CN111602655A - Antiviral double-shell microcapsule, preparation method thereof, disinfection coating with antiviral double-shell microcapsule, preparation method and application thereof - Google Patents

Antiviral double-shell microcapsule, preparation method thereof, disinfection coating with antiviral double-shell microcapsule, preparation method and application thereof Download PDF

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CN111602655A
CN111602655A CN202010385362.2A CN202010385362A CN111602655A CN 111602655 A CN111602655 A CN 111602655A CN 202010385362 A CN202010385362 A CN 202010385362A CN 111602655 A CN111602655 A CN 111602655A
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double
antiviral
shell microcapsule
microcapsule
shell
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喻学锋
吴列
杨新耕
康翼鸿
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Wuhan Zhongke Advanced Technology Research Institute Co ltd
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Wuhan Zhongke Advanced Technology Research Institute Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28Microcapsules or nanocapsules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16Homopolymers or copolymers of vinylidene fluoride
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses an antiviral double-shell microcapsule, a preparation method thereof, a disinfection coating with the antiviral double-shell microcapsule, a preparation method and application thereof. The capsule is prepared by taking polyethylene oxide or/and polyethylene glycol as inner-layer wall materials and disinfectant materials as core materials and preparing porous microcapsules by a phase separation method; then, taking inorganic oxide or/and metal particles as outer-layer wall materials, taking the obtained porous microcapsule as a core material, and preparing the antiviral double-shell microcapsule by in-situ polymerization; the disinfectant material is a volatile or semi-volatile disinfectant. A disinfecting paint contains sol containing multi-block fluoric copolymer and antiviral double-shell microcapsule. The capsule has effects of sustained release of disinfectant and synergistic virucidal effect with shell material. The disinfection coating comprises the antivirus double-shell microcapsule and the multiblock fluorine-containing copolymer, can reduce the adhesion of viruses when being prepared into a coating, and has high virus killing efficiency of the disinfection coating.

