CN112341708A - Novel wormwood PP plastic applied to toilet lid - Google Patents
Novel wormwood PP plastic applied to toilet lid Download PDFInfo
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Abstract
The invention provides a novel wormwood PP plastic applied to a toilet lid, which is prepared by blending wormwood PP master batches and common PP slices; the addition amount of the wormwood PP master batch is 1-10% of the total mass of the PP plastic; the wormwood PP master batch comprises the following raw materials: 90-100 parts of PP (polypropylene), 8-10 parts of wormwood functional particles, 15-20 parts of glass fibers, 3-5 parts of triphosphite, 2-3 parts of modified bentonite, 1-2 parts of calcium stearate, 1-2 parts of diphenyl carbonate, 2-3 parts of tetrabutylammonium hydrogen sulfate, 0.5-1 part of antioxidant and 1-5 parts of coupling agent. The novel wormwood PP plastic applied to the toilet lid has the bacteriostasis rate of 98.1-99.4% on staphylococcus aureus, escherichia coli, candida albicans and other bacteria; the mildew-proof grade is 0 grade; the tensile strength is 35-37MPa, and the shrinkage rate is 0.42-0.66%.
Description
Technical Field
The invention relates to the field of PP (polypropylene) plastics, in particular to a novel wormwood PP plastic applied to a toilet lid.
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 antibacterial polypropylene occupies an important share in the antibacterial plastics, and the domestic consumption exceeds 5 ten thousand tons per year.
The PP plastic is also called polypropylene plastic, is thermoplastic synthetic resin with excellent performance, and is colorless translucent thermoplastic light general plastic. Has chemical resistance, heat resistance, electric insulation, high-strength mechanical property, good high-wear-resistance processing property and the like. Since the advent of PP plastics, PP plastics have rapidly gained wide development and application in many fields such as machinery, automobiles, electronic appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like. Due to its plasticity, PP plastic products are gradually replacing traditional wood products, with huge application space.
Due to the excellent performance of PP plastics, more and more manufacturers use PP plastics as a raw material for producing toilet lids. At present, the method of adding the antibacterial master batch containing chemical or biological antibacterial agent into the PP polypropylene raw material is generally adopted in China to prepare the antibacterial product so as to realize the antibacterial function and kill or inhibit bacteria stained on the surface of the PP plastic toilet cover within a certain period of time.
The applicant finds that in the process of daily use, after frequent contact with human skin, frequent wiping and cleaning and long-term humid environment, the antibacterial ingredient on the surface of the PP plastic antibacterial toilet cover is quickly lost, the migration rate of the antibacterial ingredient in the PP plastic antibacterial toilet cover to the surface is not ideal, and the surface of the PP plastic antibacterial toilet cover cannot keep better antibacterial performance for a long time.
Meanwhile, in the process of preparing the master batch or preparing the PP plastic, the processing stability of the antibacterial component is poor, the antibacterial component is easy to lose or lose efficacy due to the influence of process conditions in the processing process, and the antibacterial performance is unstable.
Chinese patent CN105504493A discloses an antibacterial reinforced PP plastic and a preparation method thereof, which endows the PP plastic with antibacterial performance by adding one or more antibacterial agents of vanillin, ethyl vanillin, acylaniline, imidazole, thiazole, isothiazole ketone, quaternary ammonium salt, biguanidine and phenolic compound into the PP plastic raw material. The disadvantages are that: the antibacterial component has poor processing stability, is easy to be influenced by process conditions in the processing process to cause loss or failure, and has unstable antibacterial performance; meanwhile, when the PP plastic antibacterial toilet cover is used for manufacturing the toilet cover, in the daily use process, through frequent contact with human skin, frequent wiping and cleaning and long-term humid environment, the PP plastic antibacterial toilet cover has the advantages that the loss of antibacterial components on the surface is fast, and the better antibacterial performance cannot be maintained for a long time.
Further, the applicant also found that the existing method for preparing the PP plastic by adding the antibacterial master batch containing the chemical or biological antibacterial ingredients into the raw materials has undesirable distribution of the antibacterial ingredients in the PP plastic; and to some extent also to a decrease in the physical properties of the PP plastic.
