CN113527588A - Antibacterial emulsion and preparation method and application thereof - Google Patents

Antibacterial emulsion and preparation method and application thereof Download PDF

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CN113527588A
CN113527588A CN202010308903.1A CN202010308903A CN113527588A CN 113527588 A CN113527588 A CN 113527588A CN 202010308903 A CN202010308903 A CN 202010308903A CN 113527588 A CN113527588 A CN 113527588A
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antibacterial
emulsion
monomers
repeating units
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宋其亮
葛世才
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Shandong Erya Gene Technology Co ltd
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Shandong Erya Gene Technology Co ltd
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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

The invention provides an antibacterial emulsion, a preparation method and application thereof, which are different from chemical bactericides in the prior art and can effectively inhibit the attachment and the propagation of microorganisms on the surface from the physical effect, thereby achieving the effects of bacteriostasis and sterilization. The antibacterial emulsion microparticles are high molecular polymers with a brush structure, do not contain chemical bactericides, have good heat resistance and durability, do not generate drug resistance, and are safe and nontoxic; the paint does not contain inorganic silver ions, has good dispersion stability in the paint, low price and good antibacterial effect on fungi and mould; the photocatalyst nano metal particles are not contained, ultraviolet rays are not needed, and potential safety hazards are avoided.

Description

Antibacterial emulsion and preparation method and application thereof
Technical Field
The invention belongs to the technical field of antibacterial agents, and particularly relates to an antibacterial emulsion and a preparation method and application thereof.
Background
Microorganisms such as bacteria and mold are widely existed in the daily living environment of people, and the microorganisms are easily adhered to the surfaces of materials such as daily necessities, household appliances, building coatings, ceramics, fiber products and the like, so that the materials are damaged, and the health of people is also harmed. Therefore, antimicrobial treatment of materials is an important means to effectively prevent the growth and reproduction of various bacteria, kill bacteria, and prevent the spread of infection by bacteria. Antibacterial agents are a class of additives used to antimicrobially treat or render a material antimicrobial, and most prior art antibacterial agents are chemical antibacterial agents, generally classified as organic and inorganic antibacterial agents, which can kill bacteria by disrupting cell membranes.
For example, the Chinese patent application CN107603315A adds an organic bactericide bromochlorohydantoin, which can release hypobromous acid and hypochlorous acid in water as a chemical bactericide, and the hypobromous acid and hypochlorous acid denature proteins to achieve the bactericidal and mildewproof effects. However, it is inferior in heat resistance and safe in toxicity, and the drug resistance of the strain is developed by long-term use.
Chinese patent application CN109517414A discloses that the silver ion-containing supported diatomite coating has good antibacterial effect, the inorganic silver ion antibacterial effect is good, the inorganic silver ion antibacterial effect is broad-spectrum antibacterial, but the inorganic silver ion antibacterial coating is easy to oxidize and lose efficacy, the dispersion stability in the coating is poor, the antibacterial effect on mold and fungi is poor, and the cost is high.
The Chinese patent application CN110256916A adopts the method that antibacterial nano titanium dioxide and catalyst TiO are added into the formula2The nano particles can play the role of antibiosis and sterilization only under the irradiation of an ultraviolet lamp, and the nano metal particles are easy to migrate, and the migrated products can induce cancers, so that serious potential safety hazards exist.
Disclosure of Invention
In view of the above-mentioned defects in the prior art, the present invention aims to provide an antibacterial emulsion, a preparation method and an application thereof, which are different from the chemical bactericides in the prior art and can effectively inhibit the attachment and propagation of microorganisms on the surface from the physical effect, so as to achieve the antibacterial and bactericidal effects. The antibacterial emulsion microparticles are high molecular polymers with a brush structure, do not contain chemical bactericides, have good heat resistance and durability, do not generate drug resistance, and are safe and nontoxic; the paint does not contain inorganic silver ions, has good dispersion stability in the paint, low price and good antibacterial effect on fungi and mould; the photocatalyst nano metal particles are not contained, ultraviolet rays are not needed, and potential safety hazards are avoided.
