CN115490956A - Long-acting antibacterial anti-aging polypropylene modified material and preparation method thereof - Google Patents
Long-acting antibacterial anti-aging polypropylene modified material and preparation method thereof Download PDFInfo
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- CN115490956A CN115490956A CN202211178199.8A CN202211178199A CN115490956A CN 115490956 A CN115490956 A CN 115490956A CN 202211178199 A CN202211178199 A CN 202211178199A CN 115490956 A CN115490956 A CN 115490956A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The long-acting antibacterial anti-aging polypropylene modified material is prepared from the following components in parts by weight: homo-polypropylene resin: 100 parts of (A); silver-carrying zirconium phosphate: 0.5 to 1 part; antibacterial long-acting modification auxiliary agent: 2 to 5 parts; high-efficiency dispersant: 0.5 to 1 part; coupling agent: 0.5 to 1 part; antioxidant: 1 to 2 parts; lubricant: 1 to 2 portions. The polypropylene modified material overcomes the defects in the prior art, and has the advantages of long-acting antibiosis, aging resistance and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a long-acting antibacterial anti-aging polypropylene modified material and a preparation method thereof.
Background
Polypropylene is a polymer obtained by addition polymerization of propylene, is one of the largest varieties of general-purpose thermoplastic resins, and is widely used in various fields of industrial production. The polypropylene is resistant to acid, alkali, salt and various organic solvents, and is widely used for sanitary ware products. However, due to the humid environment of the bathroom, bacteria are easy to breed on the bathroom products, and the health of people is affected. The existing antibacterial materials pay more attention to the antibacterial performance of the products when the products leave factory, but pay little attention to the long-acting property and the weather resistance of the antibacterial materials. Most of antibacterial bathroom products have greatly reduced antibacterial performance after being used for one to two years in a bathroom through photo-aging oxidation and long-term washing.
In response to national sustainable development and reduction of carbon emissions, polymer products need to have a long service life to avoid premature disposal. And the antibacterial property is reduced too early, the antibacterial long-acting property is poor, and the service life of the product is greatly influenced.
In CN 112266447A of the present invention, a halogenated amine antibacterial polypropylene material and a preparation method thereof are disclosed, wherein a polypropylene material with high antibacterial activity, difficult exudation, washing resistance and long service life is obtained through macromolecular polymerization and the synergistic effect of polyquaternium and halogenated amine polymer in the molecular chain. However, in the practical case of the patent, the antibacterial performance is not good, and in the examples, the antibacterial rate to staphylococcus aureus is only 99.1% at most, and the antibacterial rate to escherichia coli is only 98.3% at most, and the antibacterial performance is not good.
Disclosure of Invention
The invention aims to solve the problems of the prior art and provides a long-acting antibacterial anti-aging polypropylene modified material and a preparation method thereof.
In order to achieve the above purpose, the solution of the invention is:
the long-acting antibacterial anti-aging polypropylene modified material is prepared from the following components in parts by weight:
homo-polypropylene resin: 100 parts of (A);
silver-carrying zirconium phosphate: 0.5 to 1 part;
antibacterial long-acting modification auxiliary agent: 2 to 5 parts;
high-efficiency dispersant: 0.5 to 1 part;
coupling agent: 0.5 to 1 part;
antioxidant: 1 to 2 parts;
lubricant: 1 to 2 portions.
Further, the antibacterial long-acting modification auxiliary agent is compounded by chlorinated polypropylene, nano zinc sulfide and nano zinc oxide.
Further, the nano zinc sulfide and the nano zinc oxide form a nano inorganic substance according to the proportion of 4/1 to 2/1, and the chlorinated polypropylene and the nano inorganic substance are compounded according to the proportion of 1/1 to 1/2 to obtain the antibacterial long-acting modification auxiliary agent.
Further, the efficient dispersant is A-C homopolymers.
Further, the coupling agent is a titanium aluminate coupling agent.