Chinese patent CN108948528A discloses a crash-resistant antibacterial PP plastic lunch box and a preparation method thereof, wherein the antibacterial function of PP plastic is realized by adding auxiliary agents such as bagasse, chitosan, shell powder and the like into PP plastic raw materials. The defects that auxiliary components such as bagasse, chitosan, shell powder and the like added in the patent are not well distributed in PP plastic; and to some extent, to cause the reduction in the physical properties that the PP plastic should have.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a novel wormwood PP plastic applied to a toilet lid, so as to achieve the following aims:
(1) the problems that the loss of antibacterial components on the surface of the PP plastic antibacterial toilet lid is fast and better antibacterial performance cannot be kept for a long time are solved;
(2) the problems that the processing stability of the antibacterial component is poor and the antibacterial component is easy to be influenced by the process conditions in the processing process to cause loss or failure are solved;
(3) the problems that the added antibacterial component is not ideal to be distributed in the PP plastic and the due physical properties of the PP plastic are reduced are solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a novel wormwood PP plastic applied to a toilet lid is characterized by being prepared by blending wormwood PP master batches and common PP slices;
the addition amount of the wormwood PP master batch is 1-10% of the total mass of the PP plastic;
the wormwood PP master batch comprises the following raw materials in parts by weight: 90-100 parts of PP (polypropylene), 8-10 parts of wormwood functional particles, 15-20 parts of glass fibers, 3-5 parts of triphosphite, 2-3 parts of modified bentonite, 1-2 parts of calcium stearate, 1-2 parts of diphenyl carbonate, 2-3 parts of tetrabutylammonium hydrogen sulfate, 0.5-1 part of antioxidant and 1-5 parts of coupling agent;
the preparation of the wormwood PP master batch comprises the steps of mixing the raw materials in the predetermined parts, carrying out melt extrusion, and then carrying out drawing and granulation to obtain the wormwood PP master batch;
the preparation method of the wormwood functional particles comprises the following steps: preparing a molecular nest precursor and preparing molecular nest particles;
the molecular nest precursor is prepared from aminopropyltriethoxysilane, dodecyl trimethyl ammonium bromide, ethanol, ethyl orthosilicate and ammonia water;
preparing the molecular nest particles, namely heating, molding and cooling the molecular nest precursor, putting the molecular nest precursor into an ultrasonic extracting solution of the wormwood extract, standing, and removing ethanol to obtain the molecular nest particles;
the molecular nest particles are silicon dioxide particles;
the glass fiber is silanized glass fiber.
Further, preparing the molecular nest precursor under the reaction condition of three times of heat preservation and pressure maintaining reaction;
the first heat preservation and pressure maintaining reaction is carried out in a normal pressure environment, the temperature is heated to 30-35 ℃, and the stirring is carried out for 3-4 hours;
performing the second heat-preservation and pressure-maintaining reaction, pressurizing to 2-3MPa, heating to 60-65 ℃, and performing the heat-preservation and pressure-maintaining reaction for 1-2h under the condition that the stirring speed is 100-120 RPM;
and (3) carrying out heat preservation and pressure maintaining reaction for the third time, pressurizing to 3-5MPa, heating to 80-100 ℃, and carrying out heat preservation and pressure maintaining reaction for 8-9h under the condition that the stirring speed is 100-120 RPM.
Further, the preparation of the molecular nest particles comprises the steps of heating the molecular nest precursor to 350 ℃, preserving heat and forming for 7-10h, and naturally cooling; soaking in 1.5 times of ultrasonic extractive solution of folium Artemisiae Argyi extract, standing for 2-3 hr, and filtering to obtain solid substance; drying at 80 deg.C until ethanol is completely volatilized to obtain molecular nest granule loaded with folium Artemisiae Argyi extract active component.
Further, the ultrasonic extracting solution of the wormwood extract is prepared by grinding the wormwood extract to 100 meshes; 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 to prepare an ultrasonic extracting solution of the wormwood extract;
the ultrasonic frequency is 25-27kHz, and the ultrasonic intensity is 12W/cm2And the ultrasonic power is 400W.