In order to achieve the above object, in a first aspect, the present invention provides an antibacterial emulsion comprising a high molecular copolymer, an initiator and water; the high-molecular copolymer is obtained by copolymerizing at least two monomers containing carbon-carbon double bonds (namely, at least a first monomer and a second monomer), and comprises a main chain and a branched chain; wherein the content of the first and second substances,
the main chain is obtained by polymerizing carbon-carbon double bonds in the monomer;
at least a part of the branched chains include repeating units containing ether bonds, and the average molecular weight of the branched chains including the repeating units containing ether bonds is 1000 or more.
Further, the repeating unit containing ether bond is selected from-OCH2CH2-、-OCH2CHCH3-、-OCHCH3CH2-、-OCH2CH2CH2CH2-one or more of (a) and (b).
Further, the repeating unit containing an ether bond is provided by the first monomer, and when the repeating unit in the first monomer is two or more, the respective repeating units are arranged randomly, blockwise or alternately.
Further, the molecular structural formula of the first monomer is selected from one or more of the following molecular structural formulas:
Figure BDA0002456881070000021
Figure BDA0002456881070000031
Figure BDA0002456881070000041
Figure BDA0002456881070000051
Figure BDA0002456881070000052
wherein R is11Is H atom or C1-C5 alkyl, R12Is H atom or alkyl, and at least one of n, m, p and q is more than or equal to 2.
It should be noted that the above molecular structural formula is only for illustrating the possible combination relationship among the four repeating units, and it is not meant that the arrangement order thereof is also limited by the above molecular structural formula. For example, according to a general understanding, the molecular formula
Figure BDA0002456881070000053
In (b), the repeating unit-OCH2CH2-and-OCH2CHCH3Repeating n times and m times respectively, the two repeating units being in block copolymerization relationship. However, in the present invention, this molecular formula represents only the presence of-OCH2CH2-and-OCH2CHCH3Two repeating units, the total number of which is n and m, respectively, but which may form a block copolymerization relationship, or may form a random copolymerization or alternating copolymerization relationship.
It should also be noted that all the above-mentioned repeating units are not limited to their mutual connection directionality, and the repeating units may also be connected end to end; all of the above-mentioned repeating units are not limited to isomers that may be produced during the formation thereof, and the repeating units may be represented by other isomers. E.g. repetitionUnit-OCH2CH2-can both represent- (OCH)2CH2)nThe connection form of- (CH) may be2CH2O)n-connection means. Also for example, methallyl polypropylene oxide
Figure BDA0002456881070000061
Repeating unit of-OCH2CHCH3Is formed by the polymerization of propylene oxide, which may also give-OCHCH during the polymerization3CH2Isomers of repeating units, thus methallylpolypropyleneoxide may also be represented by
Figure BDA0002456881070000062
Or
Figure BDA0002456881070000063
The three are isomers.
Further, when the repeating unit containing an ether bond is provided by the first monomer, the molecular weight of the branch chain formed by the first monomer means the molecular weight of the group of the repeating unit containing an ether bond linked to the carbon-carbon double bond in the first monomer. For example, when the first monomer is
Figure BDA0002456881070000064
When the carbon-carbon double bond is polymerized, it will become a part of the main chain and the group attached to the carbon-carbon double bond
Figure BDA0002456881070000065
(i.e., -CH)2CH2(OCH2CH2)n(OCH2CHCH3)mR12) A branch chain is formed, the molecular weight of which is greater than 2000.
Further, the average molecular weight of the branched chain comprising the repeating unit containing the ether bond is preferably 1500 to 10000; more preferably 2000 to 5000. The molecular weight of the branched chain plays an important role in the physical antibacterial effect of the antibacterial emulsion, the branched chain within the molecular weight range can reach enough length, and the ether bond has larger flexibility, so that the surface of the microsphere particles obtained by emulsion polymerization has a brush-type structure, and large protein molecules can be effectively prevented from being attached, enriched and propagated on the surface, and the antibacterial and bacteriostatic effects are achieved.
Further, the adding amount of the first monomer accounts for 0.5-50% of the total weight of all the monomers.
