CN112341575A - Water-based acrylic emulsion with lasting antibacterial function - Google Patents
Water-based acrylic emulsion with lasting antibacterial function Download PDFInfo
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Abstract
The invention discloses a water-based acrylic emulsion with lasting antibacterial property, which comprises the following raw materials in parts by weight: 100 portions of vinyl monomer, 3 to 5 portions of emulsifier, 0.3 to 0.9 portion of initiator, 5 to 7 portions of auxiliary agent, 6 to 10 portions of stabilizer and 100 portions of deionized water and 200 portions; the water-based acrylic emulsion is prepared by the following steps: firstly, adding 20% of emulsifier and 10-20% of initiator into 20% of deionized water, and adding vinyl monomer and 20% of auxiliary agent after dissolving to obtain pre-emulsion; and secondly, adding the rest of the emulsifier into the rest of the deionized water, sequentially adding the rest of the initiator, the rest of the auxiliary agent and the stabilizer, heating under the protection of nitrogen, dropwise adding the pre-emulsion obtained in the first step, cooling the reactant to 30-50 ℃ after the reaction is finished, adjusting the pH value to 7-8, and finally filtering to obtain the water-based acrylic emulsion with the lasting antibacterial property.
Description
Technical Field
The invention belongs to the technical field of acrylic emulsion, and particularly relates to a water-based acrylic emulsion with lasting antibacterial property.
Background
The water-based acrylic emulsion is often used as a coating, and compared with the traditional solvent-based coating, the water-based coating has the advantages of low price, safe use, resource and energy conservation, environmental pollution and public nuisance reduction, and the like, thereby becoming the main direction for developing the coating industry at present. The water-based paint is an important direction for the development of environment-friendly paint due to low VOC. Compared with the traditional solvent-based coating, the water-based coating has the advantages of low price, safe use, resource and energy conservation, environmental pollution and public nuisance reduction, and the like, thereby becoming the main direction for developing the coating industry at present.
The antibacterial coating is a coating with antibacterial property by adding an antibacterial agent into the coating, and has the effects of improving indoor environment and protecting human health by killing mold and bacteria such as escherichia coli, staphylococcus and the like, and the research and application of the antibacterial coating are concerned. Antibacterial agents can be classified into three major categories, natural, organic, inorganic, and the like: the natural antibacterial agent is chitosan, natural extracts and other extracts, the natural antibacterial agent is mainly some extracts of natural plants, and the natural antibacterial agent has the problems of poor stability, chromaticity and the like due to the limitation of the conditions such as sources, extraction levels, cost and the like, so the application and popularization of the natural antibacterial agent are difficult to a certain extent. Acrylic water-based paints have attracted attention because of their excellent weather resistance, acid and alkali resistance, water resistance, and the like.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a water-based acrylic emulsion with durable antibacterial property.
The technical problems to be solved by the invention are as follows:
antibacterial agents can be classified into three major categories, natural, organic, inorganic, and the like: the natural antibacterial agent is chitosan, natural extracts and other extracts, the natural antibacterial agent is mainly some extracts of natural plants, and the natural antibacterial agent has the problems of poor stability, chromaticity and the like due to the limitation of the conditions such as sources, extraction levels, cost and the like, so the application and popularization of the natural antibacterial agent are difficult to a certain extent.
