CN111763391A - Antibacterial toy plastic and preparation method thereof - Google Patents
Antibacterial toy plastic and preparation method thereof Download PDFInfo
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Abstract
The invention provides an antibacterial toy plastic and a preparation method thereof. The antibacterial toy plastic is composed of the following raw materials: PVC, ABS, plant antioxidant, plastic antibacterial agent, tributyl citrate and calcium stearate. The antibacterial toy plastic disclosed by the invention has good antibacterial performance and oxidation resistance.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to antibacterial toy plastic and a preparation method thereof.
Background
Toys are one of the most commonly used items for children during their growth, and close contact between toys and children occurs almost every day. The plastic is a plastic material formed by processing and molding or a rigid material formed by curing and crosslinking by taking a high molecular weight synthetic resin as a main component and adding proper additives such as a plasticizer, a stabilizer, an antioxidant, a flame retardant, a colorant and the like. The plastic is the most common material for toy application because of its advantages of easy processing and forming, light weight, and firmness.
However, many existing plastic toys have the defects of poor falling resistance, poor wear resistance, easy oxidation and discoloration, easy generation of bacterial breeding and the like, and the service life and the experience feeling of the toys are seriously influenced. Therefore, it is very important to improve the antibacterial property and the oxidation resistance of the toy plastic while ensuring the safety of the toy plastic, which makes the toy plastic safer to use and more suitable for children.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an antibacterial toy plastic which has safety, antibacterial property and good comprehensive performance.
The invention is realized by the following technical scheme:
an antibacterial toy plastic is composed of the following raw materials: 50-70 parts of PVC, 30-50 parts of ABS, 0.1-1.0 part of plant antioxidant, 0.1-2.0 parts of plastic antibacterial agent, 0.1-1 part of tributyl citrate and 1-5 parts of calcium stearate.
The plant antioxidant adopted by the invention is safe, nontoxic and good in oxidation resistance, and is very suitable to be used as an additive of toy plastics.
Preferably, the plant antioxidant is pomegranate seed antioxidant and/or grape seed extract. Further preferably, the plant antioxidant is a mixture of pomegranate seed antioxidant and grape seed extract in a mass ratio of (1-3) to 1.
The pomegranate seed antioxidant is prepared by the following method: pulverizing cleaned and dried semen Granati, and sieving with 50-150 mesh sieve to obtain semen Granati powder; adding pomegranate seed powder into 70-80 wt% ethanol water solution, and ultrasonically stirring for 10-30min, wherein the mass ratio of the pomegranate seed powder to the 70-80 wt% ethanol water solution is 1 (30-50), the ultrasonic frequency is 20-30kHz, the ultrasonic power is 500-1000W, and the stirring speed is 100-200 rpm; heating to 50-80 deg.C, and stirring at 100-200rpm for 20-50 min; filtering, concentrating the filtrate under reduced pressure, and drying at 60-80 deg.C for 10-20 h.
The plastic antibacterial agent takes a porous bead body formed by cross-linking reaction of polystyrene butadiene copolymer and chloromethyl styrene and pore-forming as a carrier, and loaded nano zinc oxide and nano titanium dioxide as active components; the content of the nano zinc oxide is 0.5-2 wt%; the content of the nano titanium dioxide is 0.1-1 wt%. As a further improvement of the invention, the porous bead body is a porous channel microsphere with 1200-1500 nm; the particle size of the nano zinc oxide is 10-50 nm; the particle size of the nano titanium dioxide is 10-80 nm.
The preparation method of the plastic antibacterial agent comprises the following steps:
s1, dissolving a proper amount of polystyrene butadiene copolymer and chloromethyl styrene in a first solvent, adding a proper amount of chloromethyl methyl ether and triethylamine, fully and uniformly stirring, introducing nitrogen, adding a catalyst, heating to 70-100 ℃, and carrying out ultrasonic stirring reaction for a period of time to form solid microspheres;
s2, adding the solid microspheres obtained in the step S1 into a second solvent, adding a proper amount of NaCl and glycerol, fully stirring, reacting for a period of time to fully pore-form the microspheres, and sequentially performing absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying on the obtained beads to obtain porous beads;
s3, preparing the porous beads obtained in the step S2 into aqueous suspension, adding a certain amount of zinc chloride aqueous solution, carrying out ultrasonic treatment for more than 0.5h under a dark condition, adding a proper amount of ammonia aqueous solution while stirring, continuing to react for a period of time, adding tetrabutyl titanate, fully stirring and reacting, and finally sequentially carrying out anhydrous ethanol and water washing, centrifugal separation, vacuum drying and heating baking on the product to obtain the plastic antibacterial agent.
