CN112300533B - Wormwood ABS plastic applied to children toys - Google Patents
Wormwood ABS plastic applied to children toys Download PDFInfo
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Abstract
The invention provides a novel wormwood ABS plastic applied to children toys, which is prepared by blending wormwood ABS master batches and common ABS slices; the addition amount of the wormwood ABS master batch is 1-8% of the total mass of the ABS plastic; the wormwood ABS master batch comprises the following raw materials: 90-100 parts of ABS, 15-20 parts of wormwood functional particles, 1-3 parts of compatilizer, 1-2 parts of antioxidant, 1-2 parts of stearic acid, 3-5 parts of epoxidized soybean oil, 2-3 parts of triethyl phosphate and 2-3 parts of modified vinyl silicone oil. The invention has the beneficial effects that: the bacteriostasis rate to staphylococcus aureus, colibacillus, candida albicans and other bacteria is 97.7-99.5%; the tensile strength is 42-48MPa, the elongation at break is 33.5-37.1%, and the bending strength is 89-92MPa.
Description
Technical Field
The invention relates to the field of ABS (acrylonitrile butadiene styrene) plastics, in particular to novel wormwood ABS plastics applied to children toys.
Background
China is a big toy producing country, and more than 70% of toys worldwide are made by China. The main producing areas of the Chinese toys are Guangdong, zhejiang, jiangsu, fujian and Shandong. China is a big country for toy production and export, pays high attention to the quality safety of toy products, closely follows international standards and relevant regulations of various foreign countries and regions, continuously improves the standards of toy products in China, and supervises and checks the detection, authentication, supervision and spot check and the like, and strictly closes the quality safety of toy products. Children are the main consumer group of toys, and unqualified toys can jeopardize the health and life safety of children.
ABS plastics are terpolymers of three monomers of acrylonitrile (A), butadiene (B) and styrene (S), and have the common characteristics of the three components, wherein the acrylonitrile (A) enables the acrylonitrile (A) to resist chemical corrosion and heat and has certain surface hardness, the butadiene (B) enables the acrylonitrile (A) to have high elasticity and toughness, and the styrene (S) enables the styrene (B) to have the processing and forming characteristics of thermoplastic plastics and improve electrical properties. It can be seen that ABS plastic is a tough, hard and rigid material with easily available raw materials, good comprehensive performance, low price and wide application. Due to the excellent comprehensive performance, the ABS plastic is widely applied to children toys and is an important raw material for the children toys.
There are various kinds of microorganisms in nature, and the bacteria seriously endanger the health of human beings and even life. According to statistical data, the number of people killed by bacterial infection is nearly 2000 million every year all over the world, and the serious consequences brought by bacteria improve the attention of people on bacterial control to an unprecedented level. Therefore, research and development on antibacterial ABS plastics applied to children's toys are also becoming more and more widespread.
From the microbiological point of view, the antibacterial concept is distinguished from disinfection in the control of germs, and it does not require immediate killing of microorganisms harmful to human health or living, production environment, but rather focuses on inhibiting the growth and reproduction of bacteria during long-term use, and continuously maintaining the cleanliness and hygiene of the object surface.
In order to improve the antibacterial performance of ABS plastics, it is common in the prior art to add chemical or biological antibacterial agents to ABS plastics to make the plastics have certain antibacterial property, so that the ABS plastics can kill or inhibit bacteria stained on the surface within a certain period of time.
The applicant finds that in the process of processing the ABS plastic product by mixing the chemical or biological antibacterial agent added into the conventional ABS plastic with the plastic raw material, the processing stability of the antibacterial agent is poor, and the antibacterial agent is easily influenced by the process conditions in the processing process, so that the antibacterial performance of different batches of ABS plastics is unstable. Meanwhile, in the daily use process of the prepared ABS plastic, the long-term stability of the chemical or biological antibacterial agent is poor, the ABS plastic is easy to lose efficacy due to the influence of the external environment, and the prepared ABS plastic cannot keep good antibacterial performance for a long time.
Chinese patent No. 103044849A discloses an antibacterial ABS plastic, which is endowed with certain antibacterial property by adding a composite antibacterial agent containing cedar wood oil, chitosan, nano titanium dioxide, nano silver oxide, polyhexamethylene biguanide hydrochloride and N- (trichloromethylthio) phthalimide into the ABS plastic raw material. The defects are that the composite antibacterial agent added in the antibacterial ABS plastic has poor long-term stability, and cannot keep good antibacterial performance for a long time after long-term use and multiple cleaning in the daily use process.