The purpose of the invention can be realized by the following technical scheme:
a water-based acrylic emulsion with lasting antibacterial function comprises the following raw materials in parts by weight:
100 portions of vinyl monomer, 3 to 5 portions of emulsifier, 0.3 to 0.9 portion of initiator, 5 to 7 portions of auxiliary agent, 6 to 10 portions of stabilizer and 100 portions of deionized water and 200 portions;
the water-based acrylic emulsion with durable antibacterial property is prepared by the following steps:
firstly, adding 20% of emulsifier and 10-20% of initiator into 20% of deionized water, and adding vinyl monomer and 20% of auxiliary agent after dissolving to obtain pre-emulsion;
and secondly, adding the rest of the emulsifier into the rest of the deionized water, sequentially adding the rest of the initiator and the rest of the auxiliary agent, adding the stabilizer, heating the solution to 70-90 ℃ under the protection of nitrogen, dripping the pre-emulsion obtained in the first step, controlling the dripping speed, keeping the dripping time at 2-4h, continuously heating to 80-100 ℃ after finishing dripping, reacting for 2-4h, cooling the reactant to 30-50 ℃ after the reaction is finished, adjusting the pH value to 7-8, and finally filtering to obtain the water-based acrylic emulsion with lasting antibacterial property.
Further, the vinyl monomer is one or more of methacrylic acid, alkyl methacrylate, hydroxyalkyl methacrylate and isobornyl methacrylate which are mixed in any proportion; the emulsifier is one or more of sodium dodecyl sulfate, nonylphenol polyoxyethylene ether and ethoxylated ammonium alkylphenol sulfate which are mixed in any proportion; the initiator is one of azobisisobutyronitrile hydrochloride and azobiscyanovaleric acid.
Further, the auxiliary agent is prepared by the following steps:
step S11, adding guanidine hydrochloride and hexamethylene diamine into a three-neck flask, setting the temperature at 150 ℃ and the rotating speed at 200r/min, starting stirring after reactants are melted, reducing the temperature to 120 ℃, reacting for 1-2 hours, then increasing the temperature to 160 ℃, continuing to react for 40-60 minutes, reducing the temperature to room temperature after the reaction is finished to obtain a solid, dissolving the obtained solid with deionized water to obtain a mixed solution, freezing the mixed solution at 0 ℃ for 24 hours, and then freeze-drying in a freeze dryer for 70-72 hours to obtain white powder, wherein the white powder is polyhexamethylene guanidine hydrochloride;
step S12, adding white powder and dimethyl sulfoxide into a round-bottom flask, starting stirring until the white powder is completely dissolved at room temperature and the rotating speed of 300r/min, adding methacrylic anhydride and 4-dimethylaminopyridine, stirring at room temperature in a dark place for 48-50h, adding dichloromethane into the obtained reaction solution at 0-5 ℃, generating a precipitate, filtering, washing the obtained precipitate with dichloromethane three times, dissolving the washed precipitate with deionized water, dialyzing for 20h with a dialysis bag with the molecular weight cutoff of 500Da, replacing the deionized water every 2h, after the dialysis is finished, freezing the obtained mixed solution at 0 ℃ for 24h, and freeze-drying in a freeze dryer for 70-72h to obtain a product, namely the auxiliary agent; the dialysis process removes unreacted methacrylic anhydride, dimethyl sulfoxide and 4-dimethylaminopyridine.
The white powder prepared in the step S11 is polyhexamethylene guanidine hydrochloride, the polyhexamethylene guanidine hydrochloride and methacrylic anhydride are subjected to amidation reaction under the catalytic action of 4-dimethylaminopyridine to generate an auxiliary agent, the structure of the auxiliary agent contains the polyhexamethylene guanidine hydrochloride, and the polyhexamethylene guanidine hydrochloride is an environment-friendly cationic polymer and has extremely strong broad-spectrum antibacterial and bactericidal capabilities.
Further, the molar ratio of guanidine hydrochloride to hexamethylenediamine in step S11 is 1: 1-1.3; the dosage ratio of the white powder to the dimethyl sulfoxide in the step S12 is 10-12 g: 30 mL; the mass ratio of the white powder to the methacrylic anhydride to the 4-dimethylaminopyridine is 1: 1.2-1.4: 0.1.
