CN112962315A - Coating with virus killing function formed on surface of article and coating method thereof - Google Patents

Coating with virus killing function formed on surface of article and coating method thereof Download PDF

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CN112962315A
CN112962315A CN202110136024.XA CN202110136024A CN112962315A CN 112962315 A CN112962315 A CN 112962315A CN 202110136024 A CN202110136024 A CN 202110136024A CN 112962315 A CN112962315 A CN 112962315A
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solution
article
coating
derivative
virus
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汪大洋
王博
解仁国
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Jilin University
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Jilin University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002—Pretreatement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/02—Compounds containing nitrogen-to-halogen bonds
    • C07C239/06—N-halogenated carboxamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D133/00—Coating 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D133/00—Coating 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

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  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Inorganic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

A coating with antivirus function on the surface of an article is a polyamine derivative containing partial halogen amination, and the structural formula of the coating is [ NRX]m[NHR]1‑mWherein R is H (CH)2) n, n is 0 to 20, X is Cl, Br or I atom, m is the mole fraction m of the repeat unit of the amine group monomer of the haloamination is 0.1-0.9, and 1-m is the mole fraction of the repeat unit of the amine group monomer. N-X of nitrogen-halogen bond exists in polyamine derivative partially subjected to halogen amination, and the nitrogen-halogen bond is subjected to hydrolysis reaction when meeting water to release X with strong oxidizing property and capable of killing viruses+The action force of hydrogen bonds formed by amino groups in the partially halamine polyamine derivatives and polar surfaces realizes the adhesion of the derivatives on the surfaces of articles to form coatings with virucidal functions.

Description

Coating with virus killing function formed on surface of article and coating method thereof
Technical Field
The invention relates to a coating with a virus killing function formed on the surface of an article and a coating method thereof.
Technical Field
The virus is a sub-microscopic pathogen which can only reproduce in living cells of organisms, is in a non-cellular form consisting of a nucleic acid molecule (DNA or RNA) and a protein, is an organism-like organism, cannot show life phenomena by itself, depends on living parasitism, and is an organic species between living bodies and non-living bodies. It is a stretch of DNA or RNA surrounded by a protective outer shell, and by the mechanism of infection, these simple organisms can self-replicate using the host's cellular system, but cannot grow and replicate independently. Viruses can infect all living organisms with cellular structures. The transmission modes of the viruses are various, and different methods are adopted for different types of viruses. For example: influenza viruses can be transmitted via coughing and sneezing; norovirus can be transmitted by the hand-foot-mouth pathway, i.e.: by contact with virus-bearing hands, food and water; rotavirus is often transmitted directly by contact with infected children.
COVID-19 is an infectious disease caused by severe acute respiratory syndrome coronavirus 2 (abbreviated as SARS-CoV-2). The disease is outbreak and spread rapidly in large scale in all countries around the world, and becomes one of the epidemic diseases with the most fatalities in human history. The COVID-19 virus is transmitted primarily through the oral nasal secretions, including respiratory droplets resulting from coughing, sneezing and speaking. These droplets generally do not travel long distances in the air. Suggested measures to prevent infection include frequent hand washing, social distance to others, quarantine, cough masking, avoidance of eye, nose, mouth touch. Wearing protective articles in public places can reduce the risk of transmission. The method for controlling the epidemic situation not only causes the shortage of medical protective materials, but also brings great working pressure to medical workers, thereby causing the risk of secondary infection caused by human negligence. Generally, the specific biological structure of the virus determines that the living way can only be hosted in living organisms, so it is very critical how to effectively protect the virus before it invades into the human body, because once the virus enters into the human body to breed, there is no effective specific medicine for treating the virus to kill the virus, and the general protection means is based on some physical protection, for example: protective clothing worn by medical personnel, the basic principle of protection is to prevent viruses from attaching to clothes and skin of people, but the implementation of the physical protection is impractical and practically impossible for the public. Therefore, how to kill the virus attached to the protective articles is very suitable for the actual requirement.