Furthermore, the wormwood extract has the drying weight loss 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 preparation method of the silanized glass fiber comprises the following steps: adding hydrogen peroxide into the glass fiber, uniformly mixing, heating to 120-130 ℃, and carrying out heat preservation reaction for 1-1.5 h; filtering out solid materials, and drying by hot air at 80-90 ℃ until the moisture content is less than 2%; then the mixture is put into acetone for even dispersion, isobutyl triethoxysilane with a predetermined portion is dripped in at the speed of 5ml/min, the temperature is raised to 90 ℃, the reaction is carried out for 2-3h under the condition of heat preservation, solid materials are filtered out, the solid materials are dried and ground until the particle diameter D50 is 100-120nm, and the silanized glass fiber is prepared.
Further, the hydrogen peroxide: glass fiber: acetone: the ratio of parts by weight of the isobutyl triethoxysilane is 20: 1: 40: 8;
the glass fiber has a length of 30-40 μm and a diameter of 10-12 μm.
Further, the modified bentonite is prepared by mixing bentonite with sodium metasilicate pentahydrate, sodium dodecyl sulfate and microcrystalline cellulose, and grinding the mixture until the particle size D50 is 200-300 mu m; adding into deionized water with 3 times of volume, and stirring for 10-12 h; filtering out solid materials, and drying until the moisture content is less than 5%; grinding until the particle size D50 is 30-40nm to obtain the modified bentonite.
Further, the bentonite: sodium metasilicate pentahydrate: sodium lauryl sulfate: the weight ratio of the microcrystalline cellulose is 100:6:2: 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) the novel wormwood PP plastic applied to the toilet lid has good processing stability of wormwood active ingredients, can effectively avoid the influence of the preparation process on the wormwood active ingredients, and has the bacteriostasis rate of 98.1-99.4% on staphylococcus aureus, escherichia coli, candida albicans and other bacteria.
(2) The novel wormwood PP plastic applied to the toilet lid effectively solves the problem that the loss of antibacterial components on the surface of the PP plastic antibacterial toilet lid is fast, the bacteriostasis rate of bacteria such as staphylococcus aureus, escherichia coli, candida albicans and the like is reduced by less than 3% after the PP plastic is sprayed with water and wiped dry, and the excellent antibacterial performance of the PP plastic toilet lid in daily use can be guaranteed.
(3) According to the novel wormwood PP plastic applied to the toilet lid, no mildew grows on the surface of the PP plastic toilet lid through a mildew-proof test, and the mildew-proof grade is 0.
(4) According to the novel wormwood PP plastic applied to the toilet lid, the distribution of wormwood active ingredients in the PP plastic is good, and the wormwood active ingredients existing in the PP plastic can uniformly and stably migrate to the surface, so that the PP plastic can always keep excellent performance.
(5) The novel wormwood PP plastic applied to the toilet lid is strong in self-cleaning capability, and the toilet lid made of the novel wormwood PP plastic is not easy to be stained and easy to clean, and can keep the surface smooth and sanitary for a long time.
(6) The novel wormwood PP plastic applied to the toilet lid is good in physical performance, the tensile strength is 35-37MPa, and the shrinkage rate is 0.42-0.66%.
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 folium Artemisiae Argyi PP plastic used for toilet lid is prepared by mixing folium Artemisiae Argyi PP master batch and common PP slice, and making into various plastic products by conventional process (such as injection molding). The addition amount of the wormwood PP master batch is 1 percent of the total mass of the PP plastic.
The wormwood PP master batch comprises the following raw materials in parts by weight: 90 parts of PP, 8 parts of wormwood functional particles, 15 parts of glass fibers, 3 parts of triphosphite, 2 parts of modified bentonite, 1 part of calcium stearate, 1 part of diphenyl carbonate, 2 parts of tetrabutylammonium hydrogen sulfate, 0.5 part of antioxidant and 1 part of coupling agent.
