CN114507321A - Antibacterial soap-free polymer dispersion and preparation method and application thereof - Google Patents

Antibacterial soap-free polymer dispersion and preparation method and application thereof Download PDF

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CN114507321A
CN114507321A CN202210050397.XA CN202210050397A CN114507321A CN 114507321 A CN114507321 A CN 114507321A CN 202210050397 A CN202210050397 A CN 202210050397A CN 114507321 A CN114507321 A CN 114507321A
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monomer
monomer composition
vinyl
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antibacterial
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朱忠敏
胡清
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DONGLAI COATING TECHNOLOGY (SHANGHAI) CO LTD
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DONGLAI COATING TECHNOLOGY (SHANGHAI) 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C09D151/003—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 by reactions only involving unsaturated carbon-to-carbon 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Abstract

The invention relates to a polymer dispersion, in particular to an antibacterial soap-free polymer dispersion as well as a preparation method and an application thereof, and the preparation method comprises the following steps: s1: mixing a first monomer composition a1, a surfactant a2, and an initiator a 3; s2: emulsion polymerization is carried out on the emulsion A obtained in the step S1; s3: adding a second monomer composition b1 to the first polymer particle dispersion P1 obtained in step S2; s4: emulsion polymerization is carried out on the mixture B obtained in the step S3; s5: a crosslinking agent is added to the second polymer particle dispersion P2 obtained in step S4 to obtain an antibacterial soap-free polymer dispersion. Compared with the prior art, the polymer dispersion does not contain free emulsifier, and various properties are improved; the solid content is high, the film forming time is short, and the production efficiency is high; no amine and no odor; the further prepared coating has strong killing capability on various microorganisms, and still has strong sterilization effect after the anionic detergent is used.

Description

Antibacterial soap-free polymer dispersion and preparation method and application thereof
Technical Field
The invention relates to a polymer dispersion, in particular to an antibacterial soap-free polymer dispersion as well as a preparation method and application thereof.
Background
How to reduce the threat of emerging diseases and microorganisms to humans has been a century-long topic. Therefore, developing a coating that can inhibit bacteria and viruses on the surface of a material for a long time is a currently critical research and development task for coating engineers.
The antibacterial coating is subjected to abrasion and continuous loss of the antibacterial agent in the long-term use process, for example, silver, copper and other nano particles can continuously release silver ions or copper ions in the coating, so that the antibacterial effectiveness of the surface of the coating is continuously reduced along with the time. In order to obtain excellent and durable surface contact antibacterial performance, the monomer with the antibacterial functional group can be polymerized into the coating resin, so that the substance with the antibacterial effect has no migration and loss, and the aim of long-acting protection is fulfilled.
The antibacterial coating resin synthesized by adopting the emulsion polymerization process has the advantages of energy conservation and environmental protection, the surfactant is an indispensable component in emulsion polymerization, the traditional surfactant is adsorbed to the surface of latex particles through physical action, the adsorption force is very weak, so that the surfactant can be desorbed from the surface of the latex particles, and the instability of latex, poor adhesive force of a paint film, sensitivity to water and poor glossiness can be caused.
CN 111184025B discloses a preparation method of a silver ruthenium bimetal antibacterial material, silver ruthenium bimetal forms a micro-battery structure, and when the silver ruthenium bimetal antibacterial material is used, active oxygen substances can be continuously obtained through a two-electron oxygen reduction reaction and a Fenton-like reaction without illumination, so that the aim of broad-spectrum antibacterial is fulfilled. The method has the disadvantages that when the antibacterial material is added into the paint for use, the antibacterial material cannot be stably dispersed in the paint, and is easy to agglomerate to cause the defect of a paint film.
CN 112552803B discloses an antibacterial coil coating with water resistance, and describes that a citronellol modified silk extract fibroin is compounded with an acrylic emulsion to obtain a water-resistant antibacterial emulsion which is applied to an antibacterial coating. However, the modified silk fibroin and the acrylic emulsion are simply and physically mixed, and the long-term stability of the emulsion in storage cannot be guaranteed. The modified silk fibroin with a linear structure is not chemically connected with polymer particles in the acrylic emulsion, so that the chemical resistance and the wear resistance of a paint film are not facilitated. The antibacterial performance of the paint film is not evaluated experimentally, and no specific antibacterial parameter exists.