The halamine compound is used as a green bactericide, and practice proves that the halamine compound has a good bactericidal effect and is non-irritating to human skin. Meanwhile, researchers find that the halamine compound has a good killing effect on viruses, and the halogen cations with strong oxidizing property are released after the nitrogen-halogen bonds in the halamine compound are hydrolyzed, so that the protein shell on the surface of the viruses can be denatured, the transcription process of DNA or RNA of genetic materials in the viruses cannot be completed, specific proteins invading living bodies cannot be generated, and no specific protein combined with host cells exists. The virus cannot synthesize its genetic material and the desired protein coat from host's own materials such as ribonucleic acid and amino acids, and the halamine compound can fundamentally inactivate the virus, thereby preventing it from invading the host cell to propagate. Therefore, it is of great importance to the public health and safety of human beings to prepare a coating which can form a virucidal function on an article. However, no report has been found to prevent COVID-19 using a halamine compound.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention designs a coating based on partially haloaminated polyamine derivatives with virucidal function. Polyamine derivatives are halogenated to obtain partially haloaminated polyamine derivatives, which contain nitrogen-halogen bonds (N-X) which are hydrolyzed to generate strong oxidative halide cations capable of killing viruses. Meanwhile, the adsorption is realized by the action force of hydrogen bonds formed between the non-halogenated amino groups and the surface of the polar article. And for the surface of a non-polar object, the partially halated polyamine derivative realizes the adsorption by utilizing the hydrophobic force formed by the carbon chain of the partially halated polyamine derivative and the surface of the non-polar object. In order to further enhance the adhesion of the partially halated polyamine derivative to form a coating with a virucidal function on the surface of an article, polar macromolecules capable of enhancing the hydrogen bonding force and the hydrophobic force formed between the coating and the surface of the article are added into the coating liquid. In addition, the polyphenol derivative added into the coating liquid can enhance the hydrogen bond acting force and the pi-pi acting force formed between the coating and the surface of an article through oxidative self-polymerization. The polar polymer and the polyphenol derivative are blended to further strengthen the hydrogen bond acting force, the hydrophobic acting force and the pi-pi acting force formed between the coating and the surface of an article, so that the coating with the function of killing viruses is formed on the surface of any article.
Specifically, the first aspect of the invention provides a halamine capable of forming a virucidal coating on the surface of an article, wherein the halamine is a partially halaminated polyamine derivative having the formula [ NRX]m[NHR]1-mIn the structural formula, R is H (CH)2) n, n is 0 to 20, X is Cl, Br or I atom, m is the mole fraction of its haloaminated amine group monomer repeat units, m is 0.1-0.9, 1-m is the mole fraction of its amine group monomer repeat units.
In a second aspect of the present invention, there is provided a process for preparing the haloamine of the first aspect of the present invention, wherein the polyamine derivative is halogenated with a halogenating agent to obtain the partially haloaminated polyamine derivative having the formula:
Figure RE-GDA0003007991120000021
the preparation method comprises the following steps:
step 1, preparing a polyamine derivative solution of 100 mg/mL;
step 2, preparing effective halide cation (X) in halogenating agent+) A halogenating agent solution in an amount of 0.1 to 10% by weight;
step 3, when the mole part m of the repeat unit of the amine group monomer of the halation in the polyamine derivative is 0.1-0.9, calculating the consumption of the required effective halide cation (X +), then dropwise adding the halogenating agent solution prepared in the step 2 into the solution prepared in the step 1, and stirring while dropwise adding to ensure that the mixture reacts uniformly;
and 4, dialyzing the solution subjected to the halogenation reaction in the step 3 to obtain the halamine of the polyamine derivative with partial halation. The concentration is 1-100mg/mL, and the effective halide cation (X) is titrated by standard starch potassium iodide solution+) The content is 0.1-20 wt%;
or after the step 4, performing a step 5:
and 5, adding polar macromolecules such as: polyvinyl alcohol (PVA), polyethylene glycol (PEG), Alginic Acid (Alginic Acid) and Polyetherimide (polyethylenide) with the concentration of 0-5 mg/mL;
or step 6 is carried out after step 4:
and 6, adding polyphenol derivatives such as: tannic acid (Tannic acid), Dopamine (Dopamine), the concentration of which is 0-5 mg/mL;
or after step 4, performing step 7:
and 7, adding the polar polymer and the polyphenol derivative into the solution obtained in the step 4, wherein the mixture comprises the following components: polyvinyl alcohol (PVA) and Tannic acid (Tannic acid) or polyethylene glycol (PEG) and Dopamine (Dopamine) or Tannic acid (Tannic acid) and polyethylene glycol (PEG), wherein the molar ratio of the polar polymer to the polyphenol derivative is 0.2-0.8, and the concentrations of the polar polymer and the polyphenol derivative are 0.05-5mg/mL respectively.
By using the solution treated in the step 5, the step 6 or the step 7 as a coating solution, a hydrogen bond acting force, a hydrophobic acting force and a pi-pi acting force which are formed between the coating and the surface of the article can be further strengthened, and the coating with the function of killing viruses can be formed on the surface of any article.
Preferably, the polyamine derivatives in step 1 include: polyallylamine, dopamine derivatives, chitosan, hyaluronic acid, polyacrylamide, poly (N-isopropylacrylamide), polyethyleneimine or N-methylformamide.
Preferably, the halogenating agent in step 2 is hypo-X acid, sodium hypo-X acid or calcium hypo-X acid.
Preferably, the effective halide cation (X) in the halogenating agent described in step 2+) The content of (B) is 0.5-5 wt%.
Preferably, m, which is the mole fraction of the monomeric repeating units of the amine group of the haloaminated amine group in the polyamine derivative in step 3, is 0.2-0.8.
Preferably, the partially haloaminated polyamine derivative of step 4 has a concentration of 10-80mg/mL of halamine, and the effective halide cation of the partially haloaminated polyamine derivative is titrated from the halamine solution in a standard potassium iodide starch solution (X)+) The content is 0.5-10 wt%.