As a further improvement of the invention, the first solvent is one or a mixture of several of dichloromethane, trichloromethane, acetonitrile, acetone and tetrahydrofuran; the second solvent is one or more of water, an ethanol-water mixed solution, a tetrahydrofuran-water mixed solution, a methanol-water mixed solution and an acetone-water mixed solution, and the water content of the ethanol-water mixed solution, the tetrahydrofuran-water mixed solution, the methanol-water mixed solution and the acetone-water mixed solution is not less than 50 wt%.
As a further improvement of the invention, the catalyst is one or a mixture of several of anhydrous zinc chloride, stannic chloride, ferric trichloride and aluminum trichloride.
As a further improvement of the invention, the stirring rotating speed is 1000-1500 r/min.
As a further improvement of the present invention, in step S1, the polystyrene-butadiene copolymer is 50 to 100 parts by weight, chloromethyl styrene is 30 to 50 parts by weight, chloromethyl methyl ether is 1 to 5 parts by weight, triethylamine is 5 to 10 parts by weight, and catalyst is 0.1 to 1 part by weight; in the step S2, 5-10 parts by weight of NaCl and 5-15 parts by weight of glycerol are added; in the step S3, the zinc chloride aqueous solution accounts for 20-70 parts by weight, and the zinc chloride content in the zinc chloride aqueous solution is 5-10 wt%; 5-10 parts of ammonia water and NH in the ammonia water3The content of (B) is 15-30 wt%, and the weight of tetrabutyl titanate is 0.5-2 parts.
As a further improvement of the invention, the porous beads in step S3 are formulated in an aqueous suspension of 0.5-1 mg/mL.
As a further improvement of the invention, the method comprises the following steps:
s1, dissolving 50-100 parts by weight of polystyrene butadiene copolymer and 30-50 parts by weight of chloromethyl styrene in 300 parts by weight of 100-one-phase solvent, adding 1-5 parts by weight of chloromethyl methyl ether and 5-10 parts by weight of triethylamine, uniformly stirring, introducing nitrogen, adding 0.1-1 part by weight of catalyst, heating to 70-100 ℃, and carrying out ultrasonic stirring reaction for 8-10 hours to form solid microspheres;
s2, adding the solid microspheres obtained in the step S1 into 50-150 parts by weight of a second solvent, adding 5-10 parts by weight of NaCl and 5-15 parts by weight of glycerol, fully stirring, reacting for 2-4h, fully pore-forming, and sequentially carrying out absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying on the obtained beads to obtain porous beads;
s3, preparing the porous beads obtained in the step S2 into 0.5-1mg/mL aqueous suspension, adding 20-70 parts by weight of 5-10 wt% zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.5-5h under a dark condition, adding 5-10 parts by weight of 15-30 wt% ammonia aqueous solution while stirring, continuing to react for 0.5-1h, adding 0.5-2 parts by weight of tetrabutyl titanate, fully stirring and reacting for 1-3h, finally, sequentially carrying out anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the product, heating to 200-220 ℃ and baking for 1-2h to obtain the plastic antibacterial agent.
Preferably, the preparation method of the antibacterial toy plastic comprises the following steps: weighing 50-70 parts by weight of PVC, 30-50 parts by weight of ABS, 0.1-1.0 part by weight of plant antioxidant, 0.1-2.0 parts by weight of plastic antibacterial agent, 0.1-1 part by weight of tributyl citrate and 1-5 parts by weight of calcium stearate, uniformly mixing, and blending at 80-100 ℃ for 10-30 min; sending the mixture into an extruder for extrusion granulation, wherein the temperature of a material cylinder is 150-; and (5) injection molding.