Description

Antiviral double-shell microcapsule, preparation method thereof, disinfection coating with antiviral double-shell microcapsule, preparation method and application thereof
Technical Field
The invention relates to the technical field of disinfection products, in particular to an antiviral double-shell microcapsule, a preparation method thereof, a disinfection coating with the antiviral double-shell microcapsule, a preparation method and an application thereof.
Background
Common disinfectant products can be divided into chlorine-containing disinfectants, alcohol disinfectants, phenol disinfectants, photocatalytic nano-material disinfectants, metal disinfectants and the like according to the components. At present, chlorine-containing disinfectants are most widely used, but the chlorine-containing disinfectants also have the defects of overhigh concentration, short action time, residue after use, short action time and the like caused by instant release. Photocatalytic nanomaterials and metal nanoparticles are the direction of current research, however these solutions suffer from various drawbacks. For example, photocatalytic disinfection requires an additional light source, requires a long time, is sensitive to humidity, and the catalyst surface is susceptible to contamination. The use of silver nanoparticles increases material and manufacturing costs. In addition, widespread use and abuse has led to an increase in drug resistance. For these reasons, the use of secondary technologies and inclusion of slow-release disinfectants remains a concern for manufacturability, safety, and long-term stability.
Disclosure of Invention
The invention aims to provide an antiviral double-shell microcapsule with good virus killing effect and a preparation method thereof, and a disinfection coating with the antiviral double-shell microcapsule, which has high virus killing efficiency, long action time, sustainable and stable release and less residue, and a preparation method and application thereof, aiming at the defects in the prior art.
The invention relates to an antiviral double-shell microcapsule, which is prepared by taking polyethylene oxide or/and polyethylene glycol as inner-layer wall materials and disinfectant materials as core materials through a phase separation method; then, taking inorganic oxide or/and metal particles as outer-layer wall materials, taking the obtained porous microcapsule as a core material, and preparing the antiviral double-shell microcapsule by in-situ polymerization; the disinfectant material is a volatile or semi-volatile disinfectant.
Further, the disinfectant material includes one or more of chlorine dioxide, hypochlorite, peroxide.
Further, the anti-virus double-shell microcapsule comprises 20-50 wt% of disinfectant material by mass.
Furthermore, the particle size of the antiviral double-shell microcapsule is 500 nm-5 μm.
A preparation method of an antiviral double-shell microcapsule is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing a disinfectant mixed solution: uniformly mixing a disinfectant material and an aqueous solution containing a metal ion compound;
s2: porous microcapsules: dropwise adding the disinfectant mixed solution prepared in the step S1 into a polyethylene oxide and/or polyethylene glycol solution for emulsification, and then adding a coagulant to form porous microcapsules;
s3: antiviral double-shell microcapsule: dissolving inorganic oxide or/and metal particles in an organic solvent, uniformly mixing with the porous microcapsule obtained in the step S2, and adding a proper amount of HNO3Stirring for a period of time to obtain the antiviral double-shell microcapsule.
A disinfecting paint contains sol containing multi-block fluoric copolymer and antiviral double-shell microcapsule.
Further, the disinfection coating comprises the following raw materials in parts by weight: 15-25 parts of curing agent, 30-50 parts of ethanol, 25-30 parts of multi-block fluorine-containing copolymer and 10-15 parts of antiviral double-shell microcapsule.
Further, the curing agent comprises epoxy resin or/and silicon ether resin.
A preparation method of the disinfection coating comprises the steps of dissolving a curing agent in ethanol, adding the antiviral double-shell capsule and the segmented fluorine-containing copolymer ethanol dispersion liquid, stirring uniformly, adding a fluoride with low surface energy, and mixing to obtain the disinfection coating.
The application of the disinfection paint comprises the steps of coating the disinfection paint on a substrate, and curing at high temperature to obtain a hydrophobic coating with an antiviral function; the target viruses that the hydrophobic coating can resist are single-stranded RNA viruses, double-stranded RNA viruses, single-stranded DNA viruses and double-stranded DNA viruses.
The invention provides an antiviral double-shell microcapsule, which comprises at least one volatile or semi-volatile disinfectant, wherein a microcapsule shell material comprises a mixture of one or more polymers and one or more metal compounds so as to achieve the slow and controlled release of the disinfectant and the synergistic virus killing effect with the shell material. Compared with the traditional solid polymer particles, the invention has the advantages of high specific surface area, higher porosity, strong adsorption force, increased brittleness and the like.
The invention provides a multi-effect hydrophobic disinfection coating, which comprises an antiviral double-shell microcapsule and a multi-block fluorine-containing copolymer, and can reduce the attachment of viruses when a coating is prepared.
Drawings
FIG. 1 is a schematic contact angle diagram of the hydrophobic coating obtained in examples 1-3;
fig. 2 is a graph showing the sustained release of chlorine dioxide by the antiviral double-shell microcapsule obtained in example 1.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
Example 1
(1) Adding NaClO2The powder was dissolved in 100ml of deionized water to prepare NaClO with a concentration of 0.5 wt% to 50 wt%2And (3) solution. The obtained NaClO2The solution is mixed with 0.2g-2g of 30 wt% H2O2And (4) mixing.
(2) Preparing polyethylene glycol 400 into a 30% polyethylene glycol aqueous solution by mass fraction, and dropwise adding the disinfectant mixture obtained in the step (1) into the polyethylene glycol solution under the condition of vigorous stirring at 1500r/min for emulsification. Sodium sulfate as a coagulant was added to the system to form porous microcapsules.
(3) Tetrabutyl silicate (8ml) is dissolved in isopropanol (24ml), and is uniformly mixed with the porous microcapsules obtained in the step (2), and then a proper amount of HNO3 is added under vigorous stirring to obtain an opaque suspension. Further stirred at 80 ℃ for 6h, then cooled to room temperature and stirred overnight to give transparent silica-polyethylene glycol double-shell microcapsules.