Further, the antioxidant is compounded by 1/1 of antioxidant 168 and 1010.
Further, the lubricant is vinyl bis stearamide.
A preparation method of a long-acting antibacterial anti-aging polypropylene modified material comprises the following steps:
step 1, weighing the raw materials of each component in the long-acting antibacterial aging-resistant polypropylene modified material according to a proportion, adding nano zinc sulfide and nano zinc oxide into a high-speed vacuum kneading mixer, uniformly stirring at a high speed in vacuum, adding chlorinated polypropylene, and continuously uniformly stirring at a high speed in vacuum to obtain an antibacterial long-acting modified auxiliary agent;
step 2, opening the high-speed vacuum kneading mixer, continuously adding the zirconium phosphate silver-carrying, the antioxidant and the coupling agent, and uniformly stirring and mixing at a high speed to obtain a mixture 1;
step 3, adding 5 to 10 parts of homopolymerized polypropylene resin, a dispersing agent and a lubricating agent into a stirrer, and uniformly stirring; adding the mixture 1 into a stirrer, and continuously stirring to obtain a mixture 2;
step 4, adding the mixture 2 into a granulator, heating, extruding, cooling and granulating to obtain polypropylene antibacterial master batches;
and 5, adding the polypropylene antibacterial master batch and the rest 90-95 parts of polypropylene resin into a stirrer, uniformly stirring, adding into a granulator, heating, extruding, cooling, and granulating to obtain the long-acting antibacterial anti-aging polypropylene modified material.
Further, the vacuum degree of the high-speed vacuum kneading mixer in the step 1 is 1 to 10kPa, and the stirring speed is 800 to 1000rpm.
Further, the granulator in the step 5 is a co-rotating parallel twin-screw extrusion granulator, the extrusion temperature of the granulator is 190 to 210 ℃, and the rotation speed of the screws is 200 to 400 rpm.
Has the advantages that: according to the invention, through reasonable design of each component of the polypropylene modified material and improved process operation steps, the polypropylene modified material with the advantages of long-acting antibiosis, aging resistance and the like is prepared, the application field of the polypropylene material is expanded, the popularization value is achieved, and the effect is good particularly when the polypropylene modified material is applied to toilet cover plates of bathroom products.
Detailed Description
The invention discloses a long-acting antibacterial anti-aging polypropylene modified material which is prepared from the following components in parts by weight:
homo-polypropylene resin: 100 parts of (A);
silver-carrying zirconium phosphate: 0.5 to 1 part;
antibacterial long-acting modification auxiliary agent: 2 to 5 parts;
high-efficiency dispersant: 0.5 to 1 part;
coupling agent: 0.5 to 1 part;
antioxidant: 1 to 2 parts;
lubricant: 1 to 2 parts.
The polypropylene resin adopted by the invention is common homopolymerized polypropylene with a melt index of 10-18g/10 min, and is used for producing toilet cover plates of bathroom accessories, so that good processability and higher product glossiness are ensured.
The zirconium phosphate silver-carrying agent is used as an antibacterial agent, and the particle size is 0.5-5 mu m. The silver ions can generate chemical reaction on the surface of the antibacterial product to generate free radicals and active oxygen ions with oxidizing capability, and the structures of bacteria are damaged, so that the aim of sterilization is fulfilled. The silver-carrying concentration of the zirconium phosphate silver-carrying agent is high and can reach 20000ppm, while the silver-carrying concentration of the common glass silver-carrying antibacterial agent is only 10000ppm. After the action of silver ions on the surface of zirconium phosphate, the silver ions are transferred to the surface from the inside through concentration difference for supplementation. Compared with the mechanism that the silver ions are slowly released by dissolving the carrier in the glass-carried silver, the silver ions released by the zirconium phosphate-carried silver are slower and more stable, and the antibacterial performance of the zirconium phosphate-carried silver is longer.