The invention has the beneficial effects that: the antibacterial toy plastic disclosed by the invention has good antibacterial performance and ageing resistance. The prepared porous bead plastic antibacterial agent has a very large comparative area, a plurality of pore channels are formed in beads through a pore-foaming agent, the beads are soaked in a zinc chloride solution, zinc chloride enters the pore channels and reacts with ammonia water to generate zinc hydroxide precipitate, tetrabutyl titanate enters the pore channels to be hydrolyzed to generate nano titanium dioxide, the obtained porous beads are further roasted, and the zinc hydroxide is decomposed to obtain nano zinc oxide, so that the porous bead antibacterial agent loaded with the nano zinc oxide and the nano titanium dioxide is obtained;
polystyrene butadiene copolymer and chloromethyl styrene take place the cross-linking reaction of friendship under the influence of catalyst, under the participation of chloromethyl methyl ether of chloromethylation reagent, produce methylene bridge, thus achieve the goal of cross-linking balling, the spheroid formed has very large specific surface area, further through salting out function and filler effect, under NaCl and glycerin effects, form very many pore canals, further increase the specific surface area of the spheroid, facilitate the later stage nanometer zinc oxide and deposition of nanometer titanium dioxide, achieve the highly loaded antiseptic spheroid;
the porous bead plastic antibacterial agent has the characteristics of high stability of inorganic matters and easy dispersibility of the organic matters, and is easy to load antibacterial active ingredients with high load;
the antibacterial active ingredients in the porous bead plastic antibacterial agent loaded with the nano zinc oxide and the nano titanium dioxide exist in a molecular state, and have the advantages of safety, low toxicity and good stability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Pomegranate seeds, produced from the spring of the river.
PVC, trade mark:
3201-90NT, Tenoerio Paeus, USA, available from Dongguan Ming quan engineering plastics, Inc.
ABS, brand:
GP-22, the benzene Collar of Enlisha helveticus, available from Toguan Jingchen plastics, Inc.
Polystyrene butadiene copolymer CAS number 9003-55-8; chloromethyl styrene CAS number 1592-20-7; chloromethyl methyl ether CAS number 107-30-2; triethylamine CAS number 121-44-8; anhydrous zinc chloride CAS number 7646-85-7; tetrabutyl titanate CAS number 5593-70-4; ferric trichloride CAS number 7705-08-0; stannic chloride CAS number 7646-78-8; antioxidant 1076CAS number 134701-20-5; tributyl citrate CAS No. 77-94-1, calcium stearate CAS No. 1592-23-0. All purchased from the national medicine group.
Example 1
An antibacterial toy plastic is composed of the following raw materials: 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate.
The preparation method of the antibacterial toy plastic comprises the following steps: weighing 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate, uniformly mixing, and blending for 15min at 85 ℃; feeding the mixture into an extruder to extrude and granulate, wherein the temperature of a charging barrel is 180 ℃, and the rotating speed of a screw is 20 rpm; and (5) injection molding.
The plant antioxidant is a pomegranate seed antioxidant, and the pomegranate seed antioxidant is prepared by the following method: crushing the cleaned and dried pomegranate seeds and sieving the crushed pomegranate seeds with a 100-mesh sieve to obtain pomegranate seed powder; adding pomegranate seed powder into a 73 wt% ethanol aqueous solution, and ultrasonically stirring for 20min, wherein the mass ratio of the pomegranate seed powder to the 73 wt% ethanol aqueous solution is 1:39, the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 150 rpm; heating to 60 ℃, and continuing stirring for 30min at the stirring speed of 150 rpm; filtering, concentrating the filtrate under reduced pressure, and drying at 65 deg.C for 12 h.
The preparation method of the plastic antibacterial agent comprises the following steps:
s1, dissolving 70g of polystyrene butadiene copolymer and 40g of chloromethylstyrene in 200g of trichloromethane, adding 3g of chloromethylmethyl ether and 7g of triethylamine, uniformly stirring for 10min at the stirring speed of 1250r/min, introducing nitrogen, adding 0.5g of stannic chloride, heating to 85 ℃, and carrying out ultrasonic stirring reaction for 9h to obtain 108g of solid microspheres, wherein the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 1250 r/min;
s2, adding all the solid microspheres obtained in the step S1 into 100g of acetone-water mixed solution, wherein the acetone-water mixed solution is mixed solution of acetone and water according to a mass ratio of 45: 55; adding 7g of NaCl and 10g of glycerol, stirring for reaction for 3 hours at the stirring speed of 1250r/min to fully pore-form the beads, and sequentially performing anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the beads to obtain 102g of porous beads;
s3, preparing all the porous beads obtained in the step S2 into 0.75mg/mL aqueous suspension, adding 50g of 7 wt% zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.6h under the condition of keeping out of the sun, wherein the ultrasonic frequency is 25kHz and the ultrasonic power is 800W, adding 7g of 22 wt% ammonia water solution under the stirring of 1250r/min, continuing to react for 1h, adding 1.2g of tetrabutyl titanate, carrying out stirring reaction for 2h at 1250r/min, and finally heating the product to 210 ℃ for baking for 2h after absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying are sequentially carried out on the product to obtain the plastic antibacterial agent. The plastic antibacterial agent is 1200-1500nm porous microspheres.