Further, the average molecular weight M of the branches (in 1) is related to the amount w of the first monomer added (in wt% based on the total weight of all monomers): m w is more than or equal to 2000. This relationship is an empirical equation obtained by the inventors through extensive experimentation, which indicates that when M is small, the branches containing ether linkages are short, and therefore it is necessary to introduce enough branches (i.e., a large w) into the main chain to allow interaction between the branches. For example, when the average molecular weight M of the ether bond-containing branches is 2000, at least 1 wt% of the first monomer is added to ensure that the main chain has enough branches to achieve the physical antibacterial and bacteriostatic effects.
Furthermore, the monomers forming the high molecular copolymer also comprise a water-soluble second monomer, and the second monomer is selected from one or more of acrylic acid, acrylamide and methacrylic acid monomers.
Further, the second monomer is pre-neutralized with a base (e.g., sodium hydroxide or potassium hydroxide) before polymerization, and the degree of neutralization is 0.1 to 99%, preferably 20 to 90%, and more preferably 70 to 90%.
Further, the addition amount of the second monomer is 1 to 99.5 percent of the total weight of all monomers, and preferably 1 to 50 percent.
Furthermore, the monomers for forming the high molecular copolymer also comprise a third monomer, and the glass transition temperature Tg of the homopolymer corresponding to the third monomer is more than or equal to 70 ℃. The addition of the monomer with higher glass transition temperature is beneficial to improving the scratch resistance of the coating when the antibacterial emulsion is used in the coating.
Further, the molecular structural formula of the third monomer is:
Figure BDA0002456881070000071
wherein the content of the first and second substances,
R31is H atom or alkyl group, R32Is an aromatic hydrocarbon radical, -OOCCH3or-COOCH3。
Further, the third monomer is selected from one or more of styrene, methyl methacrylate and vinyl acetate.
Further, the addition amount of the third monomer is 5-60% of the total weight of all the monomers.
Furthermore, the monomers forming the high molecular copolymer also comprise a fourth monomer, and the glass transition temperature Tg of the homopolymer corresponding to the fourth monomer is less than or equal to 30 ℃. The addition of the monomer with lower glass transition temperature makes the antibacterial emulsion of the invention beneficial to improving the film forming property of the coating when being used in the coating.
Further, the molecular structural formula of the fourth monomer is:
Figure BDA0002456881070000072
wherein the content of the first and second substances,
R41is H or alkyl, R42Is an alkyl group.
Further, the fourth monomer is selected from one or more of butyl methacrylate, n-octyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, butyl acrylate, n-octyl acrylate, isobutyl acrylate, dodecyl acrylate and hexadecyl acrylate.
Further, the adding amount of the fourth monomer is 20-60% of the total weight of all the monomers.
Furthermore, the monomers forming the high molecular copolymer also comprise a fifth monomer, and the fifth monomer is quaternary ammonium salt with carbon-carbon double bonds. The quaternary ammonium salt has positive charge and is an organic antibacterial agent, and the antibacterial emulsion has physical antibacterial property and chemical antibacterial property due to the addition of the quaternary ammonium salt monomer, so that the antibacterial effect is further enhanced.
Further, the molecular structural formula of the fifth monomer is:
Figure BDA0002456881070000073
wherein R is51Is H or alkyl, R52Is alkyl quaternary ammonium salt.
Furthermore, the fifth monomer is selected from one or more of N-vinyl imidazole, vinyl pyrrolidone, dimethyl diallyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride.
Furthermore, the addition amount of the fifth monomer is 0.1-10% of the total weight of all the monomers.
Further, the antibacterial emulsion also comprises a surfactant, wherein the surfactant is an ionic surfactant.
Further, the surfactant is selected from one or more of alkyl sodium sulfonate, alkyl sodium sulfate, alkyl quaternary ammonium salt and aryl quaternary ammonium salt.
Further, the addition amount of the surfactant is 0.1-5% of the total weight of the antibacterial emulsion.
Further, in the antibacterial emulsion of the present invention, the initiator includes a first initiator, and the first initiator is an aqueous phase initiator.
Further, the first initiator is selected from one or more of potassium persulfate, sodium persulfate, ammonium persulfate and hydrogen peroxide.
Further, the adding amount of the first initiator is 0.05-5% of the total weight of all monomers.
Further, in the antibacterial emulsion of the present invention, the initiator further includes a second initiator, and the second initiator is an oil phase initiator.