Chinese patent CN104530629A discloses an antibacterial ABS composite material for plastic toys and a preparation method thereof, which also adopts a mode of adding a composite antibacterial agent into ABS plastic raw materials to endow ABS plastic with certain antibacterial performance. The composite antibacterial agent is a mixture of silver-loaded zirconium phosphate and a licorice extract. The defects are that the applicant finds through experiments that the licorice extract in the added composite antibacterial agent is easily influenced by the process conditions in the processing process and hardly plays the due antibacterial performance in the process of mixing with the plastic raw material to prepare the ABS plastic product; the silver-loaded zirconium phosphate in the composite antibacterial agent has poor long-term stability, and cannot keep good antibacterial performance for a long time after long-term use and multiple cleaning in the daily use process.
Furthermore, in the research and development process of the novel wormwood ABS plastic, the applicant also finds that after the wormwood extract or the functional master batch is added into the ABS plastic, the wormwood extract or the functional master batch has poor distribution in the ABS plastic, and the antibacterial effect is not ideal; meanwhile, due physical properties of the ABS plastic are also reduced to a great extent, and excellent physical properties cannot be guaranteed.
Chinese patents CN111087750A and CN111019288A both disclose ABS plastics containing plant extracts, and both adopt specific preparation methods to load one or more of wormwood extract, sarcandra glabra extract, lavender extract, valerian extract and seaweed extract on a carrier, then coat EVA on the outer layer to prepare functional master batch, and then add the functional master batch into ABS plastic raw materials to improve ABS plastic products. However, the functional master batch has the disadvantages that the functional master batch is not well distributed in ABS plastics, so that the antibacterial effect is not ideal; meanwhile, the migration rate of the active ingredients in the functional master batch in the ABS plastic to the surface of the ABS plastic is low, and the plastic product cannot keep good long-term antibacterial performance after being scrubbed, washed and cleaned for many times.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a novel wormwood ABS plastic applied to children toys, which aims to realize the following purposes:
(1) The problem of poor processing stability of the wormwood active ingredient added into the ABS plastic is solved, the influence of a preparation process can be effectively avoided, and the ABS plastic has stable performances such as antibiosis and the like;
(2) The problem that the long-term stability of the wormwood active ingredient added into the ABS plastic is poor is solved, and the wormwood active ingredient can be effectively prevented from being influenced by the external environment, so that the wormwood active ingredient can keep good long-term antibacterial performance and other performances;
(3) The distribution of the wormwood active ingredient added into the ABS plastic is improved, and the influence of the wormwood active ingredient added into the ABS plastic on the physical properties of the ABS plastic is avoided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a novel wormwood ABS plastic for children toys is prepared by blending wormwood ABS master batches and common ABS slices;
the addition amount of the wormwood ABS master batch is 1-8% of the total mass of the ABS plastic;
the wormwood ABS master batch comprises the following raw materials in parts by weight: 90-100 parts of ABS, 15-20 parts of wormwood functional particles, 1-3 parts of compatilizer, 1-2 parts of antioxidant, 1-2 parts of stearic acid, 3-5 parts of epoxidized soybean oil, 2-3 parts of triethyl phosphate and 2-3 parts of modified vinyl silicone oil;
the preparation method of the wormwood ABS master batch comprises the steps of mixing the raw materials in the predetermined parts, carrying out melt extrusion, and carrying out drawing and granulation to obtain the wormwood ABS master batch;
the wormwood functional particles are prepared by the following method:
s101, mixing aminopropyltriethoxysilane, dodecyl trimethyl ammonium bromide, ethanol, tetraethoxysilane and ammonia water, and carrying out heat preservation and pressure maintaining reaction to obtain silicon dioxide gel;
s102, heating the silica gel to 300-350 ℃, preserving heat, forming, naturally cooling to room temperature, soaking into an ultrasonic extracting solution of the wormwood extract, and standing; filtering out solid matter, drying at low temperature until the solvent is completely volatilized, and preparing the molecular nest particles loaded with the active ingredients of the wormwood extract;
s103, mixing the molecular nest particles loaded with the active ingredients of the wormwood extract and silicone powder, putting into a wall material solution containing beta-cyclodextrin, and performing coating treatment by adopting an ultrasonic embedding method to prepare the wormwood functional particles.