further, the stabilizer is prepared by the following steps:
step S21, mixing deionized water, absolute ethyl alcohol and nano silicon dioxide, performing ultrasonic treatment for 30-40min under the condition of the frequency of 50-60kHz, adjusting the pH value to 3-4 by formic acid after the ultrasonic treatment is finished, adding a silane coupling agent, setting the temperature to 90-100 ℃ and the rotating speed to 300r/min, stirring for 10-12h, cooling to room temperature after the stirring is finished, performing vacuum filtration on reaction liquid to remove filtrate, and drying the obtained filter cake to constant weight under the condition of 90-100 ℃ to obtain modified silicon dioxide micropowder;
and S22, adding carboxymethyl cellulose and hydroxyethyl cellulose into deionized water, dissolving at room temperature, setting the temperature to be 40 ℃ and the rotating speed to be 300r/min, dropwise adding an aluminum sulfate solution during stirring for 20min, adding the modified silica micropowder prepared in the step S21 after dropwise adding, continuously stirring for 50-60min to obtain a mixed solution, cooling the obtained mixed solution, carrying out vacuum filtration, removing filtrate, and drying the obtained filter cake at 90-100 ℃ to constant weight to obtain the stabilizer.
Further, in the step S21, the silane coupling agent is γ -aminopropyltriethoxysilane, and the mass ratio of the deionized water, the absolute ethyl alcohol and the nano-silica is 5: 50: 8-10; the dosage of the silane coupling agent is 4-6% of the total mass of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide; in step S22, the molar concentration of the aluminum sulfate solution is 2.4mol/L, and the dosage ratio of the carboxymethyl cellulose, the hydroxyethyl cellulose, the aluminum sulfate solution, the deionized water and the modified silicon dioxide micropowder is 3 g: 1 g: 4-6 mL: 100mL of: 1-3 g.
Gamma-aminopropyl triethoxy silane has a unique bifunctional structure, one side can react with Si-OH on the surface of nano silicon dioxide, on the other hand, the gamma-aminopropyl triethoxy silane is a polar molecule and has good compatibility with polymers, the gamma-aminopropyl triethoxy silane can generate a large amount of-OH groups by hydrolysis and generate polycondensation reaction with the Si-OH on the surface of the nano silicon dioxide, thereby reducing the agglomeration phenomenon of the nano silicon dioxide, the macromolecular chain segment of carboxymethyl cellulose is more inclined to intramolecular cross-linking rather than intermolecular cross-linking, the introduction of hydroxyethyl cellulose can lead the chain segment of the carboxymethyl cellulose to be more stretched, thereby avoiding the intramolecular cross-linking of the macromolecular chain segment, aluminum sulfate has good performance and lower biological toxicity as a cross-linking agent, and leads the carboxymethyl cellulose and the hydroxyethyl cellulose to be cross-linked, and then the modified silicon dioxide micropowder is added for blending, so that the prepared water-based acrylic emulsion has good dispersibility and good performance after film forming.
The invention has the beneficial effects that:
the white powder prepared in the step S11 is polyhexamethylene guanidine hydrochloride, the polyhexamethylene guanidine hydrochloride and methacrylic anhydride are subjected to amidation reaction under the catalytic action of 4-dimethylaminopyridine to generate an auxiliary agent, the structure of the auxiliary agent contains the polyhexamethylene guanidine hydrochloride, and the polyhexamethylene guanidine hydrochloride is an environment-friendly cationic polymer and has extremely strong broad-spectrum antibacterial and bactericidal capabilities.