Further, the second initiator is selected from one or more of azo initiators and diacyl peroxide initiators.
Further, the adding amount of the second initiator is 0.05-5% of the total weight of all monomers.
Further, in the antibacterial emulsion of the present invention, the weight of water is 30 to 90% of the total weight of the antibacterial emulsion, preferably 40 to 60%.
In a second aspect, the present invention provides a preparation method of the above antibacterial emulsion, comprising the following steps:
(4) dissolving a second monomer in water, and adding a first monomer after preneutralization; optionally, other monomers such as a third monomer and/or a fourth monomer and/or a fifth monomer are added according to needs;
(5) adding a surfactant, stirring until the mixture is fully emulsified, introducing nitrogen, and heating to 55-65 ℃;
(6) adding an initiator quickly, heating to 70-80 ℃, keeping the reaction for 1-3 hours, and cooling to room temperature; thus obtaining the antibacterial emulsion.
Further, in the step (1), the second monomer is pre-neutralized by sodium hydroxide or potassium hydroxide, and the neutralization degree is 0.1-99%, preferably 20-90%, and more preferably 70-90%.
Further, the step (1) "according to the requirement" means according to the application scenario of the antibacterial emulsion, if the final product needs better scratch resistance, a proper amount of a third monomer can be added; if better film forming properties are desired, a suitable amount of a fourth monomer may be added; if better chemical antimicrobial properties are desired, an appropriate amount of a fifth monomer may be added.
Further, the temperature rise temperature in the step (2) is preferably 60 ℃.
Further, the temperature rise temperature in step (3) is preferably 75 ℃.
Further, the reaction time in step (3) is preferably 2 hours.
In a third aspect, the antimicrobial emulsions of the present invention are useful in architectural coatings or dispersion adhesives.
Further, the building coating is emulsion paint.
Further, the dispersion adhesive is glass cement.
The antibacterial emulsion has remarkable beneficial technical effects, and is at least reflected in the following aspects:
(1) the surface of the antibacterial emulsion microparticle synthesized by the invention has a brush structure, and can effectively inhibit the attachment and reproduction of microorganisms on the surface, thereby achieving the physical antibacterial effect, and the antibacterial rate and the durable antibacterial rate can basically reach more than 95%. The antibacterial emulsion can contain no chemical bactericide, has good heat resistance, can not generate drug resistance, and is safe and nontoxic; the paint does not contain inorganic silver ions, has good dispersion stability in the paint, low price and good antibacterial effect on fungi and mould; the photocatalyst nano metal particles are not contained, ultraviolet rays are not needed, and potential safety hazards are avoided.
(2) The antibacterial emulsion of the invention can select proper monomers according to the requirements of functions and performances so as to endow different performances such as scratch resistance, film forming performance, chemical antibacterial performance and the like to a final coating product.
(3) The antibacterial emulsion disclosed by the invention is simple in synthesis and use method, low in cost and suitable for large-scale industrial application.
Drawings
FIG. 1 is a comparative illustration of the washing liquid photographs of the antibacterial emulsion sample group and the blank sample control group after 24 hours of nutrient solution culture according to a preferred embodiment of the present invention;
FIG. 2 is a comparative illustration of the washing liquid photographs after the incubation of the nutrient solution for 24 hours after the durability test of the antibacterial emulsion sample group and the blank sample control group according to the embodiment of the present invention.
Detailed Description
The following examples are given to illustrate the present invention in detail, and the following examples are given to illustrate the detailed embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
In a preferred embodiment, the antibacterial emulsion of the present invention is prepared by using the following materials as monomers, surfactants and initiators respectively:
a first monomer: methylallylethylene ether 2000
Figure BDA0002456881070000091
5.7g
A second monomer: acrylic acid 4.7g
A third monomer: styrene 40.8g
A fourth monomer: butyl acrylate 30.2g
A fifth monomer: dimethyldiallylammonium chloride 0.5g
Surfactant (b): sodium dodecyl sulfonate 0.8g
A first initiator: sodium persulfate 1.3g
A second initiator: azobisisobutyronitrile (AIBN)0.9g
Solvent: 120g of water
The antibacterial emulsion of example 1 was prepared as follows:
(1) dissolving a second monomer in water, pre-neutralizing by using sodium hydroxide, wherein the neutralization degree is 50%, and then adding the first monomer and other monomers;
(2) adding surfactant, stirring to emulsify, introducing nitrogen, and heating to 60 deg.C;
(3) quickly adding a first initiator and a second initiator, heating to 75 ℃, maintaining the reaction for 2 hours, and cooling to room temperature; thus obtaining the antibacterial emulsion.