Preferably, the polar polymer is added in step 5 at a concentration of 0.1-2 mg/mL.
Preferably, the concentration of the polyphenol derivative added in the step 6 is 0.1-2 mg/mL.
Preferably, in step 7, the polar polymer and the polyphenol derivative are added in a molar ratio of 0.2 to 0.8, and the concentrations thereof are 0.05 to 5mg/mL, respectively.
In a third aspect of the present invention, there is provided a method for forming a coating having a virucidal function on a surface of an article, in which a coating liquid is applied to the surface of the article by a dipping method or a spraying method, comprising the steps of:
step 1, cleaning impurity treatment is carried out on the surface of an article to be coated to obtain a surface-cleaned article;
and 2, soaking the article obtained in the step 1 in a halamine solution containing the partially halated polyamine derivative provided by the first aspect and the second aspect of the invention for 0.5-24h, and washing the soaked article with water.
Or after step 1, performing the following steps:
step 3, spraying a halamine solution containing the partially halated polyamine derivative provided by the first and second aspects of the invention on the surface of the sample obtained in step 1, wherein the spraying frequency is more than 1; the preferred number of spraying is 3 or more.
Preferably, the article in step 2 is: artificially synthesized or natural polymer, inorganic non-metal material and metal product.
Preferably, the soaking time in the step 3 is 10-15 h.
Preferably, the spraying times in the step 4 are 4-8 times.
In a fourth aspect of the invention, a method is provided for verifying that a coating formed on a surface of an article has a virucidal effect.
The virucidal mechanism is shown:
Figure RE-GDA0003007991120000041
the sterilization mechanism is briefly described as follows: the presence of N-X bonds in partially haloaminated polyamine derivatives produces X which is oxidative and virucidal in hydrolysis+Ions.
A method for verifying virucidal effects, comprising the steps of:
step 1, preparing a virus solution: preparing the virus to a concentration of 1X 108PFU/mL of 10mL virus solution;
step 2, after the virucidal article prepared in the third aspect was controlled to a size of 2cm × 2cm, it was placed in the virus solution prepared in step 1, and the suspension (0.1mL) was sampled immediately after the addition of the sample (time zero), and then sampled at intervals described in the results. Virucidal effect was evaluated by serial 10-fold dilutions of samples in quarter strength Ringer solution and double agar assay to determine the number of viable viruses in each dilution.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Detailed Description
The exemplary embodiments will be described herein in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely representative examples of the invention. The excellent effects of the present invention in practical application are more prominent by these exemplary embodiments.
The technical solution of the present invention will be described in detail below with specific examples.
Example 1
Step 1, preparing a polyallylamine solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing available chlorine cations (Cl) in chlorinating agent+) A chlorinating agent solution in an amount of 5.00 wt%;
step 3, when the mole fraction m of the monomer repeating units of the amine groups subjected to the haloamination in the polyallylamine solution is 0.4, calculating the consumption of the required effective chlorine cations (Cl +), dropwise adding the chlorinating agent solution prepared in the step 2 into the solution prepared in the step 1, and stirring while dropwise adding to ensure that the solution is subjected to uniform reaction;
and 4, dialyzing the solution prepared in the step 3 to obtain a polyamine derivative solution with partial chloramination. The concentration is 50mg/mL, and the available chlorine cation (Cl) is titrated by a standard starch potassium iodide solution+) The content is 2.00 wt%;
step 5, selecting cotton cloth as a coated substrate article (material);
step 6, treating the cotton cloth for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the cotton cloth for multiple times by using ultrapure water;
and 7, soaking the sample in the step 6 in the solution in the step 4 for 8 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washed clean with water.
The titration results for the chloramine coating are shown in table 1: articles in the presence of available chlorine cations (Cl)+) Available chlorine cation (Cl) after soaking for 8 hours in a solution of partially chloraminated polyamine derivative with the content of 2.00 wt%+) The content was 1.30 wt%.
The cotton cloth loaded with the halamine coating can be obtained through the steps.
The virucidal effect of the cotton cloth bearing the halamine-loaded coating was evaluated as follows.
Step 9, preparing an H9N2 virus solution: preparing the virus to a concentration of 1X 108PFU/mL of 10mL virus solution;
and 10, controlling the size of the prepared object in the step 7 to be 2cm multiplied by 2cm, placing the object in the virus solution prepared in the step 9, culturing for 48 hours, then continuously diluting the virus solution in one-quarter strength Ringer solution for 10 times of samples, and measuring the number of the surviving viruses in each dilution by a double-layer agar method.
Step 11, detecting a nucleic acid kit on the surface of the article, and evaluating whether the virus on the surface of the article has activity and further has infection capacity: positive is that the virus has activity and has the ability of infection; negative means that the virus is inactive and has no infectious capacity. And (3) carrying out nucleic acid kit detection on the surface of the article soaked in the step (10), wherein the nucleic acid detection result is negative.