Further, in the step S101, the heat-preserving and pressure-maintaining reaction includes a third heat-preserving and pressure-maintaining reaction stage;
in the first heat-preservation and pressure-maintaining reaction stage, heating to 30-35 ℃ in a normal pressure environment, preserving heat, and stirring for 3-4 hours;
in the second heat-preserving and pressure-maintaining reaction stage, pressurizing to 2-3MPa, heating to 60-65 ℃, and carrying out heat-preserving and pressure-maintaining reaction for 1-2h under the condition of stirring rotation speed of 100-120 RPM;
in the third heat-preserving and pressure-maintaining reaction stage, pressurizing to 3-5MPa, heating to 80-100 ℃, and carrying out heat-preserving and pressure-maintaining reaction for 8-9h under the condition of stirring rotation speed of 100-120 RPM;
the aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1.
Further, in the step S102, the heat preservation forming time is 7-10h;
soaking in 1.5 times of the ultrasonic extractive solution of folium Artemisiae Argyi extract, and standing for 2-3 hr;
drying at 80 deg.C until ethanol is completely volatilized to obtain molecular nest granule loaded with folium Artemisiae Argyi extract active ingredient.
Further, the molecular nest particles are silica particles;
the particle size range of the molecular nest particles loaded with the active ingredients of the wormwood extract is 15-20nm.
Further, in the step S103, the wall material solution is a saturated solution of β -cyclodextrin;
maltodextrin, arabic gum and xanthan gum are also dissolved in the wall material solution;
the weight ratio of the beta-cyclodextrin to the maltodextrin to the gum arabic to the xanthan gum is 20;
the coating treatment is carried out, wherein the coating temperature is 30-50 ℃, the coating time is 30-40min, and the ultrasonic power is 300-900W;
the weight ratio of the molecular nest particles to the silicone powder is 2.
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 60-70 deg.C, dispersing, and standing for 1-2 hr; then carrying out ultrasonic extraction for 40-50min, and filtering solid particles to obtain the ultrasonic extracting solution of the wormwood extract.
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 modified vinyl silicone oil is prepared by mixing the vinyl silicone oil with polyethylene glycol in a predetermined part, dropwise adding HCl to adjust the pH value to 2-4, heating to 130-140 ℃, and carrying out heat preservation reaction for 1-2 hours; then adding maleic anhydride, uniformly mixing, heating to 150-160 ℃, and reacting for 1h under the condition of heat preservation; naturally cooling to normal temperature; adjusting the pH value of the material to 7.0-7.5 by adopting 0.5mol/L sodium bicarbonate solution; and preparing the modified vinyl silicone oil.
Further, the vinyl silicone oil: polyethylene glycol: the weight ratio of the maleic anhydride is 100;
the hydroxyl value of the polyethylene glycol ranges from 26 to 30mgKOH/g.
Further, the compatilizer is a mixture of chlorinated polypropylene and maleic anhydride grafted polypropylene; the chlorinated polypropylene: the weight part ratio of the maleic anhydride grafted polypropylene is 3-5;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 1076; the antioxidant 1010: the antioxidant 1076 has a weight ratio of 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) The novel wormwood ABS plastic applied to children toys has good processing stability of wormwood active ingredients, can effectively avoid the influence of the preparation process on the wormwood active ingredients, and has a bacteriostasis rate of 97.7-99.5% on staphylococcus aureus, escherichia coli, candida albicans and other bacteria.
(2) The novel wormwood ABS plastic applied to the children toy can keep good antibacterial performance for a long time; the novel wormwood ABS plastic is soaked in water for 5min, then washed with water, and repeated for 50 times, and the bacteriostasis rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is 91.5-94.2%.
(3) According to the novel wormwood ABS plastic applied to the children toy, the distribution of wormwood active ingredients in the ABS plastic is good, the wormwood active ingredients existing in the ABS plastic can uniformly and stably migrate to the surface of the ABS plastic, and excellent performance can be always kept.
(4) The novel wormwood ABS plastic applied to the children toys has good insect and mosquito expelling functions due to the natural insect and mosquito expelling characteristics of wormwood.
(5) The novel wormwood ABS plastic applied to the children toy has excellent physical properties, and the toy product is firm and durable; the tensile strength is 42-48MPa, the elongation at break is 33.5-37.1%, and the bending strength is 89-92MPa.
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 ABS plastic for children toys is prepared by blending wormwood ABS master batches and common ABS slices and then preparing a novel wormwood ABS plastic product for children toys by a conventional process method (such as an injection molding process). The addition amount of the wormwood ABS master batch is 2% of the total mass of the ABS plastic.
The wormwood ABS master batch comprises the following raw materials in parts by weight: 90 parts of ABS, 15 parts of wormwood functional particles, 1 part of compatilizer, 1 part of antioxidant, 1 part of stearic acid, 3 parts of epoxidized soybean oil, 2 parts of triethyl phosphate and 2 parts of modified vinyl silicone oil.
