to 60 ℃, and ultrasonically dispersing uniformly; then, microwave treatment is adopted; adding hydrogen peroxide under stirring, and reacting for 0.5-1 h; naturally cooling, and filtering out solid matters; washing with deionized water until the pH value is 7.0-7.5; drying until the moisture content is less than 2%, and finishing the step of pretreatment of the molecular nest;
the molecular nest is a single-walled carbon nanotube;
and the loading step is carried out by mixing the pretreated molecular nest with the wormwood extracting solution, heating and stirring, drying at low temperature until ethanol is completely volatilized, and thus the molecular nest loaded with the wormwood active ingredients is prepared.
Further, the coating step, the molecular nest loaded with the wormwood active ingredient is put into a 3% polyvinyl alcohol aqueous solution with 50 times of volume, the stirring is carried out for 1 to 2 hours, and solid substances are filtered out; then putting the solid matter into 30 times volume of ethanol dissolved with azodiisobutyronitrile, heating to 70 ℃, and preserving heat; under the condition of stirring, dripping styrene with a predetermined part, heating to 85 ℃, and preserving heat for 1 h; filtering out solid substances, and vacuum drying to obtain the wormwood functional granules.
Further, the preparation of the wormwood extracting solution comprises the steps of grinding the wormwood extract to 100 meshes at the rotating speed of 200-300 RPM; adding into 8-10 times volume of anhydrous ethanol, heating to 65 deg.C, dispersing, and standing for 2 hr; then carrying out ultrasonic extraction for 40-50min, and filtering solid particles to obtain the wormwood extracting solution.
Further, the modified bentonite is prepared by mixing bentonite with sodium metasilicate pentahydrate, sodium dodecyl sulfate and microcrystalline cellulose, and grinding at 500-600RPM until the particle size D50 is 200-300 μm; then putting the ground material into deionized water with 3 times of volume, uniformly dispersing by ultrasonic, and stirring at the rotating speed of 30-40RPM for 10-12 h; filtering out solid materials, and drying at low temperature of 90-100 ℃ until the moisture content is less than 5%; grinding until the particle size D50 is 30-40nm to obtain the modified bentonite.
Further, the antioxidant is a mixture of antioxidant 1010 and antioxidant 1076; the antioxidant is 1010: the weight part ratio of the antioxidant 1076 is 5: 1;
the coupling agent is a silane coupling agent KH 570;
the particle size range of the aluminum hydroxide is 70-90 nm.
Further, in the step of pretreatment of the molecular nest, the concentration of the hydrogen peroxide is 30 percent, and the addition amount of the hydrogen peroxide is 0.3 to 0.4 time of the addition amount of the sulfuric acid;
the diameter of the single-walled carbon nanotube is 5-12nm, and the length-diameter ratio is 40-50: 1;
the concentrated sulfuric acid/concentrated nitric acid mixture is characterized in that concentrated sulfuric acid: the weight part ratio of the concentrated nitric acid is 2: 1;
the ultrasonic dispersion time is 2-3h, the ultrasonic frequency is 10-12kHz, and the ultrasonic intensity is 8W/cm2The ultrasonic power is 300-;
the microwave treatment time is 5-10min, the microwave frequency is 2.2-2.5GHz, and the microwave power is 600- & lt800W.
Further, in the coating step, the carboxylated single-walled carbon nanotubes loaded with the wormwood active ingredient: azobisisobutyronitrile: the weight ratio of styrene to styrene was 10:1: 100.
Further, the ultrasonic extraction is carried out, the ultrasonic frequency is 25-27kHz, and the ultrasonic intensity is 12W/cm2The ultrasonic power is 400-600W;
the wormwood extract has the weight loss on drying of less than 3%, the heavy metal content of less than 5PPM, the ash content of less than 2.0%, the pesticide residue of less than 2PPM, and the mesh number of 60-80 meshes.
Further, the bentonite: sodium metasilicate pentahydrate: sodium lauryl sulfate: the weight ratio of the microcrystalline cellulose is 100:6:2: 1.