Examples 2 to 16 and comparative examples 1 to 2
The preparation methods of the antibacterial emulsions of examples 2 to 16 and comparative examples 1 to 2 are substantially the same as example 1, except that the monomers, surfactants or initiators are different, and are respectively shown in the following table (only different components from example 1 are shown):
Figure BDA0002456881070000101
example 17
The antibacterial emulsion of example 17 was prepared in substantially the same manner as in example 1, except that the monomers, surfactants or initiators were selected as follows:
a first monomer: methacrylic acid polyoxyethylene ether ester 3000
Figure BDA0002456881070000111
5.7g
A second monomer: methacrylic acid 4.7g
A third monomer: methyl methacrylate 40.8g
A fourth monomer: 30.2g of n-octyl methacrylate
A fifth monomer: acryloxyethyltrimethylammonium chloride 0.5g
Surfactant (b): sodium dodecyl sulfate 0.8g
A first initiator: potassium persulfate 1.3g
A second initiator: dibenzoyl peroxide (BPO)0.9g
Solvent: 120g of water
Examples 18 to 21 and comparative examples 3 to 4
The preparation methods of the antibacterial emulsions of examples 18 to 21 and comparative examples 3 to 4 are substantially the same as those of example 17, except that the monomers, surfactants or initiators are different, and are respectively shown in the following table (only the components different from example 17 are listed):
Figure BDA0002456881070000112
examples 22 to 27
The preparation method of the antibacterial emulsion of the embodiment 22-27 is basically the same as that of the embodiment 1, and the difference is only that the selected first monomer is different, which is respectively shown in the following table:
Figure BDA0002456881070000113
Figure BDA0002456881070000121
examples 28 to 30
The preparation method of the antibacterial emulsion of the embodiment 28 to 30 is basically the same as that of the embodiment 17, and the difference is only that the first monomer is different, which is respectively shown in the following table:
Figure BDA0002456881070000122
according to the antibacterial coating antibacterial determination method of the national standard GB21866-2008, the antibacterial effect of the antibacterial emulsion prepared by the embodiment is tested, and the test method is as follows:
1. main equipment
Constant temperature incubator (37 +/-1 ℃), refrigerator (0-5 ℃), super clean bench, pressure steam sterilization pot, electric heating drying box, balance (precision 0.01g), sterilization plate, sterilization test tube, sterilization pipette, inoculating loop and alcohol lamp.
2. Principal material
(1) Covering the film: a polyethylene film with the standard size of (40 +/-2) mmX (40 +/-2) mm and the thickness of 0.05-0.10 mm, soaking the polyethylene film in 70% ethanol solution for 10min, washing the polyethylene film with eluent, and naturally drying the polyethylene film.
(2) Nutrient Broth (NB): adding 5.0g beef extract, 10.0g peptone and 5.0g sodium chloride into 1000mL distilled water in sequence, heating for dissolving, adjusting pH to 7.0-7.2 with 0.1mol/L NaOH solution (analytically pure), subpackaging, placing in a pressure steam sterilizer, and sterilizing at 121 deg.C for 30 min.
(3) Nutrient agar medium (NA): adding 15mL agar into 1000mL Nutrient Broth (NB), heating to melt, adjusting pH to 7.0-7.2 with 0.1mol/L NaOH solution (analytically pure), subpackaging, placing in a pressure steam sterilizer, and sterilizing at 121 deg.C for 30 min.
(4) A disinfectant: 70% ethanol solution.
(5) Eluent: 0.85% NaCl physiological saline, 0.2% Tween 80 as sterile surfactant, 0.1mol/L NaOH solution (analytically pure) to adjust pH to 7.0-7.2, subpackaging, placing in a pressure steam sterilizer, and sterilizing at 121 deg.C for 30 min.