Wherein the compatilizer is a mixture of chlorinated polypropylene and maleic anhydride grafted polypropylene. The chlorinated polypropylene: the weight ratio of the maleic anhydride grafted polypropylene is 3.
Wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 1076. The antioxidant 1010: the antioxidant 1076 has a weight ratio of 1.
The preparation method of the wormwood ABS master batch comprises the steps of mixing the raw materials in parts by weight, putting the mixture into a double-screw extruder for melt extrusion, and then carrying out stretching and granulation to obtain the wormwood ABS master batch.
Wherein the melt extrusion temperature is 190 ℃ and the rotation speed of the twin-screw extruder is 300RPM.
Further, the wormwood functional particles are prepared by the following method:
(1) Grinding the wormwood extract to 100 mesh at 200 RPM; adding into 8 times volume of anhydrous ethanol, heating to 60 deg.C, dispersing, and standing for 1 hr; then carrying out ultrasonic extraction for 40min, and filtering solid particles to obtain the ultrasonic extracting solution of the wormwood extract.
Wherein the ultrasonic frequency of the ultrasonic extraction is 25kHz, and the ultrasonic intensity is 12W/cm 2 And the ultrasonic power is 400W.
The selected wormwood extract has the weight loss on drying of 2.8%, the heavy metal content of 4.1PPM, the ash content of 1.7%, the pesticide residue of 1.2PPM and the mesh number of 60 meshes.
(2) 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; a silica gel is prepared.
The aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1.
(3) Heating the silica gel loaded with the active ingredients of the wormwood extract to 300 ℃, preserving heat, forming for 7 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 2 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.
The molecular nest particles are silica particles.
The particle size range of the molecular nest particles loaded with the active ingredients of the wormwood extract is 19nm.
(4) Mixing the molecular nest particles loaded with the wormwood extract active ingredient and nano silicone powder, putting into a wall material solution, performing coating treatment by adopting an ultrasonic embedding method to ensure that wall material substances are uniformly coated outside the molecular nest particles loaded with the wormwood extract active ingredient, and filtering, drying and crushing to obtain the wormwood functional particles.
The wall material solution is a saturated solution of beta-cyclodextrin.
Maltodextrin, arabic gum and xanthan gum are also dissolved in the wall material solution.
The weight ratio of the beta-cyclodextrin to the maltodextrin to the gum arabic to the xanthan gum is 20: 2.
The weight ratio of the molecular nest particles to the silicone powder is 2.
The particle size range of the nano-silicone powder is 50nm.
And (3) performing coating treatment, wherein the coating temperature is 30 ℃, the coating time is 30min, and the ultrasonic power is 300W.
The modified vinyl silicone oil is prepared by mixing vinyl silicone oil in a predetermined part with polyethylene glycol, dripping HCl until the PH of the material is 2, heating to 130 ℃, and carrying out heat preservation reaction for 1h; then adding a predetermined part of maleic anhydride, uniformly mixing, heating to 150 ℃, and carrying out heat preservation reaction for 1h; naturally cooling to normal temperature; adjusting the pH value of the material to 7.0 by adopting 0.5mol/L sodium bicarbonate solution; and preparing the modified vinyl silicone oil.
The vinyl silicone oil: polyethylene glycol: the weight parts ratio of the maleic anhydride is 100.
The hydroxyl value of the polyethylene glycol is in a range of 26mgKOH/g.
The novel wormwood ABS plastic applied to the children toy has the bacteriostasis rate of 97.7 percent on staphylococcus aureus, escherichia coli, candida albicans and other bacteria; soaking in water for 5min, washing with water, and repeating soaking and washing for 50 times, wherein the antibacterial rate to Staphylococcus aureus, escherichia coli, candida albicans, etc. is 91.5%; has good insect expelling and mosquito repelling functions; the tensile strength of the steel is 42MPa, the elongation at break is 34.2%, and the bending strength is 89MPa.
Example 2
A novel wormwood ABS plastic for children toys is prepared by blending wormwood ABS master batches and common ABS slices and then preparing a novel wormwood ABS plastic product for children toys by a conventional process method (such as an injection molding process). The addition amount of the wormwood ABS master batch is 6% of the total mass of the ABS plastic.
The wormwood ABS master batch comprises the following raw materials in parts by weight: 95 parts of ABS, 20 parts of wormwood functional particles, 2 parts of compatilizer, 1 part of antioxidant, 1.3 parts of stearic acid, 3.5 parts of epoxidized soybean oil, 2 parts of triethyl phosphate and 3 parts of modified vinyl silicone oil.