Gamma-aminopropyl triethoxy silane has a unique bifunctional structure, one side can react with Si-OH on the surface of nano silicon dioxide, on the other hand, the gamma-aminopropyl triethoxy silane is a polar molecule and has good compatibility with polymers, the gamma-aminopropyl triethoxy silane can generate a large amount of-OH groups by hydrolysis and generate polycondensation reaction with the Si-OH on the surface of the nano silicon dioxide, thereby reducing the agglomeration phenomenon of the nano silicon dioxide, the macromolecular chain segment of carboxymethyl cellulose is more inclined to intramolecular cross-linking rather than intermolecular cross-linking, the introduction of hydroxyethyl cellulose can lead the chain segment of the carboxymethyl cellulose to be more stretched, thereby avoiding the intramolecular cross-linking of the macromolecular chain segment, aluminum sulfate has good performance and lower biological toxicity as a cross-linking agent, and leads the carboxymethyl cellulose and the hydroxyethyl cellulose to be cross-linked, and then the modified silicon dioxide micropowder is added for blending, so that the prepared water-based acrylic emulsion has good dispersibility and good performance after film forming.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A water-based acrylic emulsion with lasting antibacterial function comprises the following raw materials in parts by weight:
100 parts of vinyl monomer, 3 parts of emulsifier, 0.3 part of initiator, 5 parts of assistant, 6 parts of stabilizer and 100 parts of deionized water;
the water-based acrylic emulsion with durable antibacterial property is prepared by the following steps:
firstly, adding 20% of emulsifier and 10% of initiator into 20% of deionized water, and adding vinyl monomer and 20% of auxiliary agent after dissolving to obtain pre-emulsion;
and secondly, adding the rest of the emulsifier into the rest of the deionized water, sequentially adding the rest of the initiator and the rest of the auxiliary agent, adding the stabilizer, heating the solution to 70 ℃ under the protection of nitrogen, dropwise adding the pre-emulsion obtained in the first step, controlling the dropwise adding speed, keeping the dropwise adding time at 2h, continuously heating to 80 ℃ after the dropwise adding is finished, reacting for 2h, cooling the reactant to 30 ℃ after the reaction is finished, adjusting the pH value to 7, and finally filtering to obtain the water-based acrylic emulsion with the lasting antibacterial property.
Wherein the vinyl monomer is methacrylic acid; emulsifier is sodium dodecyl sulfate; the initiator is azobisisobutyrimidazoline hydrochloride.
The auxiliary agent is prepared by the following steps:
step S11, adding guanidine hydrochloride and hexamethylene diamine into a three-neck flask, setting the temperature at 150 ℃ and the rotating speed at 200r/min, starting stirring after reactants are melted, reducing the temperature to 120 ℃, reacting for 1 hour, then increasing the temperature to 160 ℃, continuing to react for 40 minutes, reducing the temperature to room temperature after the reaction is finished to obtain a solid, dissolving the obtained solid with deionized water to obtain a mixed solution, freezing the mixed solution at 0 ℃ for 24 hours, and then freeze-drying in a freeze dryer for 70 hours to obtain white powder;
step S12, adding white powder and dimethyl sulfoxide into a round-bottom flask, starting stirring until the white powder is completely dissolved at room temperature and the rotating speed of 300r/min, adding methacrylic anhydride and 4-dimethylaminopyridine, stirring at room temperature in the dark for 48h, adding dichloromethane into the obtained reaction liquid at 0 ℃ to generate a precipitate, filtering, washing the obtained precipitate with dichloromethane three times, dissolving the washed precipitate with deionized water, dialyzing with a dialysis bag with the molecular weight cutoff of 500Da for 20h, replacing the deionized water every 2h, after dialysis, freezing the obtained mixed solution at 0 ℃ for 24h, and freeze-drying in a freeze dryer for 70h to obtain a product, namely the auxiliary agent.
Wherein, the molar ratio of guanidine hydrochloride to hexamethylene diamine in the step S11 is 1: 1; the amount ratio of the white powder to the dimethylsulfoxide in step S12 was 10 g: 30 mL; the mass ratio of the white powder to the methacrylic anhydride to the 4-dimethylaminopyridine is 1: 1.2: 0.1.