CN 107325210B describes a cross-linked polymer antibacterial nano latex particle and a preparation method thereof, wherein an emulsifier is not used in the emulsion polymerization stage, and the latex particle in the system is stabilized by a cationic group provided by a quaternary ammonium salt monomer. The emulsion containing the quaternary ammonium salt and the bacterial liquid are shaken uniformly in a ratio of 1:1, and as a result, the emulsion shows good antibacterial property on escherichia coli. However, the monomers used in the emulsion polymerization of the patent contain considerable styrene, the flexibility and the weather resistance of a paint film are poor, and the minimum film-forming temperature (MFT) is high, so that the construction under the low-temperature condition is not facilitated. The patent also fails to evaluate the antimicrobial properties of the paint film under practical use conditions.
Disclosure of Invention
The invention aims to solve at least one of the problems, provides an antibacterial soap-free polymer dispersion as well as a preparation method and application thereof, and realizes the polymer dispersion which can be used for preparing an antibacterial coating.
The purpose of the invention is realized by the following technical scheme:
the invention discloses a preparation method of an antibacterial soap-free polymer dispersion, which comprises the following steps:
s1: mixing the first monomer composition a1, the surfactant a2 and the initiator a3 to obtain emulsion A;
s2: emulsion polymerization is carried out on the emulsion A obtained in the step S1, and a first polymer particle dispersion P1 is obtained;
s3: adding a second monomer composition B1 to the first polymer particle dispersion P1 obtained in step S2 to obtain a mixture B;
s4: emulsion polymerization is carried out on the mixture B obtained in the step S3, and a second polymer particle dispersion P2 is obtained;
s5: adding a crosslinking agent to the second polymer particle dispersion P2 obtained in the step S4 to obtain the antibacterial soap-free polymer dispersion;
wherein the content of the first and second substances,
the first monomer composition a1 comprises a nitrogen heterocyclic ring-containing vinyl monomer, a crosslinking monomer, other vinyl monomers and a chain transfer agent;
the second monomer composition b1 comprises a nitrogen heterocyclic ring vinyl monomer and other vinyl monomers.
In the first stage of polymerization, the first monomer composition a1, surfactant a2, and initiator a3 were mixed in water to prepare emulsion a. The components of emulsion a may be added in any of several different orders known in the art, such as: the monomers in the first monomer composition a1 can be added after premixing or separately, can be added continuously or in one or more portions, can be added before, during or after the addition of water, surfactant, initiator and can be added before, during or after heating to the reaction temperature.
In the second stage of polymerization, the second monomer composition b1 may be continuously added dropwise to the reaction vessel, or may be added stepwise.
Preferably, the first monomer composition a1 comprises:
1 to 20 parts by mass of a vinyl monomer containing a nitrogen heterocycle, more preferably 2 to 15 parts by mass of a vinyl monomer containing a nitrogen heterocycle, and still more preferably 3 to 10 parts by mass of a vinyl monomer containing a nitrogen heterocycle;
1-20 parts by mass of a crosslinking monomer, more preferably 3-15 parts by mass of a crosslinking monomer, and still more preferably 5-10 parts by mass of a crosslinking monomer;
50-99 parts by mass of other vinyl monomers, further preferably 60-95 parts by mass of other vinyl monomers, and further preferably 65-90 parts by mass of other vinyl monomers;
and 0.05 to 1 part by mass of a chain transfer agent.
Preferably, the second monomer composition b1 includes 1 to 10 parts by mass of a nitrogen-containing heterocyclic vinyl monomer and 10 to 50 parts by mass of other vinyl monomers.
Preferably, the amount of the surfactant a2 is 0.05-5 wt% of the first monomer composition a 1; further preferably 0.1 to 3 wt%; more preferably 0.5 to 2 wt%.
Preferably, the amount of the initiator a3 is 0.05-5 wt% of the first monomer composition a 1; more preferably 0.2 to 3 wt%.
Preferably, the amount of the second monomer composition b1 is 15-85 wt% of the total amount of the first monomer composition a1 and the second monomer composition b 1; further preferably 25 to 75 wt%; more preferably 35 to 65 wt%.
Preferably, said first dispersion of polymer particles P1 has an average particle size of less than 90 nm; further preferably less than 60 nm; even more preferably less than 50 nm;
the Tg of the first polymer particle dispersion P1 is 5-130 ℃; further preferably 25-130 ℃; more preferably 45 to 130 ℃.
Preferably, the second polymer particle dispersion P2 is a core-shell polymer particle dispersion;
the solid content of the composite material is 40-70%, and the preferable solid content is 45-65%;
the average particle size of the second polymer particle dispersion P2 is less than 150 nm; further preferably less than 125 nm; even more preferably less than 100 nm;
wherein the content of polymer particles with a particle size of more than 100nm is less than 25 wt%; preferably less than 15 wt%; further preferably less than 10 wt%; the polymer particles having a particle size of more than 100nm may affect the gloss of the coating film of the final product, and when the content is less than 25 wt%, a coating film having better gloss may be formed, and when the content is further reduced, the gloss of the coating film is better.