Wherein the compatilizer is a mixture of chlorinated polypropylene and maleic anhydride grafted polypropylene. The chlorinated polypropylene: the weight part ratio of the maleic anhydride grafted polypropylene is 4.
Wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 1076. The antioxidant 1010: the antioxidant 1076 has a weight ratio of 1.
The preparation method of the wormwood ABS master batch comprises the steps of mixing the raw materials in parts by weight, putting the mixture into a double-screw extruder for melt extrusion, and then carrying out stretching and granulation to obtain the wormwood ABS master batch.
Wherein the melt extrusion temperature is 195 ℃ and the rotation speed of the twin-screw extruder is 330RPM.
The wormwood functional particles are prepared by the following method:
(1) Grinding the wormwood extract to 100 meshes at 260 RPM; adding into 10 times volume of anhydrous ethanol, heating to 65 deg.C, dispersing, and standing for 1.3 hr; then carrying out ultrasonic extraction for 45min, and filtering solid particles to obtain the ultrasonic extracting solution of the wormwood extract.
Wherein the ultrasonic frequency of the ultrasonic extraction is 27kHz, and the ultrasonic intensity is 12W/cm 2 And the ultrasonic power is 400W.
The selected wormwood extract has the weight loss on drying of 2.8%, the heavy metal content of 4.1PPM, the ash content of 1.7%, the pesticide residue of 1.2PPM and the mesh number of 60 meshes.
(2) Adding aminopropyltriethoxysilane and dodecyl trimethyl ammonium bromide into 2.5 times of 60% ethanol, adding the ultrasonic extractive solution of folium Artemisiae Argyi extract, heating to 35 deg.C, and stirring for 4 hr; adding tetraethoxysilane, pressurizing to 3MPa, heating to 65 ℃, 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 90 ℃, pressurizing to 5MPa, and carrying out heat preservation and pressure maintaining reaction for 8 hours; a silica gel is prepared.
The addition amount of the ultrasonic extracting solution of the wormwood extract is 9 percent of the total mass.
The aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1.
(3) Heating the silica gel loaded with the active ingredients of the wormwood extract to 350 ℃, preserving heat, forming 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.
The molecular nest particles are silica particles.
The particle size range of the molecular nest particles loaded with the active ingredients of the wormwood extract is 15nm.
(4) Mixing the molecular nest particles loaded with the wormwood extract active ingredient and nano silicone powder, putting into a wall material solution, performing coating treatment by adopting an ultrasonic embedding method to ensure that wall material substances are uniformly coated outside the molecular nest particles loaded with the wormwood extract active ingredient, and filtering, drying and crushing to obtain the wormwood functional particles.
The wall material solution is a saturated solution of beta-cyclodextrin.
Maltodextrin, arabic gum and xanthan gum are also dissolved in the wall material solution.
The weight ratio of the beta-cyclodextrin to the maltodextrin to the gum arabic to the xanthan gum is 20.
The weight part ratio of the molecular nest particles to the silicone powder is 2.
The particle size range of the nano-silicone powder is 50nm.
And (3) performing coating treatment, wherein the coating temperature is 40 ℃, the coating time is 40min, and the ultrasonic power is 600W.
The modified vinyl silicone oil is prepared by mixing vinyl silicone oil in a predetermined part with polyethylene glycol, dripping HCl until the PH of the material is 3, heating to 140 ℃, and carrying out heat preservation reaction for 2 hours; then adding maleic anhydride in a predetermined part, uniformly mixing, heating to 155 ℃, and carrying out heat preservation reaction for 1h; naturally cooling to normal temperature; adjusting the pH value of the material to 7.0 by adopting 0.5mol/L sodium bicarbonate solution; and preparing the modified vinyl silicone oil.
The vinyl silicone oil: polyethylene glycol: the weight ratio of the maleic anhydride is 100.
The hydroxyl value of the polyethylene glycol is in a range of 26mgKOH/g.
The novel wormwood ABS plastic applied to the children toy has 99.5% of bacteriostasis rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after soaking in water for 5min, washing with water, and repeating for 50 times, the antibacterial rate to Staphylococcus aureus, escherichia coli, candida albicans, etc. is 94.2%; has good insect expelling and mosquito repelling functions; the tensile strength was 48MPa, the elongation at break was 37.1%, and the bending strength was 92MPa.
Example 3
A novel wormwood ABS plastic for children toys is prepared by blending wormwood ABS master batches and common ABS slices and then preparing a novel wormwood ABS plastic product for children toys by a conventional process method (such as an injection molding process). The addition amount of the wormwood ABS master batch is 8% of the total mass of the ABS plastic.