The antibacterial long-acting modification auxiliary agent adopted by the invention is a compound mixture of chlorinated polypropylene, nano zinc sulfide and nano zinc oxide. The chlorinated polypropylene is chlorinated polypropylene particles with chlorine content of 20-40%. The chlorinated polypropylene is prepared by chlorination modification of polypropylene. Because the C-C main chain of the chlorinated polypropylene is provided with chlorine atoms and the C-Cl bond has strong polarity, the chlorinated polypropylene can guide the gradual release of effective antibacterial ingredients in the antibacterial agent, the nano zinc sulfide and the nano zinc oxide, and prolong the retention time of the antibacterial activity of the product; and the strong polarity of the polypropylene composite material enables the polypropylene composite material to have good compatibility with inorganic filler, and can play a role of a compatilizer of polypropylene, silver, nano zinc sulfide and nano zinc oxide. In addition, the Cl-group has mildew-proof and antibacterial properties, and a small amount of chlorinated polypropylene is compounded with nano zinc sulfide and nano zinc oxide, so that the antibacterial long-acting property of the product can be greatly improved.
In the antibacterial long-acting modification auxiliary agent, the particle size of nano zinc sulfide is 10-20nm, and the particle size of nano zinc oxide is 10-50nm. The zinc has antibacterial performance, and can play a synergistic role with silver, so that the antibacterial performance of the product is improved, and meanwhile, the antibacterial effect of the product can be supplemented when the antibacterial effect of silver ions is reduced, and the antibacterial effect of the product can be prolonged. In addition, the zinc sulfide has a wide forbidden band width (3.6-3.8 eV), has the capacity of absorbing ultraviolet bands in sunlight, and simultaneously, the zinc oxide has a wide energy band gap (-3.4 eV), so that the resistance to the sunlight can be enhanced by combining the zinc sulfide and the zinc oxide, and the weather resistance of the product is improved.
The antibacterial long-acting modification auxiliary agent in the formula is 2-5 parts, and if the addition amount is too small, the antibacterial long-acting improvement is insufficient, and if the addition amount is too large, the fluidity of the modified material is affected, so that the processing of the product is difficult, and the abnormality such as flow mark material flower occurs. An antibacterial long-acting modification auxiliary is prepared by adopting nano zinc sulfide and nano zinc oxide to form a nano inorganic substance according to the ratio of 4/1 to 2/1, and preparing a compound antibacterial long-acting modification auxiliary from chlorinated polypropylene and the nano inorganic substance according to the ratio of 1/1 to 1/2. The modified assistant has the functions of long-acting antibiosis and weather resistance improvement.
The invention adopts titanium aluminate as a coupling agent to treat a compounded system of chlorinated polypropylene, nano zinc sulfide and nano zinc oxide, so that the titanium aluminate can be well compatible with a material main body.
The invention adopts the high-efficiency dispersant which is an A-C homopolymer and low molecular weight polyethylene wax, and provides super-strong external lubricity for the lubricating dispersant. Due to the existence of the efficient lubricant, the processing performance of the modified material is greatly improved. The addition amount is 0.5 to 1 part.
The invention adopts a secondary extrusion granulation process, wherein an additive is mixed with 5 to 10 parts of polypropylene resin for granulation to prepare long-acting antibacterial polypropylene master batch, and then the long-acting antibacterial weather-resistant polypropylene master batch is mixed with the rest 90 to 95 parts of polypropylene resin for granulation to obtain the long-acting antibacterial weather-resistant polypropylene modified material.