The Tg of the second polymer particle dispersion P2 is at least 20 ℃ lower than the Tg of the first polymer particle dispersion P1; preferably at least 35 ℃;
typically, the Tg of the second polymer particle dispersion P2 is-60 to 60 ℃; preferably-30 to 40 ℃.
The polymer particle dispersion after polymerization is in a core-shell structure, the first polymer particle dispersion P1 forms a core, and the Tg at the stage is higher so as to increase the Tg of the polymer; the second polymer particle dispersion P2 formed a shell with a lower Tg at this stage to lower the film forming temperature. The average particle diameters of the first polymer particle dispersion P1 and the second polymer particle dispersion P2 are Z-average values measured by dynamic light scattering; the second polymer particle dispersoid P2 with a core-shell structure obtained by the second stage polymerization has small particle size, concentrated particle size distribution and excellent stability, and can prepare stable emulsion with high solid content.
Preferably, the vinyl monomer containing the nitrogen heterocyclic ring is one or more of N-sulfhydrylation beta-lactam derivative, quinoline derivative and sulfamethoxazole derivative. The alkene monomer containing the nitrogen heterocycle has an antibacterial function and can participate in polymerization, so that the prepared coating resin has no migration and loss, and the long-acting protection purpose can be achieved; the alkene monomer containing the nitrogen heterocycle is a non-salt type antibacterial monomer, has the similar effect as antibacterial peptide, acts on a cell membrane, can form a transmembrane ion channel on the membrane, destroys the integrity of the membrane, further can cause the leakage of cell contents, and thereby kills cells.
Further preferably, the vinyl monomer containing nitrogen heterocycle is selected from one or more compounds shown as formulas I to VIII:
Figure BDA0003474032070000051
wherein, the formulas I to IV are N-sulfhydrylation beta-lactam derivatives; formula V is a quinoline derivative; the formulas VI to VIII are sulfamethoxazole derivatives.
Preferably, the crosslinking monomer is one or more of allyl methacrylate, ethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane triacrylate, divinylbenzene, dicyclopentenyl acrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, acrolein, methacrolein, diacetone acrylamide, isocyanatoethyl methacrylate, and 3-isopropenyl- α, α -dimethylbenzyl isocyanate. The cross-linking monomer is introduced into the polymer so as to introduce cross-linking points, and can react with the cross-linking agent to form an interpenetrating network structure, so that the chemical resistance, hardness and other related properties of the coating film can be effectively improved.
Preferably, the other ethylenic monomer includes one or more of an ethylenically unsaturated vinyl monomer, a vinyl halide, a vinylidene halide, a vinyl ester, an alkyl ester of a monoethylenically unsaturated dicarboxylic acid, an ester of methacrylic acid, and a nonionic monomer. Other vinyl monomers are the main synthetic raw materials of the polymer, and different types and different dosages of other vinyl monomers can be selected for synthesis according to the performance requirements required by the product coating film, so that the performance requirements are met.
Preferably, the ethylenically unsaturated vinyl monomer is one or more of 1, 3-butadiene, isoprene, divinylbenzene, styrene and α -methylstyrene.
Preferably, the vinyl halide is vinyl chloride.
Preferably, the vinylidene halide is vinylidene chloride.
Preferably, the vinyl ester is one or more of vinyl acetate, vinyl propionate, butyl acrylate and vinyl laurate.
Preferably, the alkyl ester of a monoethylenically unsaturated dicarboxylic acid is di-n-butyl maleate and/or di-n-butyl fumarate.
Preferably, the ester of methacrylic acid is of formula CH2＝CR5-COOR4Of (a) in which R is5Is H or methyl, R4Is an optionally substituted C1 to C20, more preferably C1 to C8 alkyl, cycloalkyl, aryl or (alkyl) aryl group.
Preferably, the ester of methacrylic acid is selected from one or more of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isopropyl methacrylate, propyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 4-hydroxybutyl 2-methacrylate.
Preferably, the nonionic monomer is acrylonitrile and/or acrylamide. The nonionic monomer can also be an alkyl substituted acrylamide monomer or a mixture thereof.
Preferably, the chain transfer agent is one or more of mercaptan, halogenated hydrocarbon and cobalt chelate.
Further preferably, the chain transfer agent is a mercaptan.