The wormwood ABS master batch comprises the following raw materials in parts by weight: 100 parts of ABS, 17 parts of wormwood functional particles, 3 parts of compatilizer, 2 parts of antioxidant, 2 parts of stearic acid, 5 parts of epoxidized soybean oil, 3 parts of triethyl phosphate and 2 parts of modified vinyl silicone oil.
The compatilizer is a mixture of chlorinated polypropylene and maleic anhydride grafted polypropylene. The chlorinated polypropylene: the weight ratio of the maleic anhydride grafted polypropylene is 5.
The antioxidant is a mixture of an antioxidant 1010 and an antioxidant 1076. The antioxidant 1010: the antioxidant 1076 has a weight ratio of 1.
The preparation method of the wormwood ABS master batch comprises the steps of mixing the raw materials in parts by weight, putting the mixture into a double-screw extruder for melt extrusion, and then carrying out stretching and granulation to obtain the wormwood ABS master batch.
The melt extrusion temperature was 200 ℃ and the twin screw extruder speed was 350RPM.
The wormwood functional particles are prepared by the following method:
(1) Grinding the wormwood extract to 100 mesh at 300 RPM; adding into 10 times volume of anhydrous ethanol, heating to 70 deg.C, dispersing, and standing for 1.5 hr; then ultrasonic extraction is carried out for 50min, and the ultrasonic extracting solution of the wormwood extract is prepared after solid particles are filtered.
Wherein the ultrasonic frequency of the ultrasonic extraction is 27kHz, and the ultrasonic intensity is 12W/cm 2 And the ultrasonic power is 400W.
The selected wormwood extract has the weight loss on drying of 2.9%, the heavy metal content of 4.8PPM, the ash content of 1.5%, the pesticide residue of 1.8PPM and the mesh number of 80 meshes.
(2) Adding aminopropyltriethoxysilane and dodecyl trimethyl ammonium bromide into 3 times of 60% ethanol by weight, heating to 35 deg.C, and stirring for 4 hr; 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; a silica gel is prepared.
The aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1.
(3) Heating the silica gel loaded with the active ingredients of the wormwood extract to 350 ℃, preserving heat, forming for 10 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 2 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.
The molecular nest particles are silica particles.
The particle size range of the molecular nest particles loaded with the active ingredients of the wormwood extract is 20nm.
(4) Mixing the molecular nest particles loaded with the wormwood extract active ingredient and nano silicone powder, putting into a wall material solution, performing coating treatment by adopting an ultrasonic embedding method to ensure that wall material substances are uniformly coated outside the molecular nest particles loaded with the wormwood extract active ingredient, and filtering, drying and crushing to obtain the wormwood functional particles.
The wall material solution is a saturated solution of beta-cyclodextrin.
Maltodextrin, arabic gum and xanthan gum are also dissolved in the wall material solution.
The weight parts of the beta-cyclodextrin, the maltodextrin, the arabic gum and the xanthan gum are 20.
The weight ratio of the molecular nest particles to the silicone powder is 2.
The particle size range of the nano-silicone powder is 50nm.
And (3) performing coating treatment, wherein the coating temperature is 50 ℃, the coating time is 30min, and the ultrasonic power is 300W.
The modified vinyl silicone oil is prepared by mixing vinyl silicone oil in a predetermined part with polyethylene glycol, dripping HCl until the PH of the material is 4, heating to 140 ℃, and carrying out heat preservation reaction for 2 hours; then adding maleic anhydride in a predetermined part, uniformly mixing, heating to 150 ℃, and carrying out heat preservation reaction for 1h; naturally cooling to normal temperature; adjusting the pH value of the material to 7.5 by adopting 0.5mol/L sodium bicarbonate solution; and preparing the modified vinyl silicone oil.
The vinyl silicone oil: polyethylene glycol: the weight parts ratio of the maleic anhydride is 100.
The hydroxyl value of the polyethylene glycol ranges from 30mgKOH/g.
The novel wormwood ABS plastic applied to the children toys has the bacteriostasis rate of 98.4 percent on bacteria such as staphylococcus aureus, escherichia coli, candida albicans and the like; after soaking in water for 5min, washing with water, and repeating for 50 times, the antibacterial rate to Staphylococcus aureus, escherichia coli, candida albicans, etc. is 93.4%; has good insect expelling and mosquito repelling functions; the tensile strength is 44MPa, the elongation at break is 36.9 percent, and the bending strength is 90MPa.