Further, the preparation method of the wormwood HIPS master batch comprises the steps of uniformly mixing the raw materials in a predetermined part, and performing melt extrusion; then the product is prepared by drawing and granulating;
the temperature of the melting section of the double-screw extruder is 160-180 ℃, the temperature of the mixing section is 190-220 ℃, the temperature of the metering section is 220-230 ℃, and the temperature of the die head is 230-240 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the novel wormwood HIPS plastic applied to the refrigerator is used as the inner container of the refrigerator, and has the bacteriostasis rate of 98.5-99.7% to staphylococcus aureus, escherichia coli, candida albicans and other bacteria under a low-temperature environment.
(2) After the antibacterial components on the surface of the novel wormwood HIPS plastic fail, the migration rate of the antibacterial components in the HIPS plastic to the surface is stable, after the novel wormwood HIPS plastic is used for 10000 hours, the reduction rate of the antibacterial performance of the novel wormwood HIPS plastic on staphylococcus aureus, escherichia coli, candida albicans and other bacteria is about 2.3-3.4%, and the long-term comprehensive antibacterial performance is outstanding.
(3) The novel wormwood HIPS plastic applied to the refrigerator has good antibacterial component distribution in the HIPS plastic and good antibacterial effect.
(4) The novel wormwood HIPS plastic applied to the refrigerator is strong in self-cleaning capability, is not easy to be stained with oil stains or stains when used as an inner container of the refrigerator, is easy to clean, and can effectively keep the brightness and cleanness of the HIPS plastic surface.
(5) The novel wormwood HIPS plastic applied to the refrigerator effectively avoids the problem that the added antibacterial substances influence the physical properties of the novel wormwood HIPS plastic, and has excellent physical properties, wherein the tensile strength is 39.8-45.1MPa, the bending strength is 52.4-58.3MPa, and the elongation at break is 67-72%.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A novel wormwood HIPS plastic applied to a refrigerator is prepared by blending wormwood HIPS master batches and common HIPS slices and preparing novel wormwood HIPS plastic shells, accessories and the like applied to the refrigerator through a conventional process method (such as an injection molding process). The addition amount of the wormwood HIPS master batch is 1 percent of the total mass of the HIPS plastic.
The wormwood HIPS master batch comprises the following raw materials in parts by weight: 90 parts of HIPS (high impact polystyrene), 5 parts of wormwood functional particles, 2 parts of modified bentonite, 1 part of stearic acid, 1 part of liquid paraffin, 0.5 part of polypropylene grafted maleic anhydride, 2 parts of aluminum hydroxide, 0.5 part of antioxidant and 0.5 part of coupling agent.
The preparation method of the wormwood HIPS master batch comprises the steps of uniformly mixing the raw materials in parts by weight, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out strand pulling and granulation.
The temperature of the melting section of the double-screw extruder is 160 ℃, the temperature of the mixing section is 190 ℃, the temperature of the metering section is 220 ℃, and the temperature of the die head is 230 ℃.
The preparation method of the wormwood functional particles comprises the following steps: preparing a wormwood extracting solution, pretreating a molecular nest, loading and coating.
(1) Preparing the wormwood extracting solution, namely grinding the wormwood extract to 100 meshes at the rotating speed of 200 RPM; putting into absolute ethyl alcohol with the volume of 8 times, heating to 65 ℃, uniformly dispersing, and standing for 2 hours; then carrying out ultrasonic extraction for 40min, and filtering solid particles to obtain the wormwood extracting solution.
The ultrasonic frequency is 25kHz and the ultrasonic frequency is overThe sound intensity is 12W/cm2And the ultrasonic power is 400W.
The wormwood extract has the weight loss on drying of 1.9%, the heavy metal content of 2.2PPM, the ash content of 1.6%, the pesticide residue of 1.1PPM and the mesh number of 80 meshes.