The preparation method of the wormwood PP master batch comprises the steps of weighing the raw materials according to the parts by weight, mixing, heating to 120 ℃ under the stirring state of 100RPM, and keeping the temperature for 10 min; and then adding the mixed material into a double-screw extruder, carrying out melt extrusion, and carrying out drawing and granulation to obtain the composite material.
The melt extrusion temperature was 200 ℃ and the twin screw extruder speed was 320 RPM.
The wormwood functional particles are prepared by the following method:
(1) preparing an ultrasonic extracting solution: grinding the wormwood extract to 100 mesh at 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 ultrasonic extracting solution of the wormwood extract.
The ultrasonic frequency is 25kHz, and the ultrasonic intensity is 12W/cm2And the ultrasonic power is 400W.
The wormwood extract has the weight loss on drying of 2.6 percent, the heavy metal content of 3.4PPM, the ash content of 1.7 percent, the pesticide residue of 0.91PPM and the mesh number of 70 meshes.
(2) Preparing a molecular nest precursor: adding aminopropyltriethoxysilane and dodecyl trimethyl ammonium bromide into 2 times of 60% ethanol by weight, heating to 30 deg.C, and stirring for 3 hr; adding tetraethoxysilane, pressurizing to 2MPa, heating to 60 ℃, and carrying out heat preservation and pressure maintaining reaction for 1h under the condition that the stirring speed is 100 RPM; adding ammonia water to adjust the pH value to 8-9, continuously heating to 80 ℃, pressurizing to 3MPa, and carrying out heat preservation and pressure maintaining reaction for 8 hours; and preparing the molecular nest precursor.
The aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1:0.2: 0.6.
(3) Preparing molecular nest particles: heating the molecular nest precursor to 300 ℃, preserving heat, forming for 7h, naturally cooling to room temperature, soaking into the ultrasonic extracting solution of the wormwood extract with the volume of 1.5 times, standing for 2h, filtering out solid substances, drying at the low temperature of 80 ℃ until ethanol is completely volatilized, and preparing the molecular nest particles loaded with the active ingredients of the wormwood extract, namely the wormwood functional particles.
The molecular nest particles are silica particles.
The particle size range of the wormwood functional particles is 15-20 nm.
The glass fiber is silanized glass fiber. Adding predetermined parts of hydrogen peroxide into glass fibers, stirring at 50RPM, uniformly mixing, heating to 120 ℃, and carrying out heat preservation reaction for 1 hour; filtering out solid materials, and drying by hot air at 80 ℃ until the moisture content is less than 2%; then adding the mixture into acetone of a predetermined part for uniform dispersion, dripping isobutyl triethoxysilane of a predetermined part at the speed of 5ml/min, heating to 90 ℃, preserving heat for reaction for 2 hours, filtering out solid materials, drying, and grinding at the rotating speed of 500RPM until the particle size D50 is 100nm to obtain the silanized glass fiber.
The hydrogen peroxide solution: glass fiber: acetone: the ratio of parts by weight of the isobutyl triethoxysilane is 20: 1: 40:8.
The glass fiber has a length of 40 μm and a diameter of 10 μm.
The antioxidant is a mixture of antioxidant 1330, antioxidant 1010 and antioxidant 1035. The antioxidant 1330: antioxidant 1010: the antioxidant 1035 has a weight ratio of 2:1: 2.
The coupling agent is vinyl trimethoxy silane.
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 200 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 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.
Through detection, the novel wormwood PP plastic applied to the toilet lid has the bacteriostasis rate of 98.1% on staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after the PP plastic is sprayed with water and wiped dry, and the operation is repeated for 200 times, the bacteriostasis rate of the PP plastic to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is reduced by less than 3 percent; according to a mildew-proof test, no mildew grows on the surface of the PP plastic toilet cover, and the mildew-proof grade is 0; tensile strength 35MPa, shrinkage 0.66%.
Example 2
A novel folium Artemisiae Argyi PP plastic used for toilet lid is prepared by mixing folium Artemisiae Argyi PP master batch and common PP slice, and making into various plastic products by conventional process (such as injection molding). The addition amount of the wormwood PP master batch is 7% of the total mass of the PP plastic.