As can be seen from the above steps, the invention has the function of efficiently inactivating the H9N2 virus, as shown in Table 3: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 4: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thus, the chloramine coating of the present invention was verified for virucidal against the H9N2 virus.
Example 2
Step 1, preparing a polyethyleneimine solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing available chlorine cations (Cl) in chlorinating agent+) A chlorinating agent solution in an amount of 5.00 wt%;
step 3, when the mole fraction m of the monomer repeating units of the chloraminated amine group in the polyethyleneimine solution is 0.4, calculating the required available chloride cation (Cl)+) The chlorinating agent solution prepared in the step 2 is added into the solution prepared in the step 1 dropwise while stirring, so that the chlorination reaction is carried out uniformly;
and 4, dialyzing the solution prepared in the step 3 to obtain a polyamine derivative solution with partial chloramination. The concentration is 100mg/mL, and the available chlorine cation (Cl) is titrated by a standard potassium iodide starch solution+) The content is 2.00 wt%;
step 5, selecting cotton cloth as a coated substrate article (material);
step 6, treating the cotton cloth for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the cotton cloth for multiple times by using ultrapure water;
and 7, soaking the sample in the step 6 in the solution in the step 4 for 12 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washing the mixture by water;
step 8, titrating the article obtained in the step 7 by using a standard starch potassium iodide solution to determine available chlorine cations (Cl)+) Content (c);
the titration results for the chloramine coating are shown in table 1: articles in the presence of available chlorine cations (Cl)+) Available chlorine cation (Cl) after soaking for 12 hours in a solution of partially chloraminated polyamine derivative with the content of 2.00 wt%+) The content was 1.20 wt%.
The cotton cloth loaded with the chloramine coating can be obtained through the steps.
The virucidal effect of cotton cloth bearing a chloramine coating was evaluated as in example 1, step 9, step 10 and step 11.
As can be seen by evaluation, the invention has the function of efficiently inactivating the H9N2 virus, as shown in Table 3: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 4: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal effect of the chloramine coating against the H9N2 virus.
Example 3
Step 1, preparing a poly-N-methylformamide solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing available chlorine cations (Cl) in chlorinating agent+) A chlorinating agent solution in an amount of 3.00 wt%;
step 3, when the mole fraction m of the monomer repeating units of the chloraminated amine group in the N-methylformamide solution is 0.4, calculating the required available chloride cation (Cl)+) The chlorinating agent solution prepared in the step 2 is added into the solution prepared in the step 1 dropwise while stirring, so that the chlorination reaction is carried out uniformly;
and 4, dialyzing the solution prepared in the step 3 to obtain a polyamine derivative solution with partial chloramination. The concentration is 60mg/mL, and the available chlorine cation (Cl) is titrated by a standard starch potassium iodide solution+) The content is 2.50 wt%;
step 5, selecting cotton cloth as a coated substrate article (material);
step 6, treating the cotton cloth for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the cotton cloth for multiple times by using ultrapure water;
and 7, soaking the sample in the step 6 in the solution in the step 4 for 8 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washing the mixture by water;
step 8, carrying out standard starch potassium iodide solution titration on the article obtained in the step 7,determination of available chlorine cations (Cl) in coatings+) Content (c);
the titration results for the chloramine coating are shown in table 2: articles in the presence of available chlorine cations (Cl)+) Available chlorine cation (Cl) after soaking for 8 hours in a solution of partially chloraminated polyamine derivative with the content of 2.50 wt%+) The content was 1.20 wt%.
The cotton cloth loaded with the chloramine coating can be obtained through the steps.
The virucidal effect of cotton cloth bearing a chloramine coating was evaluated as in example 1, step 9, step 10 and step 11.
As can be seen by evaluation, the invention has the function of efficiently inactivating the H9N2 virus, as shown in Table 3: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 4: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal effect of the chloramine coating against the H9N2 virus.
Example 4
Step 1, preparing a polyallylamine solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing effective bromine cation (Br) in brominating agent+) A brominating agent solution with the content of 4 wt%;
step 3, when the mole fraction m of the monomer repeating units of the bromated amine group in the N-methylformamide solution is 0.5, calculating the required effective bromine cation (Br)+) The brominating agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the brominating agent solution reacts uniformly;
and 4, dialyzing the solution prepared in the step 3 to obtain a polyamine derivative solution with partial bromine amination. The concentration is 60mg/mL, and the effective bromine cation (Br) is titrated by standard starch potassium iodide solution+) The content is 2.00 wt%;
step 5, selecting non-woven fabric as a coated substrate article (material);
step 6, processing the non-woven fabric for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the non-woven fabric for multiple times by using ultrapure water;
and 7, soaking the sample in the step 6 in the solution in the step 4 for 8 hours, and continuously stirring the solution to uniformly distribute the solution. Then washing the mixture by water;
step 8, titrating the article obtained in the step 7 by a standard starch potassium iodide solution to determine effective bromine cations (Br) in the coating+) Content (c);
the titration results for the bromamine coating are shown in table 1: articles in the presence of effective bromine cation (Br)+) Effective bromine cation (Br) after soaking for 8 hours in 2.00 wt% of partially bromaminated polyamine derivative solution+) Bromamine in an amount of 1.25 wt%.