(2) The molecular nest pretreatment, wherein the adopted molecular nest is single-walled carbon nanotubes (SWCNTs). Putting a predetermined part of the single-walled carbon nanotube into a concentrated sulfuric acid/concentrated nitric acid mixture with the volume 5 times that of the single-walled carbon nanotube, heating the mixture to 60 ℃ in a water bath, and ultrasonically dispersing the mixture for 2 hours; then carrying out microwave treatment for 5 min; dropwise adding 30% hydrogen peroxide under the stirring state at 100RPM, and continuously stirring and reacting for 0.5h after the hydrogen peroxide is added; naturally cooling to room temperature, filtering out solid substances, and washing with deionized water until the pH value is 7.5; and drying the carbon nano tube at 110 ℃ in a vacuum environment until the moisture content is less than 2%, and finishing the carrier pretreatment step to obtain the carboxylated single-walled carbon nano tube (SWCNTs-COOH).
The single-walled carbon nanotube has the diameter of 12nm and the length-diameter ratio of 50: 1.
The concentrated sulfuric acid/concentrated nitric acid mixture is characterized in that concentrated sulfuric acid: the weight ratio of the concentrated nitric acid is 2: 1.
The addition amount of the hydrogen peroxide is 0.3 time of that of the sulfuric acid.
The ultrasonic dispersion is carried out, the ultrasonic frequency is 10kHz, and the ultrasonic intensity is 8W/cm2And the ultrasonic power is 300W.
And (3) performing microwave treatment, wherein the microwave frequency is 2.2GHz, and the microwave power is 600W.
(3) The loading step, mixing the carboxylated single-walled carbon nanotubes with 10 times of the volume of the wormwood extracting solution, heating to 40 ℃, and stirring for 1h at the rotating speed of 500 RPM; centrifugally separating out solid matters, drying at 80 ℃ until the ethanol is completely volatilized, and preparing the carboxylated single-walled carbon nanotube loaded with the wormwood active ingredient.
(4) The coating is carried out, the carboxylated single-walled carbon nanotubes loaded with the wormwood active ingredient are put into a 3% polyvinyl alcohol aqueous solution with the volume 50 times that of the wormwood active ingredient, the mixture is stirred for 1 hour under the condition of 200RPM (revolution speed), and solid substances are filtered out; then putting the solid matter into 30 times volume of ethanol dissolved with azodiisobutyronitrile, heating to 70 ℃, and preserving heat; under the condition of the rotating speed of 30RPM, adding styrene in a predetermined part at the speed of 5ml/min, heating to 85 ℃ after finishing dripping, and preserving heat for 1 h; filtering out solid substances, and vacuum drying to obtain the wormwood functional granules.
The carboxylated single-wall carbon nanotube loaded with the wormwood active ingredient comprises the following components in percentage by weight: azobisisobutyronitrile: the weight ratio of styrene to styrene was 10:1: 100.
The modified bentonite is prepared by mixing bentonite with sodium metasilicate pentahydrate, sodium dodecyl sulfate and microcrystalline cellulose, putting the mixture into a ball mill, and grinding the mixture at 500RPM until the particle size D50 is 300 mu m; then putting the ground material into deionized water with 3 times of volume, uniformly dispersing by ultrasonic, and stirring at the rotating speed of 30RPM for 10 hours; filtering out solid materials, and drying at low temperature of 90 ℃ until the moisture content is less than 5%; grinding until the particle size D50 is 40nm to obtain the modified bentonite.
The bentonite: sodium metasilicate pentahydrate: sodium lauryl sulfate: the weight ratio of the microcrystalline cellulose is 100:6:2: 1.
The antioxidant is a mixture of an antioxidant 1010 and an antioxidant 1076; the antioxidant is 1010: the antioxidant 1076 has a weight ratio of 5: 1.
The coupling agent is a silane coupling agent KH 570.
The particle size of the aluminum hydroxide is 90 nm.
Through detection, the novel wormwood HIPS plastic applied to the refrigerator is used as the inner container of the refrigerator, and has an inhibition rate of 98.5% on bacteria such as staphylococcus aureus, escherichia coli, candida albicans and the like in a low-temperature environment; after the antibacterial components on the surface of the HIPS plastic fail, the migration rate of the antibacterial components in the HIPS plastic to the surface is stable, and after the HIPS plastic is used for 10000 hours, the reduction rate of the antibacterial performance of the HIPS plastic to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is about 3.4%; the self-cleaning performance is strong, oil stain or stain is not easy to be stained, the tensile strength is 39.8MPa, the bending strength is 53.8MPa, and the elongation at break is 67%.