The wormwood PP master batch comprises the following raw materials in parts by weight: 95 parts of PP, 10 parts of wormwood functional particles, 18 parts of glass fibers, 3 parts of triphosphite, 3 parts of modified bentonite, 1.3 parts of calcium stearate, 1.5 parts of diphenyl carbonate, 2 parts of tetrabutylammonium hydrogen sulfate, 0.7 part of antioxidant and 2 parts of coupling agent.
The preparation method of the wormwood PP master batch comprises the steps of weighing the raw materials according to the parts by weight, mixing, heating to 120 ℃ under the stirring state of 130RPM, and keeping the temperature for 10 min; and then adding the mixed material into a double-screw extruder, carrying out melt extrusion, and carrying out drawing and granulation to obtain the composite material.
The melt extrusion temperature was 220 ℃ and the twin screw extruder speed was 340 RPM.
The wormwood functional particles are prepared by the following method:
(1) preparing an ultrasonic extracting solution: grinding the mugwort extract to 100 mesh at 240 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 ultrasonic extracting solution of the wormwood extract.
The ultrasonic frequency is 27kHz, and the ultrasonic intensity is 12W/cm2And the ultrasonic power is 400W.
The wormwood extract has the weight loss on drying of 2.6 percent, the heavy metal content of 3.4PPM, the ash content of 1.7 percent, the pesticide residue of 0.91PPM and the mesh number of 70 meshes.
(2) Preparing a molecular nest precursor: adding aminopropyltriethoxysilane and dodecyl trimethyl ammonium bromide into 55% ethanol 3 times by weight, adding the ultrasonic extractive solution of folium Artemisiae Argyi extract, heating to 35 deg.C, and stirring for 4 hr; adding tetraethoxysilane, pressurizing to 2.5MPa, heating to 65 ℃, and carrying out heat preservation and pressure maintaining reaction for 1h under the condition that the stirring speed is 120 RPM; adding ammonia water to adjust the pH value to 8-9, continuously heating to 90 ℃, pressurizing to 4.2MPa, and carrying out heat preservation and pressure maintaining reaction for 9 hours; and preparing the molecular nest precursor.
The aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1:0.2: 1.
(3) Preparing molecular nest particles: heating the molecular nest precursor to 350 ℃, preserving heat, forming for 10 hours, and naturally cooling; cooling to 115 deg.C, soaking in 1.5 times volume of the ultrasonic extractive solution of folium Artemisiae Argyi extract, standing for 3 hr, filtering to obtain solid substance, oven drying at 80 deg.C until ethanol is completely volatilized, and making into molecular nest granule loaded with folium Artemisiae Argyi extract active ingredient, i.e. folium Artemisiae Argyi functional granule.
The molecular nest particles are silica particles.
The particle size range of the wormwood functional particles is 15-20 nm.
The glass fiber is silanized glass fiber. Adding predetermined parts of hydrogen peroxide into glass fibers, stirring at 60RPM, uniformly mixing, heating to 130 ℃, and carrying out heat preservation reaction for 1.2 h; filtering out solid materials, and drying by hot air at 85 ℃ until the moisture content is less than 2%; then adding the mixture into acetone of a predetermined part for uniform dispersion, dripping isobutyl triethoxysilane of a predetermined part at the speed of 5ml/min, heating to 90 ℃, preserving heat for reaction for 2.5 hours, filtering out solid materials, drying, and grinding at the rotating speed of 500RPM until the particle size D50 is 100nm to obtain the silanized glass fiber.
The hydrogen peroxide solution: glass fiber: acetone: the ratio of parts by weight of the isobutyl triethoxysilane is 20: 1: 40:8.
The glass fiber has a length of 40 μm and a diameter of 12 μm.
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 550RPM 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 40RPM for 12 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 35nm 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 antioxidant 1330, antioxidant 1010 and antioxidant 1035. The antioxidant 1330: antioxidant 1010: the antioxidant 1035 has a weight ratio of 2:1: 2.
The coupling agent is a mixture of vinyl trimethoxy silane and gamma-aminopropyl triethoxy silane in equal parts by weight.