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.
The novel wormwood ABS plastic applied to the children toys in the comparative example has a bacteriostasis rate of 72.5% on staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after soaking in water for 5min, washing with water, and repeating for 50 times, the antibacterial rate to Staphylococcus aureus, escherichia coli, candida albicans, etc. is 53.7%; it has poor insect expelling and mosquito repelling functions; the tensile strength is 44MPa, the elongation at break is 36.8 percent, and the bending strength is 90MPa.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: the modified vinyl silicone oil is replaced by the vinyl silicone oil.
The novel wormwood ABS plastic applied to the children toys in the comparative example has the bacteriostasis rate of 98.7 percent on staphylococcus aureus, escherichia coli, candida albicans and other bacteria; after soaking in water for 5min, washing with water, and repeating for 50 times, the antibacterial rate to Staphylococcus aureus, escherichia coli, candida albicans, etc. is 85.4%; it has effects in expelling parasite and mosquito; the tensile strength was 37MPa, the elongation at break was 26.9%, and the flexural strength was 77MPa.
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 (4)
1. A wormwood ABS plastic applied to children toys is characterized by being prepared by blending wormwood ABS master batches and common ABS slices;
the addition amount of the wormwood ABS master batch is 1-8% of the total mass of the ABS plastic;
the wormwood ABS master batch comprises the following raw materials in parts by weight: 90-100 parts of ABS, 15-20 parts of wormwood functional particles, 1-3 parts of compatilizer, 1-2 parts of antioxidant, 1-2 parts of stearic acid, 3-5 parts of epoxidized soybean oil, 2-3 parts of triethyl phosphate and 2-3 parts of modified vinyl silicone oil;
the preparation method of the wormwood ABS master batch comprises the steps of mixing the raw materials in parts by weight, performing melt extrusion, and performing stretching and granulation to obtain the wormwood ABS master batch;
the wormwood functional particles are prepared by the following method:
s101, mixing aminopropyltriethoxysilane, dodecyl trimethyl ammonium bromide, ethanol, ethyl orthosilicate and ammonia water, and carrying out heat preservation and pressure maintaining reaction to obtain silicon dioxide gel;
in the step S101, the heat preservation and pressure maintaining reaction comprises a third heat preservation and pressure maintaining reaction stage;
in the first heat-preserving and pressure-maintaining reaction stage, heating to 30-35 ℃ in a normal pressure environment, preserving heat, and stirring for 3-4h;
in the second heat-preserving and pressure-maintaining reaction stage, pressurizing to 2-3MPa, heating to 60-65 ℃, and carrying out heat-preserving and pressure-maintaining reaction for 1-2h under the condition of stirring rotation speed of 100-120 RPM;
in the third heat-preserving and pressure-maintaining reaction stage, pressurizing to 3-5MPa, heating to 80-100 ℃, and carrying out heat-preserving and pressure-maintaining reaction for 8-9h under the condition of stirring rotation speed of 100-120 RPM;
the aminopropyltriethoxysilane: dodecyl trimethyl ammonium bromide: the molar ratio of ethyl orthosilicate is 1;
s102, heating the silica gel to 300-350 ℃, preserving heat, forming, naturally cooling to room temperature, soaking into an ultrasonic extracting solution of the wormwood extract, and standing; filtering out solid substances, drying at low temperature until the solvent is completely volatilized, and preparing molecular nest particles loaded with the active ingredients of the wormwood extract;
in the step S102, the heat preservation forming time is 7-10h; soaking in 1.5 times of the ultrasonic extractive solution of folium Artemisiae Argyi extract, and standing for 2-3 hr; drying at 80 deg.C until ethanol is completely volatilized to obtain molecular nest granule loaded with folium Artemisiae Argyi extract active component;
s103, mixing the molecular nest particles loaded with the active ingredients of the wormwood extract with silicone powder, putting into a wall material solution containing beta-cyclodextrin, and performing coating treatment by adopting an ultrasonic embedding method to prepare wormwood functional particles;
in the step S103, the wall material solution is a saturated solution of β -cyclodextrin;
maltodextrin, arabic gum and xanthan gum are also dissolved in the wall material solution; the weight ratio of the beta-cyclodextrin to the maltodextrin to the gum arabic to the xanthan gum is 20;
the coating treatment is carried out, wherein the coating temperature is 30-50 ℃, the coating time is 30-40min, and the ultrasonic power is 300-900W;
the weight ratio of the molecular nest particles to the silicone powder is 2;
the modified vinyl silicone oil is prepared by mixing vinyl silicone oil in a predetermined part with polyethylene glycol, dropwise adding HCl to adjust the pH value to 2-4, heating to 130-140 ℃, and carrying out heat preservation reaction for 1-2 hours; then adding maleic anhydride, uniformly mixing, heating to 150-160 ℃, and reacting for 1h under the condition of heat preservation; naturally cooling to normal temperature; adjusting the pH of the material to 7.0-7.5 by adopting 0.5mol/L sodium bicarbonate solution; preparing modified vinyl silicone oil;
the vinyl silicone oil: polyethylene glycol: the weight parts ratio of the maleic anhydride is 100;
the hydroxyl value of the polyethylene glycol ranges from 26 to 30mgKOH/g;
the compatilizer is a mixture of chlorinated polypropylene and maleic anhydride grafted polypropylene; the chlorinated polypropylene: the weight part ratio of the maleic anhydride grafted polypropylene is 3-5;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 1076; the antioxidant 1010: the antioxidant 1076 has a weight ratio of 1.