Example 2
A novel wormwood HIPS plastic applied to a refrigerator is prepared by blending wormwood HIPS master batches and common HIPS slices and preparing novel wormwood HIPS plastic shells, accessories and the like applied to the refrigerator through a conventional process method (such as an injection molding process). The addition amount of the wormwood HIPS master batch is 7% of the total mass of the HIPS plastic.
The wormwood HIPS master batch comprises the following raw materials in parts by weight: 95 parts of HIPS (high impact polystyrene), 10 parts of wormwood functional particles, 4 parts of modified bentonite, 1.5 parts of stearic acid, 2 parts of liquid paraffin, 0.8 part of polypropylene grafted maleic anhydride, 2.5 parts of aluminum hydroxide, 1 part of antioxidant and 1 part of coupling agent.
The preparation method of the wormwood HIPS master batch comprises the steps of uniformly mixing the raw materials in a predetermined part, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out strand pulling and granulation to obtain the wormwood HIPS master batch.
The temperature of the melting section of the double-screw extruder is 170 ℃, the temperature of the mixing section is 210 ℃, the temperature of the metering section is 230 ℃, and the temperature of the die head is 240 ℃.
The preparation method of the wormwood functional particles comprises the following steps: preparing a wormwood extracting solution, pretreating a molecular nest, loading and coating.
(1) Preparing the wormwood extracting solution, namely grinding the wormwood extract to 100 meshes at the rotating speed of 250 RPM; adding into 10 times volume of anhydrous ethanol, heating to 65 deg.C, dispersing, and standing for 2 hr; then carrying out ultrasonic extraction for 50min, and filtering solid particles to obtain the wormwood extracting solution.
The ultrasonic frequency is 26kHz, and the ultrasonic intensity is 12W/cm2And the ultrasonic power is 550W.
The wormwood extract has the weight loss on drying of 1.9%, the heavy metal content of 2.2PPM, the ash content of 1.6%, the pesticide residue of 1.1PPM and the mesh number of 80 meshes.
(2) The molecular nest pretreatment, wherein the adopted molecular nest is single-walled carbon nanotubes (SWCNTs). Putting a predetermined part of the single-walled carbon nanotube into a concentrated sulfuric acid/concentrated nitric acid mixture with the volume 5 times that of the single-walled carbon nanotube, heating the mixture to 60 ℃ in a water bath, and ultrasonically dispersing the mixture for 3 hours; then carrying out microwave treatment for 10 min; dropwise adding 30% of hydrogen peroxide under the stirring state at 120RPM, and continuously stirring and reacting for 1h after the hydrogen peroxide is added; naturally cooling to room temperature, filtering out solid substances, and washing with deionized water until the pH value is 7.0; and drying at 120 ℃ in a vacuum environment until the moisture content is less than 2%, and finishing the carrier pretreatment step to obtain the carboxylated single-walled carbon nanotube (SWCNTs-COOH).
The diameter of the single-walled carbon nanotube is 8nm, and the length-diameter ratio of the single-walled carbon nanotube is 40: 1.
The concentrated sulfuric acid/concentrated nitric acid mixture is characterized in that concentrated sulfuric acid: the weight ratio of the concentrated nitric acid is 2: 1.
The addition amount of the hydrogen peroxide is 0.35 time of the addition amount of the sulfuric acid.
The ultrasonic dispersion has the ultrasonic frequency of 12kHz and the ultrasonic intensity of 8W/cm2And the ultrasonic power is 400W.
And (3) performing microwave treatment, wherein the microwave frequency is 2.4GHz, and the microwave power is 650W.
(3) The loading step, mixing the carboxylated single-walled carbon nanotubes with 10 times of the volume of the wormwood extracting solution, heating to 45 ℃, and stirring for 1.2h at the rotating speed of 600 RPM; centrifugally separating out solid matters, drying at 85 ℃ until the ethanol is completely volatilized, and preparing the carboxylated single-walled carbon nanotube loaded with the wormwood active ingredient.