The invention also discloses a preparation method of the long-acting antibacterial anti-aging polypropylene modified material, which comprises the following steps:
step 1, weighing the raw materials of each component in the long-acting antibacterial aging-resistant polypropylene modified material according to a proportion, adding nano zinc sulfide and nano zinc oxide into a high-speed vacuum kneading mixer, uniformly stirring at a high speed in vacuum, adding chlorinated polypropylene, and continuously uniformly stirring at a high speed in vacuum to obtain an antibacterial long-acting modified auxiliary agent;
step 2, opening the high-speed vacuum kneading mixer, continuously adding the zirconium phosphate silver-carrying, the antioxidant and the coupling agent, and uniformly stirring and mixing at a high speed to obtain a mixture 1;
step 3, adding 5 to 10 parts of homopolymerized polypropylene resin, a dispersing agent and a lubricating agent into a stirrer, and uniformly stirring; adding the mixture 1 into a stirrer, and continuously stirring to obtain a mixture 2;
step 4, adding the mixture 2 into a granulator, heating, extruding, cooling and granulating to obtain polypropylene antibacterial master batches;
and 5, adding the polypropylene antibacterial master batch and the rest 90 to 95 parts of polypropylene resin into a stirrer, uniformly stirring, adding into a granulator, heating, extruding, cooling, and granulating to obtain the long-acting antibacterial anti-aging polypropylene modified material.
Further, in the step 1, the vacuum degree of the high-speed vacuum kneading mixer is 1 to 10kPa, and the stirring speed is 800 to 1000rpm.
Further, the granulator in the step 5 is a co-rotating parallel twin-screw extrusion granulator, the extrusion temperature of the granulator is 190 to 210 ℃, and the rotation speed of the screws is 200 to 400 rpm.
According to the invention, a high-speed vacuum kneading mixer is adopted, the chlorinated polypropylene, the nano zinc sulfide and the nano zinc oxide are stirred at a high speed in a vacuum closed space, the mutual dispersion among the chlorinated polypropylene, the nano zinc sulfide and the nano zinc oxide is more uniform by applying the principle that the interaction force of materials in vacuum is small and the materials are more easily dispersed uniformly, meanwhile, the nano zinc sulfide can form a semi-wrapped state on the outer layer of nano zinc oxide particles due to a larger using amount, and the powder forms a wrap on the outer layer of the chlorinated polypropylene, so that a synergistic effect is generated, and the antibacterial long-acting property of the product is improved.
After the scheme is adopted, the polypropylene modified material with the advantages of long-acting antibiosis, aging resistance and the like is prepared through reasonable design of the components of the polypropylene modified material and improved process operation steps, the application field of the polypropylene material is expanded, the popularization value is realized, and the effect is good particularly when the polypropylene modified material is applied to toilet cover plates of bathroom products.
The technical scheme of the invention is further illustrated by the following embodiments. Those skilled in the art will recognize that the specific techniques or conditions, not specified in the examples, may be followed by techniques or conditions described in literature in the art or by product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The formula of the present example is shown in table 1, wherein the homo-polypropylene is made of domestic Zhonghai Shell 500N; the chlorinated polypropylene is prepared from Japan eastern DX-530P; the nano zinc sulfide adopts domestic 10nm nano zinc sulfide; the nano zinc oxide is domestic 20nm nano zinc oxide; the zirconium phosphate silver-carrying adopts the zirconium phosphate silver-carrying of the type 003H4 made in Jinda in China; the high-efficiency dispersant adopts American Honeywell A-C617A; the coupling agent adopts titanium aluminate; the antioxidant is prepared by compounding antioxidant 168 and antioxidant 1010 according to 1/1; the lubricant is vinyl bis stearamide.