2. The wormwood ABS plastic for children toys as claimed in claim 1, wherein the molecular nest particles are silica particles;
the particle size range of the molecular nest particles loaded with the active ingredients of the wormwood extract is 15-20nm.
3. The mugwort ABS plastic for children toys as claimed in claim 1, wherein the ultrasonic extract of mugwort is prepared by grinding mugwort extract to 100 mesh; adding into 8-10 times volume of anhydrous ethanol, heating to 60-70 deg.C, dispersing, and standing for 1-2 hr; then carrying out ultrasonic extraction for 40-50min, and filtering solid particles to obtain the ultrasonic extracting solution of the wormwood extract.
4. The wormwood ABS plastic for children toys as claimed in claim 3, wherein the wormwood extract has a loss on drying of less than 3%, a heavy metal content of less than 5PPM, an ash content of less than 2.0%, a pesticide residue of less than 2PPM, and a mesh number of 60-80 mesh.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159983A (en) * | 2013-03-13 | 2013-06-19 | 同济大学 | Novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic and method for preparing same |
| CN104530629A (en) * | 2014-11-13 | 2015-04-22 | 苏州威尔德工贸有限公司 | An antibacterial ABS composite material used for plastic toys and a preparing method thereof |
| CN105153630A (en) * | 2015-09-22 | 2015-12-16 | 陆思烨 | Antibacterial masterbatches used for plastic toys and preparation method of antibacterial masterbatches |
| CN108484916A (en) * | 2018-04-18 | 2018-09-04 | 东莞长联新材料科技股份有限公司 | Modified vinyl silicone oil, preparation method and stamp silica gel basis glue and stamp silica gel comprising it |
| CN110254014A (en) * | 2019-03-19 | 2019-09-20 | 三菱电机(中国)有限公司 | A kind of high-efficiency antimicrobial ABS plastic and preparation method thereof |
| CN111019288A (en) * | 2019-12-31 | 2020-04-17 | 百事基材料（青岛）股份有限公司 | Preparation method of ABS (acrylonitrile-butadiene-styrene) composite plastic product capable of reducing loss of plant extract |
-
2020
- 2020-11-14 CN CN202011272806.8A patent/CN112300533B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159983A (en) * | 2013-03-13 | 2013-06-19 | 同济大学 | Novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic and method for preparing same |
| CN104530629A (en) * | 2014-11-13 | 2015-04-22 | 苏州威尔德工贸有限公司 | An antibacterial ABS composite material used for plastic toys and a preparing method thereof |
| CN105153630A (en) * | 2015-09-22 | 2015-12-16 | 陆思烨 | Antibacterial masterbatches used for plastic toys and preparation method of antibacterial masterbatches |
| CN108484916A (en) * | 2018-04-18 | 2018-09-04 | 东莞长联新材料科技股份有限公司 | Modified vinyl silicone oil, preparation method and stamp silica gel basis glue and stamp silica gel comprising it |
| CN110254014A (en) * | 2019-03-19 | 2019-09-20 | 三菱电机(中国)有限公司 | A kind of high-efficiency antimicrobial ABS plastic and preparation method thereof |
| CN111019288A (en) * | 2019-12-31 | 2020-04-17 | 百事基材料（青岛）股份有限公司 | Preparation method of ABS (acrylonitrile-butadiene-styrene) composite plastic product capable of reducing loss of plant extract |
Non-Patent Citations (1)
| Title |
|---|
| 氨基官能化介孔二氧化硅的制备和表征;钟莉等;《天津农学院学报》;20160630;第23卷(第2期);第11-14页 * |
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