Preferably, the mercaptan is one or more of n-dodecyl mercaptan, n-octyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, isooctyl thioglycolate, 3-mercaptopropionic acid and 2-mercaptopropionic acid.
Preferably, the halogenated hydrocarbon is carbon tetrabromide and/or bromotrichloromethane.
Preferably, the molecular formula of the surfactant a2 is R[4-(l+m+n)]R1 lR2 mR3 nN+X-Wherein R is a polymerizable group; r1、R2And R3Respectively is alkyl or aryl with 1-20 carbon atoms; x-Is Cl-、Br-、 I-、CH3OSO3 -And C2H5OSO3 -One or more of; l, m and n are each 1 or 0;
the polymeric group is unsaturated alkenyl polymerized by free radicals, and the unsaturated alkenyl polymerized by the free radicals is one or more of vinyl, allyl, acryloyl, methacryloyl, propenyl, 1-ethenylene and 1, 2-ethenylene.
The surfactant a2 is a polymerizable surfactant, an ionic surfactant which includes a cationic group and a hydrophobic group and further has a polymerizable group;
wherein:
the cationic group is preferably selected from primary ammonium salt ion, secondary ammonium salt ion, tertiary amine salt ion and quaternary ammonium salt ionA cationic group of (4); the primary amine salt ion can be selected from alkylammonium salt ion RNH3 +(ii) a The secondary ammonium salt ion may be selected from dialkyl ammonium ion R2NH2 +(ii) a The tertiary ammonium salt ion can be selected from trialkyl ammonium ion R3NH+(ii) a The quaternary ammonium salt ion can be selected from R4N+(ii) a Wherein R is a hydrophobic group, and may be one or more selected from alkyl groups having 1 to 20 carbon atoms and aryl groups (phenyl groups, phenylene groups, and the like), or may have both alkyl groups and aryl groups;
the counter anion of the cationic group may be selected from Cl-、Br-、I-、CH3OSO3 -、C2H5OSO3 -；
The polymerizable group is a radical-polymerizable unsaturated alkenyl group, and may be one or more selected from vinyl, allyl, acryloyl, methacryloyl, propenyl, 1-vinylidene and 1, 2-vinylidene groups.
Further preferably, the surfactant a2 may be selected from one or more of dimethylaminoethyl octyl methacrylate hydrochloride, dimethylaminoethyl hexadecyl methacrylate hydrochloride, dimethylaminoethyl decyl methacrylate hydrochloride, dimethylaminoethyl dodecyl methacrylate hydrochloride, dimethylaminoethyl tetradecyl methacrylate hydrochloride, 11-acryloyloxy undecyl trimethyl ammonium bromide, 11-acryloyloxy undecyl triethyl ammonium bromide and methacryloyloxyethyl dodecyl dimethyl ammonium bromide.
Preferably, the initiator a3 comprises inorganic peroxide and/or organic peroxide;
the inorganic peroxide is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide and percarbonate; wherein, the percarbonate is preferably sodium percarbonate;
the organic peroxide is one or more of acyl peroxide, alkyl hydroperoxide, dialkyl peroxide and peroxyester.
The initiator a3 is a water-soluble initiator, and is used for generating free radicals to initiate vinyl polymerization, so as to complete free radical emulsion polymerization of monomers.
Preferably, the acyl peroxide is benzoyl peroxide.
Preferably, the alkyl hydroperoxide is tert-butyl hydroperoxide and/or cumene hydroperoxide.
Preferably, the dialkyl peroxide is di-tert-butyl peroxide.
Preferably, the peroxyester is tert-butyl peroxybenzoate.
Preferably, the initiator a3 further comprises a reducing agent;
the reducing agent is one or more of sodium metabisulfite, potassium metabisulfite, sodium bisulfite, potassium bisulfite, sodium formaldehyde sulfoxylate, disodium 2-hydroxy-2-sulfinatoacetate, isoascorbic acid, azobisisobutyronitrile, 2 '-azo-bis (2-methylbutyronitrile) and 4, 4' -azobis (4-cyanovaleric acid).
In some cases, the above-mentioned inorganic peroxides or organic peroxides may constitute redox initiator systems with suitable reducing agents, it being possible to use initiators which partition between an aqueous phase and an organic phase, for example a combination of tert-butyl hydroperoxide and erythorbic acid. By means of the redox initiation system, the heat required for the generation of free radicals can be reduced, in a manner which is more suitable for the temperatures required in emulsion polymerization systems, without affecting or destroying the emulsion polymerization systems.