(4) The coating is carried out, the carboxylated single-walled carbon nanotubes loaded with the wormwood active ingredient are put into a 3% polyvinyl alcohol aqueous solution with the volume 50 times that of the wormwood active ingredient, the mixture is stirred for 1.5 hours under the condition of 300RPM (revolution speed), and solid substances are filtered out; then putting the solid matter into 30 times volume of ethanol dissolved with azodiisobutyronitrile, heating to 70 ℃, and preserving heat; under the condition of 40RPM (revolution per minute) rotation speed, adding a predetermined part of styrene at the speed of 5ml/min, heating to 85 ℃ after finishing dripping, and preserving heat for 1 h; filtering out solid substances, and vacuum drying to obtain the wormwood functional granules.
The carboxylated single-wall carbon nanotube loaded with the wormwood active ingredient comprises the following components in percentage by weight: azobisisobutyronitrile: the weight ratio of styrene to styrene was 10:1: 100.
The modified bentonite is prepared by mixing bentonite with sodium metasilicate pentahydrate, sodium dodecyl sulfate and microcrystalline cellulose, putting the mixture into a ball mill, and grinding the mixture at 600RPM until the particle size D50 is 200 mu m; then putting the ground material into deionized water with 3 times of volume, uniformly dispersing by ultrasonic, and stirring at 35RPM for 12 hours; filtering out solid materials, and drying at low temperature of 95 ℃ until the moisture content is less than 5%; grinding until the particle size D50 is 30nm to obtain the modified bentonite.
The bentonite: sodium metasilicate pentahydrate: sodium lauryl sulfate: the weight ratio of the microcrystalline cellulose is 100:6:2: 1.
The antioxidant is a mixture of an antioxidant 1010 and an antioxidant 1076; the antioxidant is 1010: the antioxidant 1076 has a weight ratio of 5: 1.
The coupling agent is a silane coupling agent KH 570.
The particle size of the aluminum hydroxide is 70 nm.
Through detection, the novel wormwood HIPS plastic applied to the refrigerator is used as the inner container of the refrigerator, and has 99.7% of bacteriostasis rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria under a low-temperature environment; after the antibacterial components on the surface of the HIPS plastic fail, the migration rate of the antibacterial components in the HIPS plastic to the surface is stable, and after the HIPS plastic is used for 10000 hours, the reduction rate of the antibacterial performance of the HIPS plastic to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is about 2.3%; the self-cleaning performance is strong, oil stain or stain is not easy to be stained, the tensile strength is 45.1MPa, the bending strength is 58.3MPa, and the elongation at break is 69%.
Example 3
A novel wormwood HIPS plastic applied to a refrigerator is prepared by blending wormwood HIPS master batches and common HIPS slices and preparing novel wormwood HIPS plastic shells, accessories and the like applied to the refrigerator through a conventional process method (such as an injection molding process). The addition amount of the wormwood HIPS master batch is 9% of the total mass of the HIPS plastic.
The wormwood HIPS master batch comprises the following raw materials in parts by weight: 100 parts of HIPS (high impact polystyrene), 5 parts of wormwood functional particles, 4 parts of modified bentonite, 2 parts of stearic acid, 1 part of liquid paraffin, 0.5 part of polypropylene grafted maleic anhydride, 3 parts of aluminum hydroxide, 1 part of antioxidant and 1 part of coupling agent.
The preparation method of the wormwood HIPS master batch comprises the steps of uniformly mixing the raw materials in parts by weight, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out strand pulling and granulation.
The temperature of the melting section of the double-screw extruder is 180 ℃, the temperature of the mixing section is 220 ℃, the temperature of the metering section is 230 ℃, and the temperature of the die head is 230 ℃.
The preparation method of the wormwood functional particles comprises the following steps: preparing a wormwood extracting solution, pretreating a molecular nest, loading and coating.
(1) Preparing the wormwood extracting solution, namely grinding the wormwood extract to 100 meshes at the rotating speed of 300 RPM; adding into 10 times volume of anhydrous ethanol, heating to 65 deg.C, dispersing, and standing for 2 hr; then carrying out ultrasonic extraction for 40min, and filtering solid particles to obtain the wormwood extracting solution.