Through detection, the novel wormwood PP plastic applied to the toilet lid has 99.4% of bacteriostasis rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after the PP plastic is sprayed with water and wiped dry, and the operation is repeated for 200 times, the bacteriostasis rate of staphylococcus aureus, escherichia coli, candida albicans and other bacteria is reduced by less than 3 percent; according to a mildew-proof test, no mildew grows on the surface of the PP plastic toilet cover, and the mildew-proof grade is 0; the tensile strength is 36.7MPa, and the shrinkage is 0.42%.
Example 3
A novel folium Artemisiae Argyi PP plastic used for toilet lid is prepared by mixing folium Artemisiae Argyi PP master batch and common PP slice, and making into various plastic products by conventional process (such as injection molding). The addition amount of the wormwood PP master batch is 10% of the total mass of the PP plastic.
The wormwood PP master batch comprises the following raw materials in parts by weight: 100 parts of PP, 8 parts of wormwood functional particles, 20 parts of glass fibers, 3 parts of triphosphite, 2 parts of modified bentonite, 1 part of calcium stearate, 1 part of diphenyl carbonate, 3 parts of tetrabutylammonium hydrogen sulfate, 1 part of antioxidant and 5 parts of coupling agent.
The preparation method of the wormwood PP master batch comprises the steps of weighing the raw material components according to the preset parts, mixing, heating to 120 ℃ under the stirring state of 150RPM, and preserving heat for 10 min; and then adding the mixed material into a double-screw extruder, carrying out melt extrusion, and carrying out drawing and granulation to obtain the composite material.
The melt extrusion temperature was 230 ℃ and the twin screw extruder speed was 340 RPM.
The wormwood functional particles are prepared by the following method:
(1) preparing an ultrasonic extracting solution: grinding the wormwood extract to 100 mesh at 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 ultrasonic extracting solution of the wormwood extract.
The ultrasonic frequency is 27kHz, and the ultrasonic intensity is 12W/cm2And the ultrasonic power is 400W.
The wormwood extract has the weight loss on drying of 2.6 percent, the heavy metal content of 3.4PPM, the ash content of 1.7 percent, the pesticide residue of 0.91PPM and the mesh number of 70 meshes.
(2) Preparing a molecular nest precursor: adding aminopropyltriethoxysilane and dodecyl trimethyl ammonium bromide into 60% ethanol with the weight of 3 times of the total weight of the components, heating to 35 ℃, and stirring for 4 hours; adding tetraethoxysilane, pressurizing to 3MPa, heating to 65 ℃, and carrying out heat preservation and pressure maintaining reaction for 1.5h under the condition that the stirring speed is 100 RPM; adding ammonia water to adjust the pH value to 8-9, continuously heating to 100 ℃, pressurizing to 3MPa, and carrying out heat preservation and pressure maintaining reaction for 8 hours; and preparing the molecular nest precursor.
The aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1:0.2: 0.8.
(3) Preparing molecular nest particles: heating the molecular nest precursor to 350 ℃, preserving heat for 8 hours, naturally cooling to room temperature, soaking into the ultrasonic extracting solution of the wormwood extract with the volume of 1.5 times, standing for 3 hours, filtering out solid substances, drying at the low temperature of 80 ℃ until ethanol is completely volatilized, and preparing the molecular nest particles loaded with the active ingredients of the wormwood extract, namely the wormwood functional particles.
The molecular nest particles are silica particles.
The particle size range of the wormwood functional particles is 15-20 nm.
The glass fiber is silanized glass fiber. Adding predetermined parts of hydrogen peroxide into glass fibers, stirring at 50RPM, uniformly mixing, heating to 120 ℃, and carrying out heat preservation reaction for 1 hour; filtering out solid materials, and drying by hot air at 90 ℃ until the moisture content is less than 2%; then adding the mixture into acetone of a predetermined part for uniform dispersion, dripping isobutyl triethoxysilane of a predetermined part at the speed of 5ml/min, heating to 90 ℃, preserving heat for reaction for 3 hours, filtering out solid materials, drying, and grinding at the rotating speed of 500RPM until the particle size D50 is 120nm to obtain the silanized glass fiber.