Preferably, the crosslinking agent is a dihydrazide compound and/or a polyamine.
The cross-linking agent is used for reacting with the cross-linking monomers in the first monomer composition a1 and the second monomer composition b1, or reacting with other alkene monomers in the second monomer composition b1 in a cross-linking way. The crosslinking agent is preferably added after step S2, more preferably after step S4.
Preferably, the dihydrazide compound is one or more of oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide and terephthalic acid dihydrazide.
Preferably, the polyamine is isophorone diamine.
Further preferably, the crosslinking agent is adipic acid dihydrazide.
Preferably, the reaction temperature of the emulsion polymerization can be 40-130 ℃; further preferably 65 to 100 ℃. And (3) beginning to dropwise add the initiator after the temperature of the mixture in the reaction kettle reaches the reaction temperature.
In a second aspect, the invention discloses an antibacterial soap-free polymer dispersion prepared by the method for preparing the antibacterial soap-free polymer dispersion.
In a third aspect of the invention, there is disclosed the use of an antimicrobial soap-free polymer dispersion as described above in combination with coating ingredients to produce a coating.
Preferably, the coating composition comprises: pigments such as titanium dioxide or carbon black; extenders such as calcium carbonate, talc, clay, silica and silicates; fillers such as glass or polymer microspheres, quartz and sand; a thickener; a rheology modifier; a dye; a chelating agent; a biocide; a dispersant; an anti-freezing agent; a plasticizer; an adhesion promoter; a coalescing agent; a wetting agent; a wax; a surfactant; a slip-aid additive; a crosslinking agent; defoaming agents; a colorant; a preservative; freeze/thaw protectants and corrosion inhibitors.
Coating additives may also be added to the coating, including: co-solvents, reactive pigments, UV absorbers, antioxidants and stabilizers.
These coating ingredients and coating additives may be added in any order of addition that does not result in incompatibility between the components; components that are insoluble in the aqueous carrier (e.g., pigments and fillers) can be dispersed in the polymer dispersion or the aqueous carrier or co-solvent using a high shear mixer; the coating components and coating additives may be those commercially available.
The coatings prepared from the antimicrobial soap-free polymer dispersions are waterborne coatings that can be applied to a variety of surfaces, substrates, or articles, such as: plastics, steel, aluminum, galvanized sheet, concrete, wood, brick, masonry, gypsum board, and the like; conventional coating techniques can be used, such as: coating the mixture on a required substrate by methods of conventional spraying or airless spraying, roller coating, brush coating, curtain coating, dip coating and the like; generally, the coating can be cured at ambient temperature or dried by heating, depending on the substrate used.
Compared with the prior art, the invention has the following beneficial effects:
1. the antibacterial soap-free polymer dispersion prepared by the invention does not contain free emulsifier, and the glossiness, water resistance, chemical resistance, adhesive force and other properties of the polymer emulsion are obviously improved; the solid content is high, the production efficiency is high, and the film forming time is short; without the use of amine neutralizers, the polymer dispersion was odorless. The antibacterial monomer is a nitrogen heterocyclic ring-containing nonionic monomer, the prepared antibacterial coating has strong killing capacity on methicillin-resistant staphylococcus aureus, fungi, tubercle bacillus, hydrophilic viruses, bacterial spores and other microorganisms, has strong bactericidal effect after the surface is cleaned by using the detergent containing anions, and has the characteristic of lasting bacteriostasis.
2. The antibacterial monomer is connected with the coating resin in a polymerization mode, so that the antibacterial monomer can not migrate and lose, and long-term stability and long-term protection and sterilization capability are realized; the nitrogenous heterocyclic antibacterial functional alkene monomer is a non-salt antibacterial monomer, has the effect similar to that of antibacterial peptide, acts on a cell membrane, forms a transmembrane ion channel on the membrane, destroys the integrity of the membrane, further causes the leakage of cell contents, and can effectively kill cells.
3. By controlling the average particle diameter of the polymer dispersion to a small level, it is possible to have excellent stability, and it is possible to prepare an emulsion having a high solid content without agglomeration; meanwhile, the glass transition temperature Tg is suitable, and the glass transition temperature Tg can be suitable for being used at low temperature.
4. According to the water-based paint prepared by the polymer dispersion prepared by the invention, the antibacterial rate of the paint to golden yellow staphylococcus and escherichia coli is determined according to the standard of HG/T39502007, and the antibacterial rate can reach more than 99%; after the paint film is scrubbed by using the anionic surfactant, the bacteriostasis rate can still reach over 99 percent; in addition, other performances of the water-based paint can meet the requirements or standards of enterprises, and the water-based paint is an antibacterial paint with good performance and can be used for automobile interiors, household appliances, medical devices, wood and the like.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the present invention is not limited thereto in any way.