The ultrasonic frequency is 27kHz, and the ultrasonic intensity is 12W/cm2And the ultrasonic power is 600W.
The wormwood extract has the weight loss on drying of 1.9%, the heavy metal content of 2.2PPM, the ash content of 1.6%, the pesticide residue of 1.1PPM and the mesh number of 80 meshes.
(2) The molecular nest pretreatment, wherein the adopted molecular nest is single-walled carbon nanotubes (SWCNTs). Putting a predetermined part of the single-walled carbon nanotube into a concentrated sulfuric acid/concentrated nitric acid mixture with the volume 5 times that of the single-walled carbon nanotube, heating the mixture to 60 ℃ in a water bath, and ultrasonically dispersing the mixture for 2 hours; then carrying out microwave treatment for 5 min; dropwise adding 30% hydrogen peroxide under the stirring state at 100RPM, and continuously stirring and reacting for 0.5h after the hydrogen peroxide is added; naturally cooling to room temperature, filtering out solid substances, and washing with deionized water until the pH value is 7.2; and drying the carbon nano tube at 130 ℃ in a vacuum environment until the moisture content is less than 2%, and finishing the carrier pretreatment step to obtain the carboxylated single-walled carbon nano tube (SWCNTs-COOH).
The diameter of the single-walled carbon nanotube is 7nm, and the length-diameter ratio of the single-walled carbon nanotube is 45: 1.
The concentrated sulfuric acid/concentrated nitric acid mixture is characterized in that concentrated sulfuric acid: the weight ratio of the concentrated nitric acid is 2: 1.
The addition amount of the hydrogen peroxide is 0.4 time of that of the sulfuric acid.
The ultrasonic dispersion has the ultrasonic frequency of 12kHz and the ultrasonic intensity of 8W/cm2Ultrasound (ultrasound)The power is 500W.
And (3) performing microwave treatment, wherein the microwave frequency is 2.5GHz, and the microwave power is 800W.
(3) The loading step, mixing the carboxylated single-walled carbon nanotubes with 10 times of the volume of the wormwood extracting solution, heating to 50 ℃, and stirring for 1.2h at the rotating speed of 500 RPM; centrifugally separating out solid matters, drying at 90 ℃ until the ethanol is completely volatilized, and preparing the carboxylated single-walled carbon nanotube loaded with the wormwood active ingredient.
(4) The coating is carried out, the carboxylated single-walled carbon nanotubes loaded with the wormwood active ingredient are put into a 3% polyvinyl alcohol aqueous solution with the volume 50 times that of the wormwood active ingredient, the mixture is stirred for 1 hour under the condition of 200RPM (revolution speed), and solid substances are filtered out; then putting the solid matter into 30 times volume of ethanol dissolved with azodiisobutyronitrile, heating to 70 ℃, and preserving heat; under the condition of the rotating speed of 30RPM, adding styrene in a predetermined part at the speed of 5ml/min, heating to 85 ℃ after finishing dripping, and preserving heat for 1 h; filtering out solid substances, and vacuum drying to obtain the wormwood functional granules.
The carboxylated single-wall carbon nanotube loaded with the wormwood active ingredient comprises the following components in percentage by weight: azobisisobutyronitrile: the weight ratio of styrene to styrene was 10:1: 100.
The modified bentonite is prepared by mixing bentonite with sodium metasilicate pentahydrate, sodium dodecyl sulfate and microcrystalline cellulose, putting the mixture into a ball mill, and grinding the mixture at 500RPM until the particle size D50 is 250 mu m; then putting the ground material into deionized water with 3 times of volume, uniformly dispersing by ultrasonic, and stirring at 30RPM for 12 hours; filtering out solid materials, and drying at low temperature of 100 ℃ until the moisture content is less than 5%; grinding until the particle size D50 is 40nm to obtain the modified bentonite.
The bentonite: sodium metasilicate pentahydrate: sodium lauryl sulfate: the weight ratio of the microcrystalline cellulose is 100:6:2: 1.