Comparative example 1
An antibacterial toy plastic is composed of the following raw materials: 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate.
The preparation method of the antibacterial toy plastic comprises the following steps: weighing 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate, uniformly mixing, and blending for 15min at 85 ℃; feeding the mixture into an extruder to extrude and granulate, wherein the temperature of a charging barrel is 180 ℃, and the rotating speed of a screw is 20 rpm; and (5) injection molding.
The plant antioxidant is a pomegranate seed antioxidant, and the pomegranate seed antioxidant is prepared by the following method: crushing the cleaned and dried pomegranate seeds and sieving the crushed pomegranate seeds with a 100-mesh sieve to obtain pomegranate seed powder; adding pomegranate seed powder into a 73 wt% ethanol aqueous solution, and ultrasonically stirring for 20min, wherein the mass ratio of the pomegranate seed powder to the 73 wt% ethanol aqueous solution is 1:39, the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 150 rpm; heating to 60 ℃, and continuing stirring for 30min at the stirring speed of 150 rpm; filtering, concentrating the filtrate under reduced pressure, and drying at 65 deg.C for 12 h.
The preparation method of the plastic antibacterial agent comprises the following steps:
compared to example 1, the solid microspheres were replaced by low cross-linked polystyrene beads (available from Shanghai Biotech, Inc., with a diameter of less than 0.1 μm), all other conditions being unchanged.
S1, adding 108g of low-crosslinked polystyrene beads into 100g of acetone-water mixed solution, wherein the acetone-water mixed solution is mixed solution of acetone and water according to a mass ratio of 45: 55; adding 7g of NaCl and 10g of glycerol, stirring for reaction for 3 hours at the stirring speed of 1250r/min to fully pore-form the beads, and sequentially performing anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the beads to obtain 102g of porous beads;
s2, preparing all the porous beads obtained in the step S1 into 0.75mg/mL aqueous suspension, adding 50g of 7 wt% zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.6h under the condition of keeping out of the sun, wherein the ultrasonic frequency is 25kHz and the ultrasonic power is 800W, adding 7g of 22 wt% ammonia water solution under the stirring of 1250r/min, continuing to react for 1h, adding 1.2g of tetrabutyl titanate, carrying out stirring reaction for 2h at 1250r/min, and finally heating the product to 210 ℃ for baking for 2h after absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying are sequentially carried out on the product to obtain the plastic antibacterial agent. The plastic antibacterial agent is 1200-1500nm porous microspheres.
Comparative example 2
An antibacterial toy plastic is composed of the following raw materials: 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate.
The preparation method of the antibacterial toy plastic comprises the following steps: weighing 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate, uniformly mixing, and blending for 15min at 85 ℃; feeding the mixture into an extruder to extrude and granulate, wherein the temperature of a charging barrel is 180 ℃, and the rotating speed of a screw is 20 rpm; and (5) injection molding.
The plant antioxidant is a pomegranate seed antioxidant, and the pomegranate seed antioxidant is prepared by the following method: crushing the cleaned and dried pomegranate seeds and sieving the crushed pomegranate seeds with a 100-mesh sieve to obtain pomegranate seed powder; adding pomegranate seed powder into a 73 wt% ethanol aqueous solution, and ultrasonically stirring for 20min, wherein the mass ratio of the pomegranate seed powder to the 73 wt% ethanol aqueous solution is 1:39, the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 150 rpm; heating to 60 ℃, and continuing stirring for 30min at the stirring speed of 150 rpm; filtering, concentrating the filtrate under reduced pressure, and drying at 65 deg.C for 12 h.
The preparation method of the plastic antibacterial agent comprises the following steps:
compared with example 1, the porous beads are replaced by molecular sieves (ZSM-35 molecular sieve, diameter of 1 μm, pore diameter of 0.6nm, available from Shanghai Han chemical technology Co., Ltd.), and other conditions are not changed.