The reagents used in the following examples are not specifically described, and commercially available products that can be obtained conventionally by those skilled in the art can be used.
Table 1 below is the corresponding names and classifications of the compounds used in each of the examples and comparative examples.
TABLE 1 Classification of Compounds used in examples and comparative examples
Figure BDA0003474032070000101
Figure BDA0003474032070000111
Example 1
The operation was carried out in a 5L jacketed reactor with stirring paddles, reflux condenser and temperature regulation system.
The monomer composition, the aqueous initiator solution and the aqueous reducing agent solution were continuously fed into the reactor at flow rates controlled by a metering pump.
First, a surfactant was mixed with the first monomer composition a1 to prepare a premix according to the component ratios in table 2, and mixed to prepare a second monomer composition b 2. A10 wt% aqueous solution of APS was prepared using 0.5 part by mass of APS, a 10 wt% aqueous solution of sodium metabisulfite was prepared using 0.2 part by mass of sodium metabisulfite, and a 20 wt% aqueous solution of AADH was prepared using 1.2 parts by mass of AADH.
The pre-charge, as proportioned in table 2, was added to the reactor at room temperature, then heated to 80 ℃, 5 wt% of the pre-mix was added, then 40 wt% of the APS aqueous solution was added. After waiting for 10min, the entire remaining premix was added dropwise to the reactor over 4.5h, followed by a 45min hold. The reaction medium was then cooled to 65 ℃ and 20% by weight of the second monomer composition b2 was added in 5 min. After waiting for 5min, the remaining total of the second monomer composition b2, 30 wt% of the APS aqueous solution, and 50 wt% of the sodium metabisulfite aqueous solution were simultaneously added dropwise into the reactor over 105 min. After all of the above substances were added, the remaining total amount of the aqueous solution of APS and the aqueous solution of sodium metabisulfite was added dropwise to the reactor over 60 min. After the addition is complete, the reaction medium is cooled to 40 ℃ and then an aqueous solution of AADH is added. After waiting 10 minutes the product was discharged from the reactor.
Example 2
The preparation process is identical to that of example 1, the amounts of the substances being listed in Table 2.
Compared with example 1, the properties of the surfactant were mainly changed by replacing the polymerizable cationic surfactant AUTMAB with the polymerizable cationic surfactant MEDDAB.
Example 3
The preparation was carried out in the same manner as in example 1, the amounts of the substances being indicated in Table 2.
Compared with example 2, the properties of the antibacterial monomer are mainly changed by replacing the antibacterial monomer N-thiolated beta-lactam derivative L-D with the antibacterial monomer quinoline derivative Q-D.
Example 4
The preparation was carried out in the same manner as in example 1, the amounts of the substances being indicated in Table 2.
Compared with the example 2, the property of the antibacterial monomer is mainly changed by replacing the antibacterial monomer N-sulfhydrylation beta-lactam derivative L-D with the antibacterial monomer sulfamethoxazole derivative AMBS.
Comparative example 1
The preparation was carried out in the same manner as in example 1, the amounts of the substances being indicated in Table 2.
Compared with example 1, the antibacterial monomer N-sulfhydrylation beta-lactam derivative L-D is replaced by cationic antibacterial monomer PEDAB to change the property of the antibacterial monomer
Comparative example 2
The preparation was carried out in the same manner as in example 1, the amounts of the substances being indicated in Table 2.
The Tg of the dispersion was increased compared to example 1, primarily by increasing the amount of MMA and ST and decreasing the amount of BuA.
Comparative example 3
The preparation was carried out in the same manner as in example 1, the amounts of the substances being indicated in Table 2.
Compared with example 1, the properties of the surfactant were changed by mainly replacing the polymerizable cationic surfactant AUTMAB with the non-polymerizable cationic surfactant DC.
TABLE 2 contents (in parts by mass) of each of examples 1 to 4 and comparative examples 1 to 3
Figure BDA0003474032070000121
Figure BDA0003474032070000131
In the above table, DIW is deionized water.
And (3) testing basic performance:
the antibacterial polymer dispersions prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to performance tests according to the following test standards:
MFT: a25 μm wet film was prepared using a film scraper and the MFT, which is the lowest temperature at which the film does not show cracking, was determined in Rhopoint MFT-Bar 90 at a temperature range of 0 ℃ to 90 ℃;
particle size: particle size was determined by dynamic light scattering using a Malvern Zatasizer model Nano-S90, with the mean hydrodynamic diameter, Zmean, as the value of particle size;
rotational viscosity: rotational viscosity was measured using a rheometer model Anton Paar MCR92 at 23 ± 1 ℃.