(4) Adding the porous microcapsule described in the embodiment 6 into a normal hexane solution of polyvinylidene fluoride, and then adding a fluoride with low surface energy to obtain a hydrophobic coating solution; the hydrophobic coating solution is coated on a substrate to prepare the hydrophobic coating 1 having an antiviral function.
Example 2
Step (1) and step (2) were the same as in example 1
(3) Tetrabutyl titanate (8ml) is dissolved in isopropanol (24ml), and is uniformly mixed with the porous microcapsules obtained in the step (2), and then a proper amount of HNO3 is added under vigorous stirring to obtain an opaque suspension. Further stirred at 80 ℃ for 6h, then cooled to room temperature and stirred overnight to give transparent titanium dioxide-polyethylene glycol double-shell microcapsules.
(4) Adding the porous microcapsule obtained in the step (3) into a normal hexane solution of polyvinylidene fluoride, and then adding a low-surface-energy fluoride to obtain a hydrophobic coating solution; the hydrophobic coating solution is coated on the substrate to prepare the hydrophobic coating 2 with the antiviral function.
Example 3
Step (1) and step (2) were the same as in example 1
(3) AgNO3 was dissolved in water and mixed well with the porous microcapsules obtained in example 4, followed by addition of the appropriate amount of HNO3 under vigorous stirring to give an opaque suspension. Further stirred at 80 ℃ for 2h, then cooled to room temperature and stirred overnight to give transparent silver-polyethylene glycol double-shell microcapsules.
(4) Adding the porous microcapsule described in the embodiment 8 into a normal hexane solution of polyvinylidene fluoride, and then adding a fluoride with low surface energy to obtain a hydrophobic coating solution; the hydrophobic coating solution is coated on the substrate to prepare the hydrophobic coating 3 with the antiviral function.
Example 4
(1) Adding NaClO2The powder was dissolved in 100ml of deionized water to prepare NaClO with a concentration of 0.5 wt% to 50 wt%2And (3) solution. The obtained NaClO2The solution is mixed with 1-10ml of 2 wt% -20 wt% NaClO aqueous solution.
(2) Preparing polyethylene oxide into 25 mass percent polyethylene oxide solution, and dropwise adding the disinfectant mixture obtained in the step (1) into the polyethylene oxide solution under the condition of vigorous stirring at 1000r/min for emulsification. Sodium sulfate as a coagulant was added to the system to form porous microcapsules.
The steps (3) and (4) are the same as in example 1.
Example 5
(1) Adding NaClO2The powder was dissolved in 100ml of deionized water to prepare NaClO with a concentration of 0.5 wt% to 50 wt%2And (3) solution. The obtained NaClO2The solution is mixed with 1-10ml of 2 wt% -20 wt% AgNO3、Cu(NO3)2、Zn(NO3)2The aqueous solutions are mixed.
Steps (2) to (3) were the same as in example 5.
And (3) data testing:
first, contact Angle measurement
The water contact angle of the hydrophobic coating 1 described in example 1 was measured with a contact angle measuring instrument, and the water contact angle of the hydrophobic coating 1 described in example 1 was 125 °.
The water contact angle of the hydrophobic coating 2 described in example 2 was measured with a contact angle measuring instrument, and the water contact angle of the hydrophobic coating 2 described in example 2 was 136 °.
The water contact angle of the hydrophobic coating 3 described in example 3 was measured using a contact angle measuring instrument, and the water contact angle of the hydrophobic coating 3 described in example 11 was 131 °.
FIG. 1 is a schematic representation of the contact angles of the hydrophobic coatings obtained in examples 1-3. The result shows that the hydrophobic coating obtained by the invention has good hydrophobic property and can effectively prevent the attachment of virus-containing droplets
Second, testing the virus killing rate
Taking a 12-hole plate, cleaning, and sterilizing at high temperature for later use; treating swine influenza virus (H)1N1) Concentrate (titer 5.2 × 105TCID50/mL) was diluted 10-fold for use; collecting 5 μ L of swine influenza virus (H)1N1) The dilution was added to a well plate coated with the antiviral hydrophobic coating 1 described in example 1. And (3) standing for 2h, taking out the supernatant of the pore plate, then putting the supernatant into a constant-temperature incubator for culturing for 2 days, taking out the supernatant, dyeing the supernatant into plaques, and counting the plaques. The virus killing rate is 98%.
Taking a 12-hole plate, cleaning, and sterilizing at high temperature for later use; treating swine influenza virus (H)1N1) Concentrate (titer 5.2 × 105TCID50/mL) was diluted 10-fold for use; collecting 5 μ L of swine influenza virus (H)1N1) The dilution was added to a well plate coated with the antiviral hydrophobic coating 2 described in example 2. And (3) standing for 2h, taking out the supernatant of the pore plate, then putting the supernatant into a constant-temperature incubator for culturing for 2 days, taking out the supernatant, dyeing the supernatant into plaques, and counting the plaques. The virus killing rate is 99%.
Taking a 12-hole plate, cleaning, and sterilizing at high temperature for later use; treating swine influenza virus (H)1N1) Concentrate (titer 5.2 × 105TCID50/mL) was diluted 10-fold for use; collecting 5 μ L of swine influenza virus (H)1N1) The dilution was added to a well plate coated with the antiviral hydrophobic coating 3 described in example 3. And (3) standing for 2h, taking out the supernatant of the pore plate, then putting the supernatant into a constant-temperature incubator for culturing for 2 days, taking out the supernatant, dyeing the supernatant into plaques, and counting the plaques. The virus killing rate is 99%.
Third, testing the anti-adhesion rate of virus
100ml 108/cm3Of (2) a virusThe solution was uniformly coated on a glass surface with a hydrophobic antiviral coating and incubated at 37 ℃ for 4 hours. The number of viruses that were attached to the clean glass or coated glass, respectively, was observed under a microscope. The number of viruses adhering to the coated glass is significantly less than that of the uncoated glass. Examples 1, 2 and 3 for Swine influenza Virus (H)1N1) The anti-adhesion rate can reach 97%, 98% and 95% respectively.
Fourth, disinfectant Release test
30mL of the antiviral double-shell microcapsule obtained in example 1 was added to a beaker, and placed in a desiccator with a 20% KI solution, and free iodine was titrated with a standard solution of sodium thiosulfate. The total amount of sodium thiosulfate solution used was recorded and the average was taken 3 times.
The effective chlorine dioxide release amount and the number of days of release were combined as shown in fig. 2. The result shows that the disinfectant can well control the release slowly and has longer effective time.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.