The non-woven fabric loaded with the bromamine coating can be obtained through the steps.
The virucidal effect of the resulting bromamine-loaded coated nonwoven fabric was evaluated with reference to example 1, step 9, step 10 and step 11, except that a H6N2 virus solution was prepared.
As can be seen by evaluation, the invention has the function of efficiently inactivating the H6N2 virus, as shown in Table 3: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 4: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal activity of the bromamine coating against the H6N2 virus.
Example 5
Step 1, preparing a chitosan solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing effective bromine cation (Br) in brominating agent+) A brominating agent solution with a content of 4.00 wt%;
step 3, when the mole fraction m of the monomer repeating units of the amine group subjected to bromamination in the chitosan solution is 0.7, calculating the required effective bromine cation (Br)+) The brominating agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the brominating agent solution reacts uniformly;
and 4, dialyzing the solution prepared in the step 3 to obtain a polyamine derivative solution with partial bromine amination. The concentration is 60mg/mL, and the effective bromine cation (Br) is titrated by standard starch potassium iodide solution+) The content is 2.00 wt%;
step 5, selecting non-woven fabric as a coated substrate article (material);
step 6, processing the non-woven fabric for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the non-woven fabric for multiple times by using ultrapure water;
and 7, soaking the sample in the step 6 in the solution in the step 4 for 12 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washing the mixture by water;
step 8, titrating the article obtained in the step 7 by a standard starch potassium iodide solution to determine effective bromine cations (Br) in the coating+) Content (c);
the titration results for the bromamine coating are shown in table 1: articles in the presence of effective bromine cation (Br)+) The effective bromine cation (Br) after soaking for 12 hours in a solution of partially bromated polyamine derivative with the content of 2.00 wt%+) Bromamine in an amount of 1.20 wt%.
The non-woven fabric loaded with the bromamine coating can be obtained through the steps.
The virucidal effect of the resulting bromamine-loaded coated nonwoven fabric was evaluated with reference to example 1, step 9, step 10 and step 11, except that a H6N2 virus solution was prepared.
As can be seen by evaluation, the invention has the function of efficiently inactivating the H6N2 virus, as shown in Table 3: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 4: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal activity of the bromamine coating against the H6N2 virus.
Example 6
Step 1, preparing a chitosan solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing effective bromine cation (Br) in brominating agent+) A brominating agent solution with a content of 5.00 wt%;
step 3, when the mole fraction m of the monomer repeating units of the amine group subjected to bromamination in the chitosan solution is 0.6, calculating the required effective bromine cation (Br)+) The brominating agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the brominating agent solution reacts uniformly;
and 4, dialyzing the solution prepared in the step 3 to obtain a polyamine derivative solution with partial bromine amination. The concentration is 70mg/mL, and effective bromine cation (Br) is titrated by standard starch potassium iodide solution+) The content is 2.50 wt%;
step 5, selecting non-woven fabric as a coated substrate article (material);
step 6, processing the non-woven fabric for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the non-woven fabric for multiple times by using ultrapure water;
and 7, soaking the sample in the step 6 in the solution in the step 4 for 8 hours, and continuously stirring the solution to uniformly distribute the solution. Then washing the mixture by water;
step 8, titrating the article obtained in the step 7 by a standard starch potassium iodide solution to determine effective bromine cations (Br) in the coating+) Content (c);
the titration results for the bromamine coating are shown in table 2: articles in the presence of effective bromine cation (Br)+) Effective bromine cation (Br) after soaking for 8 hours in 2.50 wt% of partially bromaminated polyamine derivative solution+) Bromamine in an amount of 1.15 wt%.
The non-woven fabric coating loaded with the bromamine coating can be obtained through the steps.
The virucidal effect of the resulting bromamine-loaded coated nonwoven fabric was evaluated with reference to example 1, step 9, step 10 and step 11, except that a H6N2 virus solution was prepared.
As can be seen from the evaluation, the invention has the function of efficiently inactivating the H6N2 virus, and the invention has the function of efficiently inactivating the H6N2 virus, as shown in Table 3: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 4: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal activity of the bromamine coating against the H6N2 virus.