The antioxidant is a mixture of an antioxidant 1010 and an antioxidant 1076; the antioxidant is 1010: the antioxidant 1076 has a weight ratio of 5: 1.
The coupling agent is a silane coupling agent KH 570.
The particle size of the aluminum hydroxide is 90 nm.
Through detection, the novel wormwood HIPS plastic applied to the refrigerator is used as the inner container of the refrigerator, and has 99.3% of bacteriostasis rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria under a low-temperature environment; after the antibacterial components on the surface of the HIPS plastic fail, the migration rate of the antibacterial components in the HIPS plastic to the surface is stable, and after the HIPS plastic is used for 10000 hours, the reduction rate of the antibacterial performance of the HIPS plastic to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is about 2.7%; the self-cleaning performance is strong, oil stain or stain is not easy to be stained, the tensile strength is 41.6MPa, the bending strength is 52.4MPa, and the elongation at break is 72%.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: the following steps were used instead of the "molecular nest pretreatment step" and the "loading step". The method comprises the specific steps of grinding commercially available bentonite particles to 10nm, adding into an ultrasonic extraction solution of the wormwood extract, repeatedly shearing, grinding and dispersing for 5 times, and drying to obtain the bentonite particles loaded with the wormwood active ingredients.
Through detection, the novel wormwood HIPS plastic applied to the refrigerator in the comparative example is used as the inner container of the refrigerator, and has 80.5% of bacteriostasis rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria in a low-temperature environment; after the antibacterial components on the surface of the HIPS plastic fail, the migration rate of the antibacterial components in the HIPS plastic to the surface is stable, and after the HIPS plastic is used for 10000 hours, the reduction rate of the antibacterial performance of the HIPS plastic to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is about 10.8%; the self-cleaning performance is strong, oil stain or stain is not easy to be stained, the tensile strength is 40.2MPa, the bending strength is 51.4MPa, and the elongation at break is 64%.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: the modified bentonite is replaced by the commercial bentonite with the same particle size specification.
Through detection, the novel wormwood HIPS plastic applied to the refrigerator is used as the inner container of the refrigerator, and has an inhibition rate of 98.2% on bacteria such as staphylococcus aureus, escherichia coli, candida albicans and the like in a low-temperature environment; after the antibacterial components on the surface of the HIPS plastic fail, the migration rate of the antibacterial components in the HIPS plastic to the surface is stable, and after the HIPS plastic is used for 10000 hours, the reduction rate of the antibacterial performance of the HIPS plastic to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is about 3.4%; the self-cleaning performance is strong, oil stain or stain is not easy to be stained, the tensile strength is 30.5MPa, the bending strength is 41.9MPa, and the elongation at break is 55%.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A novel wormwood HIPS plastic applied to a refrigerator is characterized in that the wormwood HIPS plastic is prepared by blending wormwood HIPS master batches and common HIPS slices;
the addition amount of the wormwood HIPS master batch is 1-9% of the total mass of the HIPS plastic;
the wormwood HIPS master batch comprises the following raw materials in parts by weight: 90-100 parts of HIPS (high impact polystyrene), 5-10 parts of wormwood functional particles, 2-4 parts of modified bentonite, 1-2 parts of stearic acid, 1-2 parts of liquid paraffin, 0.5-1 part of polypropylene grafted maleic anhydride, 2-3 parts of aluminum hydroxide, 0.5-1 part of antioxidant and 0.5-1 part of coupling agent;
the preparation method of the wormwood functional particles comprises the following steps: preparing a wormwood extracting solution, pretreating, loading and coating a molecular nest;
pretreating the molecular nest, namely putting the molecular nest into a concentrated sulfuric acid/concentrated nitric acid mixture with the volume 5 times that of the molecular nest, heating to 60 ℃, and ultrasonically dispersing uniformly; then, microwave treatment is adopted; adding hydrogen peroxide under stirring, and reacting for 0.5-1 h; naturally cooling, and filtering out solid matters; washing with deionized water until the pH value is 7.0-7.5; drying until the moisture content is less than 2%, and finishing the step of pretreatment of the molecular nest;
the molecular nest is a single-walled carbon nanotube;
and the loading step is carried out by mixing the pretreated molecular nest with the wormwood extracting solution, heating and stirring, drying at low temperature until ethanol is completely volatilized, and thus the molecular nest loaded with the wormwood active ingredients is prepared.
2. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 1, wherein the coating is carried out by putting the wormwood active ingredient-loaded molecular nest into 50 times volume of 3% polyvinyl alcohol aqueous solution, stirring for 1-2h, and filtering out solid substances; then putting the solid matter into 30 times volume of ethanol dissolved with azodiisobutyronitrile, heating to 70 ℃, and preserving heat; under the condition of stirring, dripping styrene with a predetermined part, heating to 85 ℃, and preserving heat for 1 h; filtering out solid substances, and vacuum drying to obtain the wormwood functional granules.
3. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 1, wherein the wormwood extract is prepared by grinding wormwood extract to 100 mesh at 200-300 RPM; adding into 8-10 times volume of anhydrous ethanol, heating to 65 deg.C, dispersing, and standing for 2 hr; then carrying out ultrasonic extraction for 40-50min, and filtering solid particles to obtain the wormwood extracting solution.
4. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 1, wherein the modified bentonite is obtained by mixing bentonite with sodium metasilicate pentahydrate, sodium dodecyl sulfate and microcrystalline cellulose, and grinding at 500-600RPM until the particle size D50 is 200-300 μm; then putting the ground material into deionized water with 3 times of volume, uniformly dispersing by ultrasonic, and stirring at the rotating speed of 30-40RPM for 10-12 h; filtering out solid materials, and drying at low temperature of 90-100 ℃ until the moisture content is less than 5%; grinding until the particle size D50 is 30-40nm to obtain the modified bentonite.
5. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 1, wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 1076; the antioxidant is 1010: the weight part ratio of the antioxidant 1076 is 5: 1;
the coupling agent is a silane coupling agent KH 570;
the particle size range of the aluminum hydroxide is 70-90 nm.
6. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 1, wherein in the molecular nest pretreatment step, the hydrogen peroxide concentration is 30%, and the addition amount is 0.3-0.4 times of the addition amount of sulfuric acid;
the diameter of the single-walled carbon nanotube is 5-12nm, and the length-diameter ratio is 40-50: 1;
the concentrated sulfuric acid/concentrated nitric acid mixture is characterized in that concentrated sulfuric acid: the weight part ratio of the concentrated nitric acid is 2: 1;
the ultrasonic dispersion time is 2-3h, the ultrasonic frequency is 10-12kHz, and the ultrasonic intensity is 8W/cm2The ultrasonic power is 300-;
the microwave treatment time is 5-10min, the microwave frequency is 2.2-2.5GHz, and the microwave power is 600- & lt800W.
7. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 1, wherein the coating step, the wormwood active ingredient-loaded carboxylated single-walled carbon nanotubes: azobisisobutyronitrile: the weight ratio of styrene to styrene was 10:1: 100.
8. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 3, wherein the ultrasonic extraction is carried out at an ultrasonic frequency of 25-27kHz and an ultrasonic intensity of 12W/cm2The ultrasonic power is 400-600W;
the wormwood extract has the weight loss on drying of less than 3%, the heavy metal content of less than 5PPM, the ash content of less than 2.0%, the pesticide residue of less than 2PPM, and the mesh number of 60-80 meshes.
9. The novel wormwood HIPS plastic for the refrigerator as claimed in claim 4, wherein the bentonite: sodium metasilicate pentahydrate: sodium lauryl sulfate: the weight ratio of the microcrystalline cellulose is 100:6:2: 1.
10. The novel wormwood HIPS plastic applied to the refrigerator as claimed in claim 1, wherein the wormwood HIPS master batch is prepared by uniformly mixing the raw materials in a predetermined part, and performing melt extrusion; then the product is prepared by drawing and granulating;
the temperature of the melting section of the double-screw extruder is 160-180 ℃, the temperature of the mixing section is 190-220 ℃, the temperature of the metering section is 220-230 ℃, and the temperature of the die head is 230-240 ℃.
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