TABLE 1 formula table of modified polypropylene materials
The manufacturing step of the filling material: 1) Adding nano zinc sulfide and nano zinc oxide into a high-speed vacuum kneading mixer in proportion, starting high-speed stirring at the speed of 800rpm for 20min after the vacuum degree reaches 10kPa, adding chlorinated polypropylene, and continuing to stir at high speed in vacuum for 5min to obtain the antibacterial long-acting modification auxiliary agent;
2) Opening a stirring barrel of the high-speed vacuum kneading stirrer, and continuously adding the zirconium phosphate silver, the antioxidant and the coupling agent; after the vacuum degree reaches 10kPa, starting to stir at a high speed of 800rpm for 10min to obtain a mixture 1;
3) Adding 10 parts of polypropylene resin, a dispersing agent and a lubricating agent into a stirrer, and stirring for 5 min; adding the mixture 1 in the step 2) into a stirrer, and continuously stirring for 10min to obtain a mixture 2; 4) Extruding the mixture 2 by a co-rotating twin-screw parallel extrusion granulator at the extrusion temperature of 200 ℃ and the screw rotation speed of 300 r/min, and cooling and granulating to obtain antibacterial master batches;
5) And adding the polypropylene antibacterial master batch and the rest 90 parts of polypropylene resin into a stirrer, stirring for 5min, adding into an extrusion granulator, wherein the extrusion equipment is a co-rotating twin-screw parallel extrusion granulator, the extrusion temperature is 200 ℃, the screw rotation speed is 300 rpm, cooling, and finally granulating to obtain the long-acting antibacterial anti-aging polypropylene modified material.
TABLE 2 Performance test Table for modified long-acting antibacterial anti-aging polypropylene materials
The performance of the prepared material is detected as shown in the table 2, and as can be seen from the table 2, the modified material has excellent comprehensive performance and can be directly used for producing the toilet cover plate.
Wherein, the sample No. 0 is a sample without the antibacterial long-acting modification auxiliary agent, namely a blank ratio control sample.
The test adopts specific standards as follows:
the tensile strength is measured at a speed of 100mm/min according to the standard GB/T1040 determination of tensile property of plastics;
the impact strength is measured by the standard GB/T1843 'Plastic cantilever beam impact strength';
the antibacterial rate adopts the standard ISO 22196 detection for surface antibacterial property, and the strains adopt ATCC 8739 Escherichia coli and ATCC6538P staphylococcus aureus;
xenon lamp aging test adoptsThe irradiance is (0.35 +/-0.02) W/(m) measured by a standard ASTM D2565-16' standard practice for exposing outdoor plastic xenon lamps 2 Nm) @340nm, the temperature of a continuous illumination blackboard is 63 +/-5 ℃, the filter is Boro/Boro, and the exposure time is 200h and 600h;
taking out the sample after the xenon lamp aging test is finished, and testing the color change and color difference before and after the test;
after the xenon lamp aging test is finished, taking out the sample wafer, and carrying out an antibacterial rate test;
the brushing test adopts a standard GB/T9266 'determination of the washability of architectural coating' (the brushing liquid is 5% sodium hypochlorite disinfectant, and the brushing times are 500 times), a sample is taken out after the brushing test is finished, and the antibacterial rate test is carried out after the test.
As can be seen from the performance table in Table 2, the modified polypropylene material has excellent comprehensive performance, the mechanical strength is equivalent to that of the common antibacterial polypropylene before modification, and the strength and toughness all reach the level of the material for the common toilet cover plate.
Meanwhile, through a strict xenon lamp aging test, 200 hours and 600 hours of tightening test are adopted, the color difference of the modified material is obviously smaller than that of a common antibacterial polypropylene No. 0 sample, and the weather resistance of the modified material is better than that of the common antibacterial polypropylene. And the antibacterial rate after xenon lamp aging test is superior to that of the common antibacterial polypropylene 0# sample material.
After 500 times of washing and brushing tests, the antibacterial rate of the material is also obviously superior to that of the common antibacterial polypropylene 0# sample material. The antibacterial long-term effect of the modified material is obviously superior to that of the common antibacterial polypropylene material.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. A long-acting antibacterial anti-aging polypropylene modified material is characterized in that: the composition is prepared from the following components in parts by weight:
homo-polypropylene resin: 100 parts of a binder;
silver-carrying zirconium phosphate: 0.5 to 1 part;
antibacterial long-acting modification auxiliary agent: 2 to 5 parts;
high-efficiency dispersant: 0.5 to 1 part;
coupling agent: 0.5 to 1 part;
antioxidant: 1 to 2 parts;
lubricant: 1 to 2 portions.