(6) Culture solution: nutrient Broth (NB)/normal saline solution, wherein the concentration of a culture solution of escherichia coli is 1/500, the concentration of a culture solution of staphylococcus aureus is 1/100, 0.2% of sterile surfactant Tween 80 is added, the pH value is adjusted to 7.0-7.2 by 0.1mol/L NaOH solution (analytically pure), and the nutrient broth is subpackaged in a pressure steam sterilizer and sterilized at 121 ℃ for 30 min.
(7) And (3) checking strains: staphylococcus aureus and Escherichia coli
3. Sample plate
(1) Blank control panel: the control paint sample did not contain any inorganic or organic antimicrobial, mildewcide, or preservative.
(2) Antibacterial coating experiment template: adding an antibacterial emulsion component to the test plate.
4. Paint test panel preparation
Samples were taken as specified in GB/T3186 and the substrate used to prepare the test panels was a cement panel. And (3) preparing a coating according to the GB/T1727 requirement, wherein the coating is applied by two times of brush coating, the first time of surface drying is followed by the second time of brush coating, and the total thickness of the coating is less than 100 mu m of wet film. After the test plate is coated, the test plate is dried for 7 days according to the conditions specified in GB/T9278, after the test plate is ensured to be completely dried, the test plate is cut into 10 test plates with the size of 50mm multiplied by 50mm, and the test plate is sterilized by an ultraviolet sterilizing lamp for 5min before the experiment for standby.
5. Inspection program
(1) And (3) strain preservation: inoculating the strain on slant of nutrient agar culture medium (NA), culturing at 37 + -1 deg.C for 24 hr, and preserving at 0-5 deg.C (no more than 1 month) to obtain slant preserved strain.
(2) Activating strains: the strain with preservation time not more than 2 weeks is used, the slant preserved strain is transferred to a plate nutrient agar culture medium, the culture is carried out for 18-20h at 37 +/-1 ℃, and a fresh bacterial culture (transfer within 24 h) after 2 times of continuous transfer is adopted in the test.
(3) Preparing a bacterial suspension: adding a small amount of (1-2 ring scraped) fresh bacteria from the culture medium into the culture medium by using an inoculating loop, sequentially making 10-fold gradually increased diluents, and selecting the concentration of (5.0-10.0) x 105cfu/mL of the bacterial liquid was used as an inoculum liquid.
6. Sample experiment
0.4-0.5mL of test bacterial liquid is respectively dripped on the blank control plate A and the antibacterial coating plate B. Clamping the sterilization cover films by using sterilization tweezers to cover the A and the B respectively, paving the sterilization cover films without air bubbles to ensure that bacteria uniformly contact the sample plate, placing the sample plate in a sterilization plate, culturing the sample plate for 24 hours under the conditions of 37 +/-1 ℃ and relative humidity RH being more than 90 percent, and performing 3 parallel tests on each sample.
The samples cultured for 24h were taken out, 20mL of the washing solution was added, the samples A and B and the cover film were washed repeatedly, and after shaking sufficiently, the washing solution was inoculated into nutrient agar medium (NA), cultured at 37. + -. 1 ℃ for 24-48h, and then the ultraviolet absorbance at 600nm in the washing solution was measured with an ultraviolet photometer (Bio-rad Berry SmartSpec Plus, USA).
7. Calculation of detection result
R ═ B-C)/B × 100; wherein the content of the first and second substances,
r: the antibacterial rate;
b: obtaining the average ultraviolet absorbance of the washing liquid 24 hours after blank control of the sample plate;
c: the average uv absorbance of the wash was taken 24 hours after the antimicrobial paint panel.
8. Durability test
And (3) adopting a 30W ultraviolet lamp with the wavelength of 253.7nm, wherein the ultraviolet lamp accords with the GB19258 standard, irradiating the antibacterial coating test plate for 100 hours at a distance of 0.8-1.0 m from the ultraviolet lamp, and testing the antibacterial durability of the treated test plate according to the steps 6 and 7 to obtain the durable antibacterial rate.