Example 7
Step 1, preparing a polyacrylamide solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing effective iodonium cation (I) in iodizing agent+) An iodizing agent solution with the content of 5.00 wt%;
step 3, when the mole fraction m of the monomeric repeating units of the iodoaminated amine group in the polyacrylamide solution is 0.6, calculating the required available iodonium cation (I)+) The iodizing agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the reaction is uniform;
and 4, dialyzing the solution prepared in the step 3 to obtain the polyamine derivative with part of iodoamination. The concentration is 80mg/mL, and the effective iodine cation (I) is titrated by standard potassium iodide starch+) The content is 2.00 wt%;
step 5, selecting a stainless steel plate as a coated substrate article (material);
step 6, treating the stainless steel plate for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the stainless steel plate for multiple times by using ultrapure water;
and 7, soaking the sample in the step 6 in the solution in the step 4 for 8 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washing the mixture by water;
step 8, titrating the article obtained in the step 7 by a standard starch potassium iodide solution to determine effective iodine cations (I) in the coating+) Content (c);
the titration results for the iodoamine coating are shown in table 1: effective iodine cation (I) of article+) Effective iodonium cation (I) after soaking for 8 hours in 2.00 wt% of partially iodoaminated polyamine derivative solution+) Iodoamine in an amount of 1.24 wt%.
The stainless steel plate with the iodoamine coating can be obtained through the steps.
The virucidal effect of the stainless steel sheets having the iodoamine-loaded coatings obtained was evaluated with reference to step 9, step 10 and step 11 of example 1, except that a H9N1 virus solution was prepared.
As can be seen by evaluation, the invention has the function of efficiently inactivating the H9N1 virus, and the invention has the function of efficiently inactivating the H9N1 virus, as shown in Table 3: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 4: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal activity of the iodoamine coating against the H9N1 virus.
Example 8
Step 1, preparing a poly (N-isopropylacrylamide) solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing effective iodonium cation (I) in iodizing agent+) An iodizing agent solution with the content of 5.00 wt%;
step 3, when the mole fraction m of the monomer repeating units of the iodoaminated amino group in the poly (N-isopropylacrylamide) solution is 0.8, calculating the required effective iodineHalide cation (I)+) The iodizing agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the reaction is uniform;
and 4, dialyzing the solution prepared in the step 3 to obtain the polyamine derivative with part of iodoamination. The concentration is 70mg/mL, and effective iodine cation (I) is titrated by standard starch potassium iodide solution+) The content is 2.00 wt%;
step 5, adding a tannic acid solution with the concentration of 2mg/mL into the solution obtained in the step 4;
step 6, selecting a stainless steel plate as a coated substrate article (material);
step 7, treating the stainless steel plate for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the stainless steel plate for multiple times by using ultrapure water;
and 8, soaking the sample in the step 7 in the solution in the step 5 for 12 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washing the mixture by water;
step 9, titrating the article obtained in the step 8 by using a standard starch potassium iodide solution to determine effective iodine cations (I) in the coating+) Content (c);
the titration results for the iodoamine coating are shown in table 5: effective iodine cation (I) of article+) Effective iodonium cation (I) after soaking for 12 hours in 2.00 wt% of partially iodoaminated polyamine derivative solution+) Iodoamine in an amount of 1.20 wt%.
The stainless steel plate with the iodoamine coating can be obtained through the steps.
The virucidal effect of the stainless steel sheets having the iodoamine-loaded coatings obtained was evaluated with reference to step 9, step 10 and step 11 of example 1, except that a H9N1 virus solution was prepared.
As can be seen from the evaluation, the invention has the function of efficiently inactivating the H9N1 virus, and the invention has the function of efficiently inactivating the H9N1 virus, as shown in Table 8: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 9: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal activity of the iodoamine coating against the H9N1 virus.
Example 9
Step 1, preparing a polyallylamine solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing effective iodonium cation (I) in iodizing agent+) An iodizing agent solution with the content of 1.00 wt%;
step 3, when the mole fraction m of the monomeric repeating units of the iodinated amino group in the polyallylamine solution is 0.8, calculating the required available iodonium cation (I)+) The iodizing agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the reaction is uniform;
and 4, dialyzing the solution prepared in the step 3 to obtain the polyamine derivative with part of iodoamination. The concentration is 80mg/mL, and effective iodine cation (I) is titrated by standard starch potassium iodide solution+) The content is 2.50 wt%;
step 5, adding a polyethylene glycol solution with the concentration of 2mg/mL into the solution in the step 4;
step 6, selecting a stainless steel plate as a coated substrate article (material);
step 7, treating the stainless steel plate for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the stainless steel plate for multiple times by using ultrapure water;
and 8, soaking the sample in the step 7 in the solution in the step 5 for 10 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washing the mixture by water;
or after step 7, step 9
Step 9, spraying the solution in the step 5 on the sample in the step 7, spraying for 4 times to enable the solution to be uniformly distributed, and then washing the sample clean with water;
step 10, the articles obtained in the step 8 or the step 9 are put intoPerforming standard potassium iodide solution titration on starch to determine effective iodine cation (I) in the coating+) Content (c);
the titration results for the iodoamine coating are shown in table 6: effective iodine cation (I) of article+) Effective iodonium cation (I) after soaking for 10 hours in 2.50 wt% of partially iodoaminated polyamine derivative solution+) Iodoamine in an amount of 1.45 wt%.
The stainless steel plate with the iodoamine coating can be obtained through the steps.