The test results are shown in Table 3.
TABLE 3 results of Performance test of Polymer dispersions obtained in examples 1 to 4 and comparative examples 1 to 3
Figure BDA0003474032070000141
Application examples 1 to 6
The polymer dispersions prepared in examples 1-4 and comparative examples 1-2 were formulated in the proportions shown in Table 4 to give antibacterial water-based paints.
The antibacterial polymer dispersion prepared above, water and each component were added to a container of a disperser according to the ratio in table 4 under high-speed stirring, and ground to a fineness of less than 10 μm.
Table 4 formula ratios of water-based paint in application examples 1-6
Composition of Function of Mass portion of
Deionized water Diluent 37.4
Antimicrobial polymer dispersions Host resin 50
Butyl diglycol Co-solvent 5
Surfynol 104 DPM Wetting agent 0.5
BYK333 Dispersing agent 0.8
Borchi Gel L75N Thickening agent 1.3
Dowanol PnP Coalescing agent 5
Total of / 100
And (3) testing the performance of the paint film:
the water-based paint prepared in the application examples 1-6 is subjected to physical property and chemical resistance tests, and the test standards are as follows:
pencil hardness: GB/T6739-2006;
adhesion force: GB/T9286-1998;
chemical resistance: using an RJCS solvent resistant wiper (shanghai modern environmental engineering technologies limited): the times of wiping the surface of the paint film with absorbent cotton soaked by MEK are repeatedly counted once until the paint film is stripped, fallen off, damaged and the like;
water resistance: a wet film having a thickness of 200 μm was coated on a glass plate, which was then dried in a climate-controlled room (23. + -. 1 ℃ C. and 50. + -. 5% RH) for 7 days. The painted glass plates were then immersed in water at 40 ℃ for 10 days, observed for appearance and tested for adhesion.
The test results are shown in Table 5.
TABLE 5 Performance test results of Water-based paints of application examples 1 to 6
Figure BDA0003474032070000151
And (3) testing antibacterial performance:
antibacterial property: the antibacterial rate of the coating on staphylococcus aureus and escherichia coli is determined according to HG/T39502007 standard.
The antibacterial rate of the paint to staphylococcus aureus and escherichia coli is determined according to HG/T39502007 standard, and test results show that the antibacterial rate of the paint prepared by using the polymer dispersions in examples 1-4 and comparative example 1 can reach more than 99%. After a paint film is scrubbed by using a paint film containing an anionic surfactant, the bacteriostatic rate of the paint prepared by using the polymer dispersions in the embodiments 1 to 4 can still reach more than 99%, while the bacteriostatic rate of the paint prepared by using the polymer dispersion in the comparative example 1 is less than 90%, because the paint prepared by using the non-ionic nitrogen heterocyclic monomer in the polymer dispersions in the embodiments 1 to 4 can keep high antibacterial performance in the presence of anions.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A method for preparing an antimicrobial soap-free polymer dispersion, comprising the steps of:
s1: mixing the first monomer composition a1, the surfactant a2 and the initiator a3 to obtain emulsion A;
s2: emulsion polymerization is carried out on the emulsion A obtained in the step S1, and a first polymer particle dispersion P1 is obtained;
s3: adding a second monomer composition B1 to the first polymer particle dispersion P1 obtained in step S2 to obtain a mixture B;
s4: emulsion polymerization is carried out on the mixture B obtained in the step S3, and a second polymer particle dispersion P2 is obtained;
s5: adding a crosslinking agent to the second polymer particle dispersion P2 obtained in the step S4 to obtain the antibacterial soap-free polymer dispersion;
wherein the content of the first and second substances,
the first monomer composition a1 comprises a nitrogen heterocyclic ring-containing vinyl monomer, a crosslinking monomer, other vinyl monomers and a chain transfer agent;
the second monomer composition b1 comprises a nitrogen heterocyclic ring vinyl monomer and other vinyl monomers.