Claims (10)

1. An antiviral double-shell microcapsule, which is characterized in that: firstly, preparing porous microcapsules by a phase separation method by taking polyethylene oxide or/and polyethylene glycol as inner-layer wall materials and disinfectant materials as core materials; then, taking inorganic oxide or/and metal particles as outer-layer wall materials, taking the obtained porous microcapsule as a core material, and preparing the antiviral double-shell microcapsule by in-situ polymerization; the disinfectant material is a volatile or semi-volatile disinfectant.
2. An antiviral double-shell microcapsule according to claim 1, wherein: the disinfectant material includes one or more of chlorine dioxide, hypochlorite, peroxide.
3. An antiviral double-shell microcapsule according to claim 2, wherein: the pore diameter of the porous microcapsule is 10-20 nm.
4. An antiviral double-shell microcapsule according to claim 3, wherein: the particle size of the antiviral double-shell microcapsule is 500 nm-5 mu m.
5. An antiviral double shell microcapsule preparation process as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps:
s1: preparing a disinfectant mixed solution: uniformly mixing a disinfectant material and an aqueous solution containing a metal ion compound;
s2: porous microcapsules: dropwise adding the disinfectant mixed solution prepared in the step S1 into a polyethylene oxide and/or polyethylene glycol solution for emulsification, and then adding a coagulant to form porous microcapsules;
s3: antiviral double-shell microcapsule: dissolving inorganic oxide or/and metal particles in an organic solvent, uniformly mixing with the porous microcapsule obtained in the step S2, and adding a proper amount of HNO3Stirring for a period of time to obtain the antiviral double-shell microcapsule.
6. A disinfecting coating, characterized in that: comprising a sol comprising a multiblock fluorine-containing copolymer composition and an antiviral double-shell microcapsule according to any one of claims 1 to 5.
7. A disinfecting paint as claimed in claim 6, characterized in that: the disinfection coating comprises the following raw materials in parts by weight: 15-25 parts of curing agent, 30-50 parts of ethanol, 25-30 parts of multi-block fluorine-containing copolymer and 10-15 parts of antiviral double-shell microcapsule.
8. A disinfecting paint as claimed in claim 7, characterized in that: the curing agent comprises epoxy resin or/and silicon ether resin.
9. The method of claim 7, wherein the step of preparing a disinfecting coating comprises: dissolving a curing agent in ethanol, adding the antiviral double-shell capsule and the multi-block fluorine-containing copolymer ethanol dispersion, uniformly stirring, adding a low-surface-energy fluoride, and mixing to obtain the disinfection coating.
10. The use of a disinfecting coating as claimed in claim 6, characterized in that: smearing the disinfection paint on a substrate, and curing at high temperature to obtain a hydrophobic coating with an antiviral function; the target viruses that the hydrophobic coating can resist are single-stranded RNA viruses, double-stranded RNA viruses, single-stranded DNA viruses and double-stranded DNA viruses.
CN202010385362.2A 2020-05-09 2020-05-09 Antiviral double-shell microcapsule, preparation method thereof, disinfection coating with antiviral double-shell microcapsule, preparation method and application thereof Pending CN111602655A (en)

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CN112841216A (en) * 2020-12-31 2021-05-28 山东观变生物科技有限公司 Chlorine dioxide liquid microcapsule and preparation method thereof

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吕永生等: "缓释型二氧化氯固体制剂的制备方法及其缓释性能", 《环境化学》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662300A (en) * 2020-12-26 2021-04-16 武汉中科先进技术研究院有限公司 Long-acting wear-resistant slow-release antiviral coating and preparation
CN112841216A (en) * 2020-12-31 2021-05-28 山东观变生物科技有限公司 Chlorine dioxide liquid microcapsule and preparation method thereof

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