Preparing 102g of molecular sieve into 0.75mg/mL of water suspension, adding 50g of 7 wt% of zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.6h under the condition of keeping out of the sun, wherein the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, then adding 7g of 22 wt% ammonia water solution under stirring at 1250r/min, continuing to react for 1h, then adding 1.2g of tetrabutyl titanate, stirring at 1250r/min for reacting for 2h, finally, sequentially carrying out absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying on the product, and heating to 210 ℃ for baking for 2h to obtain the plastic antibacterial agent. The plastic antibacterial agent is 1200-1500nm porous microspheres.
Comparative example 3
An antibacterial toy plastic is composed of the following raw materials: 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate.
The preparation method of the antibacterial toy plastic comprises the following steps: weighing 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate, uniformly mixing, and blending for 15min at 85 ℃; feeding the mixture into an extruder to extrude and granulate, wherein the temperature of a charging barrel is 180 ℃, and the rotating speed of a screw is 20 rpm; and (5) injection molding.
The plant antioxidant is a pomegranate seed antioxidant, and the pomegranate seed antioxidant is prepared by the following method: crushing the cleaned and dried pomegranate seeds and sieving the crushed pomegranate seeds with a 100-mesh sieve to obtain pomegranate seed powder; adding pomegranate seed powder into a 73 wt% ethanol aqueous solution, and ultrasonically stirring for 20min, wherein the mass ratio of the pomegranate seed powder to the 73 wt% ethanol aqueous solution is 1:39, the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 150 rpm; heating to 60 ℃, and continuing stirring for 30min at the stirring speed of 150 rpm; filtering, concentrating the filtrate under reduced pressure, and drying at 65 deg.C for 12 h.
The preparation method of the plastic antibacterial agent comprises the following steps:
s1, dissolving 70g of polystyrene butadiene copolymer and 40g of chloromethylstyrene in 200g of trichloromethane, adding 3g of chloromethylmethyl ether and 7g of triethylamine, uniformly stirring for 10min at the stirring speed of 1250r/min, introducing nitrogen, adding 0.5g of stannic chloride, heating to 85 ℃, and carrying out ultrasonic stirring reaction for 9h to obtain 108g of solid microspheres, wherein the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 1250 r/min;
s2, adding all the solid microspheres obtained in the step S1 into 100g of acetone-water mixed solution, wherein the acetone-water mixed solution is mixed solution of acetone and water according to a mass ratio of 45: 55; adding 7g of NaCl and 10g of glycerol, stirring for reaction for 3 hours at the stirring speed of 1250r/min to fully pore-form the beads, and sequentially performing anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the beads to obtain 102g of porous beads;
s3, preparing all the porous beads obtained in the step S2 into 0.75mg/mL aqueous suspension, adding 67g of 7 wt% zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.6h under the condition of keeping out of the sun, wherein the ultrasonic frequency is 25kHz and the ultrasonic power is 800W, then adding 7g of 22 wt% ammonia water solution while stirring at 1250r/min, continuing to react for 3h, and finally heating to 210 ℃ for baking for 2h after sequentially carrying out absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying on the product to obtain the plastic antibacterial agent. The plastic antibacterial agent is 1200-1500nm porous microspheres.
Comparative example 4
An antibacterial toy plastic is composed of the following raw materials: 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate.
The preparation method of the antibacterial toy plastic comprises the following steps: weighing 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of plant antioxidant, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate, uniformly mixing, and blending for 15min at 85 ℃; feeding the mixture into an extruder to extrude and granulate, wherein the temperature of a charging barrel is 180 ℃, and the rotating speed of a screw is 20 rpm; and (5) injection molding.
The plant antioxidant is a pomegranate seed antioxidant, and the pomegranate seed antioxidant is prepared by the following method: crushing the cleaned and dried pomegranate seeds and sieving the crushed pomegranate seeds with a 100-mesh sieve to obtain pomegranate seed powder; adding pomegranate seed powder into a 73 wt% ethanol aqueous solution, and ultrasonically stirring for 20min, wherein the mass ratio of the pomegranate seed powder to the 73 wt% ethanol aqueous solution is 1:39, the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 150 rpm; heating to 60 ℃, and continuing stirring for 30min at the stirring speed of 150 rpm; filtering, concentrating the filtrate under reduced pressure, and drying at 65 deg.C for 12 h.