2. The method of claim 1, wherein the antimicrobial soap-free polymer dispersion,
the first monomer composition a1 comprises 1-20 parts by mass of a nitrogen heterocyclic ring-containing vinyl monomer, 1-20 parts by mass of a crosslinking monomer, 50-99 parts by mass of other vinyl monomers and 0.05-1 part by mass of a chain transfer agent;
the second monomer composition b1 comprises 1-10 parts by mass of a nitrogen heterocyclic ring-containing vinyl monomer and 10-50 parts by mass of other vinyl monomers;
the amount of the surfactant a2 is 0.05-5 wt% of the first monomer composition a 1;
the amount of the initiator a3 is 0.05-5 wt% of the first monomer composition a 1;
the amount of the second monomer composition b1 is 15-85 wt% of the total amount of the first monomer composition a1 and the second monomer composition b 1;
the average particle size of the first polymer particle dispersion P1 is less than 90nm, and the Tg is 5-130 ℃;
the solid content of the second polymer particle dispersion P2 is 40-70%, the average particle size is less than 150nm, the content of polymer particles with the particle size of more than 100nm is less than 25 wt%, and the Tg is-60 ℃.
3. The method of claim 1 or 2, wherein the first monomer composition a 1:
the vinyl monomer containing the nitrogen heterocyclic ring is one or more of N-sulfhydrylation beta-lactam derivatives, quinoline derivatives and sulfamethoxazole derivatives;
the crosslinking monomer is one or more of allyl methacrylate, ethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane triacrylate, divinylbenzene, dicyclopentenyl acrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, acrolein, methacrolein, diacetone acrylamide, isocyanatoethyl methacrylate and 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate;
the other vinyl monomer comprises one or more of ethylenically unsaturated vinyl monomer, vinyl halide, vinylidene halide, vinyl ester, alkyl ester of monoethylenically unsaturated dicarboxylic acid, ester of methacrylic acid, and nonionic monomer;
the chain transfer agent is one or more of mercaptan, halogenated hydrocarbon and cobalt chelate.
4. The method of claim 1, wherein the surfactant a2 has the formula R[4-(l+m+n)]R1 lR2 mR3 nN+X-Wherein R is a polymerizable group; r1、R2And R3Respectively is alkyl or aryl with 1-20 carbon atoms; x-Is Cl-、Br-、I-、CH3OSO3 -And C2H5OSO3 -One or more of; l, m and n are each 1 or 0;
the polymeric group is unsaturated alkenyl polymerized by free radicals, and the unsaturated alkenyl polymerized by the free radicals is one or more of vinyl, allyl, acryloyl, methacryloyl, propenyl, 1-ethenylene and 1, 2-ethenylene.
5. The method of claim 1, wherein the initiator a3 comprises inorganic peroxide and/or organic peroxide;
the inorganic peroxide is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide and sodium percarbonate;
the organic peroxide is one or more of acyl peroxide, alkyl hydroperoxide, dialkyl peroxide and peroxyester.
6. The method of claim 5, wherein the initiator a3 further comprises a reducing agent;
the reducing agent is one or more of sodium metabisulfite, potassium metabisulfite, sodium bisulfite, potassium bisulfite, sodium formaldehyde sulfoxylate, disodium 2-hydroxy-2-sulfinatoacetate, isoascorbic acid, azobisisobutyronitrile, 2 '-azo-bis (2-methylbutyronitrile) and 4, 4' -azobis (4-cyanovaleric acid).
7. The method of claim 1, wherein the crosslinking agent is a dihydrazide compound and/or a polyamine.
8. The method of claim 1, wherein the emulsion polymerization is carried out at a temperature of 40 to 130 ℃.
9. An antibacterial non-soap polymer dispersion, which is prepared by the method for preparing an antibacterial non-soap polymer dispersion according to any one of claims 1 to 8.
10. Use of an antimicrobial soap-free polymer dispersion according to claim 9 in the preparation of a coating by mixing the antimicrobial soap-free polymer dispersion with coating ingredients.
CN202210050397.XA 2022-01-17 2022-01-17 Antibacterial soap-free polymer dispersion and preparation method and application thereof Pending CN114507321A (en)

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CN106565912A (en) * 2016-11-11 2017-04-19 广州大学 Polyquaternium polymer emulsion antibacterial agent, preparation method thereof and application thereof
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Publication number Priority date Publication date Assignee Title
US3873703A (en) * 1970-02-13 1975-03-25 Ciba Geigy Ag Bactericidal and fungicidal compositions and methods of killing bacteria and fungi using 8-oxyguinoline-and 8-oxyguinaldine acrylates
CN103459432A (en) * 2011-04-11 2013-12-18 树脂核动力工业有限公司 Process for preparing aqueous vinyl polymer dispersions
CN106565912A (en) * 2016-11-11 2017-04-19 广州大学 Polyquaternium polymer emulsion antibacterial agent, preparation method thereof and application thereof
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