The hydrogen peroxide solution: glass fiber: acetone: the ratio of parts by weight of the isobutyl triethoxysilane is 20: 1: 40:8.
The glass fiber has a length of 40 μm and a diameter of 12 μm.
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 300 mu m; then putting the ground material into deionized water with 3 times of volume, uniformly dispersing by ultrasonic, and stirring at 40RPM 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 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 antioxidant 1330, antioxidant 1010 and antioxidant 1035. The antioxidant 1330: antioxidant 1010: the antioxidant 1035 has a weight ratio of 2:1: 2.
The coupling agent is gamma-methacryloxypropyltrimethoxysilane.
Through detection, the novel wormwood PP plastic applied to the toilet lid has the bacteriostasis rate of 98.7% on staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after the PP plastic is subjected to water spraying and wiping for 200 times of repeated operation, the bacteriostatic rate of staphylococcus aureus, escherichia coli, candida albicans and other bacteria is reduced by less than 3 percent, and mould does not grow on the surface of the PP plastic toilet cover in a mould proof test, wherein the mould proof grade is 0 grade; the tensile strength is 37MPa, and the shrinkage is 0.51%.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: the steps (2) and (3) in the preparation method of the wormwood functional particles are omitted, and the silica particles are replaced by the commercial bentonite particles with the same particle size specification. The method comprises the specific steps of putting the commercially available bentonite particles into an ultrasonic extracting solution of the wormwood extract, repeatedly shearing, grinding and dispersing for 3 times, and drying to obtain the bentonite particles loaded with the active ingredients of the wormwood extract.
Through detection, the novel wormwood PP plastic applied to the toilet lid in the comparative example has a bacteriostasis rate of 67.2% on staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after the PP plastic is sprayed with water and wiped dry, and the operation is repeated for 200 times, the bacteriostasis rate of the PP plastic on staphylococcus aureus, escherichia coli, candida albicans and other bacteria is reduced by more than 65 percent; according to a mildew-proof test, no mildew grows on the surface of the PP plastic toilet cover, and the mildew-proof grade is grade 2; the tensile strength is 35.4MPa, and the shrinkage is 0.60%.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: replacing the silanized glass fiber with the same physical size specification; the modified bentonite is replaced by the bentonite with the same physical size specification.
Through detection, the novel wormwood PP plastic applied to the toilet lid in the comparative example has 99.1% of bacteriostasis rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after the PP plastic is sprayed with water and wiped dry, and the operation is repeated for 200 times, the bacteriostasis rate of staphylococcus aureus, escherichia coli, candida albicans and other bacteria is reduced by less than 3 percent; according to a mildew-proof test, no mildew grows on the surface of the PP plastic toilet cover, and the mildew-proof grade is 0; tensile strength 29.4MPa, shrinkage 2.63%.
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 (9)
1. A novel wormwood PP plastic applied to a toilet lid is characterized by being prepared by blending wormwood PP master batches and common PP slices;
the addition amount of the wormwood PP master batch is 1-10% of the total mass of the PP plastic;
the wormwood PP master batch comprises the following raw materials in parts by weight: 90-100 parts of PP (polypropylene), 8-10 parts of wormwood functional particles, 15-20 parts of glass fibers, 3-5 parts of triphosphite, 2-3 parts of modified bentonite, 1-2 parts of calcium stearate, 1-2 parts of diphenyl carbonate, 2-3 parts of tetrabutylammonium hydrogen sulfate, 0.5-1 part of antioxidant and 1-5 parts of coupling agent;
the preparation of the wormwood PP master batch comprises the steps of mixing the raw materials in the predetermined parts, carrying out melt extrusion, and then carrying out drawing and granulation to obtain the wormwood PP master batch;
the preparation method of the wormwood functional particles comprises the following steps: preparing a molecular nest precursor and preparing molecular nest particles;
the molecular nest precursor is prepared from aminopropyltriethoxysilane, dodecyl trimethyl ammonium bromide, ethanol, ethyl orthosilicate and ammonia water;
preparing the molecular nest particles, namely heating, molding and cooling the molecular nest precursor, putting the molecular nest precursor into an ultrasonic extracting solution of the wormwood extract, standing, and removing ethanol to obtain the molecular nest particles;
the molecular nest particles are silicon dioxide particles;
the glass fiber is silanized glass fiber.