The antibacterial effect tests of the antibacterial emulsions prepared in examples 1 to 30 and comparative examples 1 to 4 were performed according to the above method, and the results are shown in fig. 1 to 2 (example 1) and the following table:
Figure BDA0002456881070000141
Figure BDA0002456881070000151
the results show that the antibacterial emulsion synthesized by the invention can effectively inhibit the attachment and reproduction of microorganisms on the surface, thereby achieving the physical antibacterial effect and having obvious antibacterial effect. Especially, when the fifth monomer is properly selected for copolymerization, the physical antibacterial property and the chemical antibacterial property can generate a synergistic effect, thereby achieving an excellent antibacterial effect. Particularly, the antibacterial rate of the antibacterial emulsion can still be basically maintained without obvious attenuation after durability tests, and visible physical antibacterial property has durability under the action of ultraviolet rays or sunlight, so that the antibacterial emulsion can provide excellent and long-term antibacterial performance when being used as an emulsion paint or a glass cement component outdoors. In addition, the antibacterial emulsion disclosed by the invention can contain no chemical bactericide, is good in heat resistance, cannot generate drug resistance, and is safe and nontoxic; the paint does not contain inorganic silver ions, has good dispersion stability in the paint, low price and good antibacterial effect on fungi and mould; the photocatalyst nano metal particles are not contained, ultraviolet rays are not needed, and potential safety hazards are avoided.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims (10)

1. An antibacterial emulsion is characterized by comprising a high-molecular copolymer, an initiator and water; the high-molecular copolymer is obtained by copolymerizing at least two monomers containing carbon-carbon double bonds, and comprises a main chain and a branched chain; wherein the content of the first and second substances,
the main chain is obtained by polymerizing carbon-carbon double bonds in the monomer;
at least a part of the branched chains include repeating units containing ether bonds, and the average molecular weight of the branched chains including the repeating units containing ether bonds is 1000 or more.
2. The antimicrobial emulsion of claim 1, wherein the ether linkage containing repeat unit is selected from the group consisting of-OCH2CH2-、-OCH2CHCH3-、-OCHCH3CH2-、-OCH2CH2CH2CH2-one or more of (a) and (b).
3. The antimicrobial emulsion of claim 2, wherein the ether linkage-containing repeating unit is provided by a first monomer; when the ether bond-containing repeating units in the first monomer are two or more, the repeating units are arranged randomly, blockwise or alternately.
4. The antibacterial emulsion of claim 3, wherein the molecular structural formula of the first monomer is selected from one or more of the following molecular structural formulas:
Figure FDA0002456881060000011
Figure FDA0002456881060000021
Figure FDA0002456881060000031
Figure FDA0002456881060000041
Figure FDA0002456881060000042
wherein R is11Is H atom or C1-C5 alkyl, R12Is H atom or alkyl, and at least one of n, m, p and q is more than or equal to 2.
5. The antibacterial emulsion according to claim 1, wherein the branched chain comprising repeating units containing an ether bond has an average molecular weight of 1500 to 10000.
6. The antimicrobial emulsion of claim 3, wherein the first monomer is added in an amount of 0.5 to 50% by weight based on the total weight of all monomers.
7. The antibacterial emulsion of claim 3, wherein the monomers forming the high molecular copolymer further comprise a water-soluble second monomer, and the second monomer is one or more selected from acrylic acid, acrylamide and methacrylic acid monomers.
8. The antimicrobial emulsion of claim 7, wherein the second monomer is pre-neutralized with a base prior to polymerization, the degree of neutralization being from 0.1 to 99%.
9. The method of preparing an antimicrobial emulsion according to any one of claims 1 to 8, comprising the steps of:
(1) dissolving the second monomer in water, and adding the first monomer and other monomers after pre-neutralization;
(2) adding a surfactant, stirring until the mixture is fully emulsified, introducing nitrogen, and heating to 55-65 ℃;
(3) quickly adding the initiator, heating to 70-80 ℃, keeping the reaction for 1-3 hours, and cooling to room temperature; thus obtaining the antibacterial emulsion.
10. Use of an antibacterial emulsion according to any one of claims 1 to 8 in architectural coatings or dispersion adhesives.
CN202010308903.1A 2020-04-19 2020-04-19 Antibacterial emulsion and preparation method and application thereof Pending CN113527588A (en)

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