2. The long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 1, wherein: the antibacterial long-acting modification auxiliary agent is compounded by chlorinated polypropylene, nano zinc sulfide and nano zinc oxide.
3. The long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 2, wherein: the nano zinc sulfide and the nano zinc oxide form a nano inorganic substance according to the proportion of 4/1 to 2/1, and the chlorinated polypropylene and the nano inorganic substance are compounded according to the proportion of 1/1 to 1/2 to obtain the antibacterial long-acting modification auxiliary agent.
4. The long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 1, wherein: the high-efficiency dispersant is A-C homopolymers.
5. The long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 1, wherein: the coupling agent is a titanium aluminate coupling agent.
6. The long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 1, wherein: the antioxidant is compounded by 1/1 of antioxidant 168 and 1010.
7. The long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 1, wherein: the lubricant is vinyl bis stearamide.
8. A preparation method of a long-acting antibacterial anti-aging polypropylene modified material comprises the following steps:
step 1, weighing the raw materials of each component in the long-acting antibacterial aging-resistant polypropylene modified material according to any one of claims 1 to 7 in proportion, adding nano zinc sulfide and nano zinc oxide into a high-speed vacuum kneading mixer, uniformly stirring at a high speed in vacuum, adding chlorinated polypropylene, and continuously uniformly stirring at a high speed in vacuum to obtain an antibacterial long-acting modification auxiliary agent;
step 2, opening the high-speed vacuum kneading mixer, continuously adding the zirconium phosphate silver-carrying agent, the antioxidant and the coupling agent, and uniformly stirring and mixing at a high speed to obtain a mixture 1;
step 3, adding 5 to 10 parts of homo-polypropylene resin, a dispersing agent and a lubricating agent into a stirrer, and uniformly stirring; adding the mixture 1 into a stirrer, and continuously stirring to obtain a mixture 2;
step 4, adding the mixture 2 into a granulator, heating, extruding, cooling and granulating to obtain polypropylene antibacterial master batches;
and 5, adding the polypropylene antibacterial master batch and the rest 90 to 95 parts of polypropylene resin into a stirrer, uniformly stirring, adding into a granulator, heating, extruding, cooling, and granulating to obtain the long-acting antibacterial anti-aging polypropylene modified material.
9. The preparation method of the long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 8, characterized in that: the vacuum degree of the high-speed vacuum kneading mixer in the step 1 is 1 to 10kPa, and the stirring speed is 800 to 1000rpm.
10. The preparation method of the long-acting antibacterial aging-resistant polypropylene modified material as claimed in claim 8, characterized in that: the granulator in the step 5 is a co-rotating parallel twin-screw extrusion granulator, the extrusion temperature of the granulator is 190 to 210 ℃, and the rotation speed of the screws is 200 to 400 rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926323A (en) * | 2022-12-30 | 2023-04-07 | 广东金发科技有限公司 | Polypropylene melt-blown material and preparation method and application thereof |
| CN116814032A (en) * | 2023-08-22 | 2023-09-29 | 禧天龙科技发展有限公司 | Preparation process of anti-mite and antibacterial storage box |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926323A (en) * | 2022-12-30 | 2023-04-07 | 广东金发科技有限公司 | Polypropylene melt-blown material and preparation method and application thereof |
| CN115926323B (en) * | 2022-12-30 | 2024-03-15 | 广东金发科技有限公司 | Polypropylene melt-blown material and preparation method and application thereof |
| CN116814032A (en) * | 2023-08-22 | 2023-09-29 | 禧天龙科技发展有限公司 | Preparation process of anti-mite and antibacterial storage box |
| CN116814032B (en) * | 2023-08-22 | 2023-11-21 | 禧天龙科技发展有限公司 | Preparation process of anti-mite and antibacterial storage box |
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