The preparation method of the plastic antibacterial agent comprises the following steps:
s1, dissolving 70g of polystyrene butadiene copolymer and 40g of chloromethylstyrene in 200g of trichloromethane, adding 3g of chloromethylmethyl ether and 7g of triethylamine, uniformly stirring for 10min at the stirring speed of 1250r/min, introducing nitrogen, adding 0.5g of stannic chloride, heating to 85 ℃, and carrying out ultrasonic stirring reaction for 9h to obtain 108g of solid microspheres, wherein the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 1250 r/min;
s2, adding all the solid microspheres obtained in the step S1 into 100g of acetone-water mixed solution, wherein the acetone-water mixed solution is mixed solution of acetone and water according to a mass ratio of 45: 55; adding 7g of NaCl and 10g of glycerol, stirring for reaction for 3 hours at the stirring speed of 1250r/min to fully pore-form the beads, and sequentially performing anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the beads to obtain 102g of porous beads;
s3, preparing all the porous beads obtained in the step S2 into 0.75mg/mL aqueous suspension, then adding 4.7g of tetrabutyl titanate, stirring and reacting for 3h at 1250r/min, finally, sequentially carrying out absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying on the product, and heating to 210 ℃ for 2h to obtain the plastic antibacterial agent. The plastic antibacterial agent is 1200-1500nm porous microspheres.
Comparative example 5
An antibacterial toy plastic is composed of the following raw materials: 60.7 parts by weight of PVC, 36 parts by weight of ABS, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate.
The preparation method of the antibacterial toy plastic comprises the following steps: weighing 60.7 parts by weight of PVC, 36 parts by weight of ABS, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate, uniformly mixing, and blending for 15min at 85 ℃; feeding the mixture into an extruder to extrude and granulate, wherein the temperature of a charging barrel is 180 ℃, and the rotating speed of a screw is 20 rpm; and (5) injection molding.
The preparation method of the plastic antibacterial agent comprises the following steps:
s1, dissolving 70g of polystyrene butadiene copolymer and 40g of chloromethylstyrene in 200g of trichloromethane, adding 3g of chloromethylmethyl ether and 7g of triethylamine, uniformly stirring for 10min at the stirring speed of 1250r/min, introducing nitrogen, adding 0.5g of stannic chloride, heating to 85 ℃, and carrying out ultrasonic stirring reaction for 9h to obtain 108g of solid microspheres, wherein the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 1250 r/min;
s2, adding all the solid microspheres obtained in the step S1 into 100g of acetone-water mixed solution, wherein the acetone-water mixed solution is mixed solution of acetone and water according to a mass ratio of 45: 55; adding 7g of NaCl and 10g of glycerol, stirring for reaction for 3 hours at the stirring speed of 1250r/min to fully pore-form the beads, and sequentially performing anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the beads to obtain 102g of porous beads;
s3, preparing all the porous beads obtained in the step S2 into 0.75mg/mL aqueous suspension, adding 50g of 7 wt% zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.6h under the condition of keeping out of the sun, wherein the ultrasonic frequency is 25kHz and the ultrasonic power is 800W, adding 7g of 22 wt% ammonia water solution under the stirring of 1250r/min, continuing to react for 1h, adding 1.2g of tetrabutyl titanate, carrying out stirring reaction for 2h at 1250r/min, and finally heating the product to 210 ℃ for baking for 2h after absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying are sequentially carried out on the product to obtain the plastic antibacterial agent. The plastic antibacterial agent is 1200-1500nm porous microspheres.
Comparative example 6
An antibacterial toy plastic is composed of the following raw materials: 60 parts of PVC, 36 parts of ABS, 0.7 part of antioxidant 1076, 1.2 parts of plastic antibacterial agent, 0.1 part of tributyl citrate and 4 parts of calcium stearate. The antioxidant 1076 of this comparative example was purchased from Hefeijian chemical Co., Ltd, CAS No.: 2082-79-3.