The virucidal effect of the stainless steel sheets having the iodoamine-loaded coatings obtained was evaluated with reference to step 9, step 10 and step 11 of example 1, except that a H9N1 virus solution was prepared.
As can be seen from the evaluation, the invention has the function of efficiently inactivating the H9N1 virus, and the invention has the function of efficiently inactivating the H9N1 virus, as shown in Table 8: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 9: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal activity of the iodoamine coating against the H9N1 virus.
Example 10
Step 1, preparing a polyacrylamide solution, wherein the concentration of the solution is 100 mg/mL;
step 2, preparing effective iodonium cation (I) in iodizing agent+) An iodinating agent solution with a content of 4.00 wt%;
step 3, when the mole fraction m of the monomeric repeating units of the iodoaminated amine group in the polyacrylamide solution is 0.7, calculating the required available iodonium cation (I)+) The halogenating agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the mixture reacts uniformly;
step 4, dialyzing the solution prepared in the step 3 to obtain polyamine with part of iodoaminationA derivative of the class. The concentration is 80mg/mL, and effective iodine cation (I) is titrated by standard starch potassium iodide solution+) The content is 3.00 wt%;
step 5, adding 1mg/mL polyethyleneimine and 1mg/mL dopamine into the solution obtained in step 4, wherein the molar ratio of the polyetherimide to the dopamine is 0.2;
step 6, selecting a stainless steel plate as a coated substrate article (material);
step 7, treating the stainless steel plate for 5min in an oxygen environment of a plasma cleaning machine, removing organic impurities on the surface, and ultrasonically cleaning the stainless steel plate for multiple times by using ultrapure water;
and 8, soaking the sample in the step 7 in the solution in the step 5 for 12 hours, and continuously stirring the solution during the soaking period to uniformly distribute the solution. Then washing the mixture by water;
or step 9 is carried out after step 8
And 9, spraying the solution in the step 5 on the sample in the step 7 for 4 times to uniformly distribute the solution. Then washing the mixture by water;
step 10, titrating the article obtained in the step 8 or the step 9 by a standard starch potassium iodide solution to determine effective iodine cations (I) in the coating+) Content (c);
the titration results for the iodoamine coating are shown in table 7: effective iodine cation (I) of article+) The effective iodine cation (I) is obtained after soaking a solution of partially iodoaminated polyamine derivative with the content of 3.00 wt% for 10 hours+) Iodoamine in an amount of 1.50 wt%.
The stainless steel plate with the iodoamine coating can be obtained through the steps.
The virucidal effect of the stainless steel sheets having the iodoamine-loaded coatings obtained was evaluated with reference to step 9, step 10 and step 11 of example 1, except that a H9N1 virus solution was prepared.
As can be seen by evaluation, the invention has the function of efficiently inactivating the H9N1 virus, as shown in Table 8: the number of the live viruses in the solution after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours is zero, while the number of the live viruses in the solution after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours is kept unchanged. As shown in table 9: after the cotton cloth coated on the experimental group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is negative, and after the cotton cloth coated on the control group is soaked in the virus solution for 48 hours, the nucleic acid detection on the surface of the article is positive. Thereby verifying the virucidal activity of the iodoamine coating against the H9N1 virus.
Table 1: effective halogen (X) in a coating on a supported article+) The content of (A) is in a statistical table along with the change of soaking time under a certain soaking concentration.
Figure RE-GDA0003007991120000141
Table 2: effective halogen (X) in a coating on a supported article+) The content of (A) is in a statistical table along with the change of the soaking concentration under a certain soaking time.
Figure RE-GDA0003007991120000142
Table 3: virucidal coatings on the loaded articles (tables 1 and 2) for viruses: H9N2, H6N2, H9N1 survival statistics table.
Figure RE-GDA0003007991120000151
Table 4: statistics of nucleic acid system detection results on the surface of the virucidal articles (tables 1 and 2).
Experimental coated article Virus Results of nucleic acid detection
Cotton cloth H9N2 Negative of
Non-woven fabric H6N2 Negative of
Stainless steel plate H9N1 Negative of
Control coated article Virus Results of nucleic acid detection
Cotton cloth H9N2 Positive for
Non-woven fabric H6N2 Positive for
Stainless steel plate H9N1 Positive for
Table 5: adding polyphenol derivative into the coating liquid for loading the article, and soaking for a certain time to obtain effective halogen (X) contained in the coating of the article+) And (4) concentration.
Figure RE-GDA0003007991120000161
Table 6: coatings on load bearing articlesAdding polar polymer into the solution, and soaking for a certain time at a certain soaking concentration to obtain effective halogen (X) contained in the coating+) And (4) concentration.
Figure RE-GDA0003007991120000162
Table 7: adding polar polymer and polyphenol derivative into the coating liquid to coat the article with effective halogen (X)+) And (4) concentration.
Figure RE-GDA0003007991120000163
Table 8: virucidal coatings on the loaded articles (tables 5 and 7) for viruses: H9N2, H6N2, H9N1 survival statistics table.