2. The novel wormwood PP plastic applied to the toilet lid as claimed in claim 1, wherein the molecular nest precursor is prepared under reaction conditions including three times of heat preservation and pressure maintaining reactions;
the first heat preservation and pressure maintaining reaction is carried out in a normal pressure environment, the temperature is heated to 30-35 ℃, and the stirring is carried out for 3-4 hours;
performing the second heat-preservation and pressure-maintaining reaction, pressurizing to 2-3MPa, heating to 60-65 ℃, and performing the heat-preservation and pressure-maintaining reaction for 1-2h under the condition that the stirring speed is 100-120 RPM;
and (3) carrying out heat preservation and pressure maintaining reaction for the third time, pressurizing to 3-5MPa, heating to 80-100 ℃, and carrying out heat preservation and pressure maintaining reaction for 8-9h under the condition that the stirring speed is 100-120 RPM.
3. The novel wormwood PP plastic for the toilet lid as claimed in claim 1, wherein the molecular nest particles are prepared by heating the molecular nest precursor to 300-; soaking in 1.5 times of ultrasonic extractive solution of folium Artemisiae Argyi extract, standing for 2-3 hr, and filtering to obtain solid substance; drying at 80 deg.C until ethanol is completely volatilized to obtain molecular nest granule loaded with folium Artemisiae Argyi extract active component.
4. The novel wormwood PP plastic for the toilet lid as claimed in claim 1, wherein the ultrasonic extract of wormwood is prepared by grinding wormwood to 100 mesh; 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 to prepare an ultrasonic extracting solution of the wormwood extract;
the ultrasonic frequency is 25-27kHz, and the ultrasonic intensity is 12W/cm2And the ultrasonic power is 400W.
5. The novel wormwood PP plastic for the toilet lid as claimed in claim 4, wherein the wormwood extract has a loss on drying of <3%, a heavy metal content of < 5PPM, an ash content of <2.0%, a pesticide residue of < 2PPM, and a mesh size of 60-80 mesh.
6. The novel wormwood PP plastic applied to the toilet lid as claimed in claim 1, wherein the preparation method of the silanized glass fiber comprises the following steps: adding hydrogen peroxide into the glass fiber, uniformly mixing, heating to 120-130 ℃, and carrying out heat preservation reaction for 1-1.5 h; filtering out solid materials, and drying by hot air at 80-90 ℃ until the moisture content is less than 2%; then the mixture is put into acetone for even dispersion, isobutyl triethoxysilane with a predetermined portion is dripped in at the speed of 5ml/min, the temperature is raised to 90 ℃, the reaction is carried out for 2-3h under the condition of heat preservation, solid materials are filtered out, the solid materials are dried and ground until the particle diameter D50 is 100-120nm, and the silanized glass fiber is prepared.
7. The novel wormwood PP plastic applied to the toilet lid as claimed in claim 6, wherein the hydrogen peroxide solution: glass fiber: acetone: the ratio of parts by weight of the isobutyl triethoxysilane is 20: 1: 40: 8;
the glass fiber has a length of 30-40 μm and a diameter of 10-12 μm.
8. The novel wormwood PP plastic for the toilet lid as claimed in claim 1, wherein the modified bentonite is prepared by mixing bentonite with sodium metasilicate pentahydrate, sodium dodecyl sulfate and microcrystalline cellulose, and grinding the mixture until the particle size D50 is 200-300 μm; adding into deionized water with 3 times of volume, and stirring for 10-12 h; filtering out solid materials, and drying until the moisture content is less than 5%; grinding until the particle size D50 is 30-40nm to obtain the modified bentonite.
9. The novel wormwood PP plastic for toilet covers as claimed in claim 8, wherein the bentonite: sodium metasilicate pentahydrate: sodium lauryl sulfate: the weight ratio of the microcrystalline cellulose is 100:6:2: 1.
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