The preparation method of the antibacterial toy plastic comprises the following steps: weighing 60 parts by weight of PVC, 36 parts by weight of ABS, 0.7 part by weight of antioxidant 1076, 1.2 parts by weight of plastic antibacterial agent, 0.1 part by weight of tributyl citrate and 4 parts by weight of calcium stearate, uniformly mixing, and blending for 15min at 85 ℃; feeding the mixture into an extruder to extrude and granulate, wherein the temperature of a charging barrel is 180 ℃, and the rotating speed of a screw is 20 rpm; and (5) injection molding.
The preparation method of the plastic antibacterial agent comprises the following steps:
s1, dissolving 70g of polystyrene butadiene copolymer and 40g of chloromethylstyrene in 200g of trichloromethane, adding 3g of chloromethylmethyl ether and 7g of triethylamine, uniformly stirring for 10min at the stirring speed of 1250r/min, introducing nitrogen, adding 0.5g of stannic chloride, heating to 85 ℃, and carrying out ultrasonic stirring reaction for 9h to obtain 108g of solid microspheres, wherein the ultrasonic frequency is 25kHz, the ultrasonic power is 800W, and the stirring speed is 1250 r/min;
s2, adding all the solid microspheres obtained in the step S1 into 100g of acetone-water mixed solution, wherein the acetone-water mixed solution is mixed solution of acetone and water according to a mass ratio of 45: 55; adding 7g of NaCl and 10g of glycerol, stirring for reaction for 3 hours at the stirring speed of 1250r/min to fully pore-form the beads, and sequentially performing anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the beads to obtain 102g of porous beads;
s3, preparing all the porous beads obtained in the step S2 into 0.75mg/mL aqueous suspension, adding 50g of 7 wt% zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.6h under the condition of keeping out of the sun, wherein the ultrasonic frequency is 25kHz and the ultrasonic power is 800W, adding 7g of 22 wt% ammonia water solution under the stirring of 1250r/min, continuing to react for 1h, adding 1.2g of tetrabutyl titanate, carrying out stirring reaction for 2h at 1250r/min, and finally heating the product to 210 ℃ for baking for 2h after absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying are sequentially carried out on the product to obtain the plastic antibacterial agent. The plastic antibacterial agent is 1200-1500nm porous microspheres.
Example 2
Compared with example 1, the plant antioxidant is grape seed extract, and other conditions are not changed.
The grape seed extract of this example was purchased from Jiangsu Aikang biomedical research and development Co., CAS No.: 84929-27-1.
Example 3
Compared with the example 1, the plant antioxidant is a mixture of pomegranate seed antioxidant and grape seed extract according to the mass ratio of 2:1, and other conditions are not changed.
The grape seed extract of this example was purchased from Jiangsu Aikang biomedical research and development Co., CAS No.: 84929-27-1.
Test example 1
And (3) testing the antibacterial performance by a film pasting method according to a test method 1 of the standard GB21551.2-2010, wherein the bacteria for detection: escherichia coli AS 1.90; staphylococcus aureus AS 1.89; each example and comparative example was tested in parallel for 5 and averaged.
TABLE 1 antibacterial Properties of antibacterial toy plastics
| Antibacterial ratio (%) of Escherichia coli | Staphylococcus aureus antibacterial ratio (%) | |
| Example 1 | 99.6 | 99.8 |
| Comparative example 1 | 81.5 | 82.9 |
| Comparative example 2 | 84.1 | 85.7 |
| Comparative example 3 | 88.2 | 90.0 |
| Comparative example 4 | 86.4 | 87.3 |
Test example 2
Artificial accelerated ageing tests (90 ℃, 500h) were carried out according to method B of standard GB/T7141-2008, 5 of each example and comparative example were tested in parallel and the average was taken.
Tensile strength retention (%) - (D-E)/Dx100
Wherein, D: tensile strength before artificial accelerated aging; e: artificially accelerated tensile strength after aging.
TABLE 2 anti-aging Properties of antibacterial toy plastics
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. An antibacterial toy plastic is characterized by comprising the following raw materials: PVC, ABS, plant antioxidant, plastic antibacterial agent, tributyl citrate and calcium stearate.
2. The antibacterial toy plastic of claim 1, which is prepared from the following raw materials: 50-70 parts of PVC, 30-50 parts of ABS, 0.1-1.0 part of plant antioxidant, 0.1-2.0 parts of plastic antibacterial agent, 0.1-1 part of tributyl citrate and 1-5 parts of calcium stearate.