Figure RE-GDA0003007991120000171
Table 9: statistics of nucleic acid system measurements on the surface of the virucidal articles (tables 5 and 7).
Experimental coated article Virus Results of nucleic acid detection
Cotton cloth H9N2 Negative of
Non-woven fabric H6N2 Negative of
Stainless steel plate H9N1 Negative of
Control coated article Virus Results of nucleic acid detection
Cotton cloth H9N2 Positive for
Non-woven fabric H6N2 Positive for
Stainless steel plate H9N1 Positive for

Claims (10)

1. A coating with antivirus function is formed on the surface of an article, the antivirus component of the coating is halamine of polyamine derivative partially halated and aminated, and the structural formula of the coating is [ NRX]m[NHR]1-mIn the structural formula, R is H (CH)2) n, n is 0 to 20, X is Cl, Br or I atom, m is the mole fraction of its haloaminated amine group monomer repeat units, m is 0.1-0.9, 1-m is the mole fraction of its amine group monomer repeat units.
2. A process for preparing a halamine of the partially haloaminated polyamine-based derivative of claim 1, which is obtained by halogenating a polyamine-based derivative with a halogenating agent, comprising the steps of:
step 1, preparing a polyamine derivative solution of 100 mg/mL;
step 2, preparing effective halide cation X in halogenating agent+A halogenating agent solution in an amount of 0.10 to 10.00% by weight;
step 3, when the mole part m of the repeated unit of the amine group monomer of the halogen amination in the polyamine derivative is 0.1-0.9, calculating the needed effective halide cation X+The halogenating agent solution prepared in the step 2 is added into the solution prepared in the step 1 drop by drop while stirring, so that the mixture reacts uniformly;
step 4, dialyzing the solution which is subjected to the halogenation reaction in the step 3 to obtain the halamine of the polyamine derivative with partial halation, wherein the concentration of the halamine is 1-100mg/mL, and titrating the effective halide cation X of the halamine by a standard potassium iodide starch solution+The content is 0.10-20.00 wt%.
3. The method of claim 2, after step 4, performing step 5:
step 5, adding a polar polymer into the solution obtained in the step 4, wherein the polar polymer is polyvinyl alcohol, polyethylene glycol, alginic acid or polyethyleneimine, and the concentration of the polar polymer is 0-5 mg/mL; or step 6 is carried out after step 4:
step 6, adding a polyphenol derivative into the solution obtained in the step 4, wherein the polyphenol derivative is tannic acid or dopamine, and the concentration of the polyphenol derivative is 0-5 mg/mL; or after step 4, performing step 7:
and 7, adding a polar polymer and a polyphenol derivative into the solution obtained in the step 4, wherein the polar polymer and the polyphenol derivative comprise: polyvinyl alcohol and tannic acid, polyethylene glycol and dopamine or tannic acid and polyethylene glycol, wherein the molar ratio of the polar polymer to the polyphenol derivative is 0.2-0.8, and the concentrations of the polar polymer and the polyphenol derivative are 0.05-5mg/mL respectively.
4. The method according to claim 2 or 3, wherein the polyamine derivative in step 1 comprises: polyallylamine, dopamine derivatives, chitosan, hyaluronic acid, polyacrylamide, poly (N-isopropylacrylamide), polyethyleneimine or N-methylformamide.
5. The process of claim 2 or 3, wherein the halogenating agent in step 2 is a hypo-X acid, sodium hypo-X acid or calcium hypo-X acid, and the effective halide cation X in the halogenating agent+The content of (B) is 0.50-5.00 wt%.
6. The method according to claim 2 or 3, wherein m is 0.2-0.8 mole fraction of the repeating units of the amine group monomer in the polyamine derivative in step 3.
7. The process of claim 2 or 3, wherein the partially haloaminated polyamine derivative of step 4 has a halamine concentration of 10-80mg/mL and an effective halide cation X+The content is 0.50-10.00 wt%.
8. The method according to claim 2 or 3,
adding polar polymer with the concentration of 0.1-2mg/mL in the step 5;
in the step 6, the concentration of the added polyphenol derivative is 0.1-2 mg/mL;
in step 7, the polar polymer and the polyphenol derivative are added in a molar ratio of 0.2 to 0.8, and the concentrations of the polar polymer and the polyphenol derivative are respectively 0.05 to 5 mg/mL.
9. A coating method for forming a coating with a virucidal function on a surface of an article, comprising the steps of:
step 1, cleaning impurity treatment is carried out on the surface of an article to be coated to obtain an article with a clean surface;
step 2, soaking the article obtained in the step 1 in the solution prepared according to any one of claims 2 to 8 for 0.5 to 24 hours, and washing the soaked article with water;
or after step 1, performing the following steps:
and 3, spraying the solution prepared in the claim 2 or 3 on the surface of the article obtained in the step 1 for more than 1 time, and washing the sprayed article with water.
10. The method of claim 8, the coated article comprising: artificially synthesized or natural polymer, inorganic non-metal material and metal product.
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Citations (7)

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