3. The antibacterial toy plastic of claim 2, wherein the plastic antibacterial agent takes porous beads formed by crosslinking reaction of polystyrene butadiene copolymer and chloromethyl styrene and pore-forming as carriers, and loaded nano zinc oxide and nano titanium dioxide as active components.
4. The antibacterial toy plastic as claimed in claim 3, wherein the porous beads are 1200-1500nm porous microspheres.
5. The antibacterial toy plastic of claim 2, wherein the preparation method of the plastic antibacterial agent comprises the following steps:
s1, dissolving 50-100 parts by weight of polystyrene butadiene copolymer and 30-50 parts by weight of chloromethyl styrene in a first solvent, adding 1-5 parts by weight of chloromethyl methyl ether and 5-10 parts by weight of triethylamine, fully and uniformly stirring, introducing nitrogen, adding 0.1-1 part by weight of catalyst, heating to 70-100 ℃, and carrying out ultrasonic stirring reaction for 8-10 hours to form solid microspheres;
s2, adding the solid microspheres obtained in the step S1 into a second solvent, adding 5-10 parts by weight of NaCl and 5-15 parts by weight of glycerol, fully stirring, reacting for 2-4h to fully pore-form, and sequentially performing absolute ethyl alcohol and water washing, centrifugal separation and vacuum drying on the obtained beads to obtain porous beads;
s3, preparing the porous beads obtained in the step S2 into 0.5-1mg/mL aqueous suspension, adding 20-70 parts by weight of 5-10 wt% zinc chloride aqueous solution, carrying out ultrasonic treatment for 0.5-5h under a dark condition, adding 5-10 parts by weight of 15-30 wt% ammonia aqueous solution while stirring, continuing to react for 0.5-1h, adding 0.5-2 parts by weight of tetrabutyl titanate, fully stirring and reacting for 1-3h, finally, sequentially carrying out anhydrous ethanol and water washing, centrifugal separation and vacuum drying on the product, heating to 200-220 ℃ and baking for 1-2h to obtain the plastic antibacterial agent.
6. The antibacterial toy plastic according to claim 5, wherein the first solvent is one or more selected from dichloromethane, chloroform, acetonitrile, acetone and tetrahydrofuran; the second solvent is one or more of water, an ethanol-water mixed solution, a tetrahydrofuran-water mixed solution, a methanol-water mixed solution and an acetone-water mixed solution, and the water content of the ethanol-water mixed solution, the tetrahydrofuran-water mixed solution, the methanol-water mixed solution and the acetone-water mixed solution is not less than 50 wt%.
7. The antibacterial toy plastic of claim 5, wherein the catalyst is one or more of anhydrous zinc chloride, stannic chloride, ferric trichloride and aluminum trichloride.
8. The antimicrobial toy plastic of claim 2, wherein the plant antioxidant is pomegranate seed antioxidant and/or grape seed extract.
9. The antibacterial toy plastic according to any one of claims 1 to 8, characterized in that the preparation method of the antibacterial toy plastic comprises the following steps: weighing PVC, ABS, a plant antioxidant, a plastic antibacterial agent, tributyl citrate and calcium stearate according to the formula, and uniformly mixing; extruding, granulating and injection molding.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113956603A (en) * | 2021-11-15 | 2022-01-21 | 山东第一医科大学附属省立医院(山东省立医院) | High-hardness antibacterial plastic handle acupuncture needle and preparation method thereof |
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| CN103965576A (en) * | 2014-05-12 | 2014-08-06 | 宁波高新区卓尔化工科技有限公司 | Antibacterial toy plastic and preparation method thereof |
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| CN103965576A (en) * | 2014-05-12 | 2014-08-06 | 宁波高新区卓尔化工科技有限公司 | Antibacterial toy plastic and preparation method thereof |
| CN106589708A (en) * | 2016-12-30 | 2017-04-26 | 郑州掌盟网络科技有限公司 | Antibacterial plastics for toys and preparation method for antibacterial plastics |
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Cited By (2)
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| CN113956603A (en) * | 2021-11-15 | 2022-01-21 | 山东第一医科大学附属省立医院(山东省立医院) | High-hardness antibacterial plastic handle acupuncture needle and preparation method thereof |
| CN113956603B (en) * | 2021-11-15 | 2022-08-23 | 山东第一医科大学附属省立医院(山东省立医院) | High-hardness antibacterial plastic handle acupuncture needle and preparation method thereof |
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