wherein the stabilizer is prepared by the following steps:
step S21, mixing deionized water, absolute ethyl alcohol and nano-silica, performing ultrasonic treatment for 30min at the frequency of 50kHz, adjusting the pH value to 3 by formic acid after the ultrasonic treatment is finished, adding a silane coupling agent, setting the temperature to be 90 ℃ and the rotating speed to be 300r/min, stirring for 10h, cooling to room temperature after the stirring is finished, performing reduced pressure suction filtration on reaction liquid to remove filtrate, and drying the obtained filter cake to constant weight at the temperature of 90 ℃ to obtain modified silica micropowder;
and S22, adding carboxymethyl cellulose and hydroxyethyl cellulose into deionized water, dissolving at room temperature, setting the temperature to be 40 ℃ and the rotating speed to be 300r/min, dropwise adding an aluminum sulfate solution during stirring for 20min, adding the modified silica micropowder prepared in the step S21 after dropwise adding, continuously stirring for 50min to obtain a mixed solution, cooling the obtained mixed solution, performing vacuum filtration, removing filtrate, and drying the obtained filter cake at 90 ℃ to constant weight to obtain the stabilizer.
Wherein the silane coupling agent in the step S21 is gamma-aminopropyltriethoxysilane, and the mass ratio of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide is 5: 50: 8; the dosage of the silane coupling agent is 4 percent of the total mass of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide; in step S22, the molar concentration of the aluminum sulfate solution is 2.4mol/L, and the dosage ratio of the carboxymethyl cellulose, the hydroxyethyl cellulose, the aluminum sulfate solution, the deionized water and the modified silicon dioxide micropowder is 3 g: 1 g: 4mL of: 100mL of: 1g of the total weight of the composition.
Example 2
A water-based acrylic emulsion with lasting antibacterial function comprises the following raw materials in parts by weight:
110 parts of vinyl monomer, 4 parts of emulsifier, 0.6 part of initiator, 6 parts of assistant, 8 parts of stabilizer and 150 parts of deionized water;
the water-based acrylic emulsion with durable antibacterial property is prepared by the following steps:
firstly, adding 20% of emulsifier and 15% of initiator into 20% of deionized water, and adding vinyl monomer and 20% of auxiliary agent after dissolving to obtain pre-emulsion;
and secondly, adding the rest of the emulsifier into the rest of the deionized water, sequentially adding the rest of the initiator and the rest of the auxiliary agent, adding the stabilizer, heating the solution to 80 ℃ under the protection of nitrogen, dropwise adding the pre-emulsion obtained in the first step, controlling the dropwise adding speed, keeping the dropwise adding time at 3h, continuously heating to 90 ℃ after the dropwise adding is finished, reacting for 3h, cooling the reactant to 40 ℃ after the reaction is finished, adjusting the pH value to 7, and finally filtering to obtain the water-based acrylic emulsion with the lasting antibacterial property.
Wherein the vinyl monomer is hydroxyalkyl methacrylate; the emulsifier is nonylphenol polyoxyethylene ether and ethoxylated ammonium alkylphenol sulfate; the initiator is one of azodicyano valeric acid.
The auxiliary agent is prepared by the following steps:
step S11, adding guanidine hydrochloride and hexamethylene diamine into a three-neck flask, setting the temperature at 150 ℃ and the rotating speed at 200r/min, starting stirring after reactants are melted, reducing the temperature to 120 ℃, reacting for 1.5h, then increasing the temperature to 160 ℃, continuing to react for 50min, reducing the temperature to room temperature after the reaction is finished to obtain a solid, dissolving the obtained solid with deionized water to obtain a mixed solution, freezing the mixed solution at 0 ℃ for 24h, and then freeze-drying in a freeze dryer for 71h to obtain white powder;
step S12, adding white powder and dimethyl sulfoxide into a round-bottom flask, starting stirring until the white powder is completely dissolved at room temperature and the rotating speed of 300r/min, adding methacrylic anhydride and 4-dimethylaminopyridine, stirring at room temperature in the dark for 49h, adding dichloromethane into the obtained reaction liquid at the temperature of 3 ℃ to generate precipitate, filtering, washing the obtained precipitate with dichloromethane three times, dissolving the washed precipitate with deionized water, dialyzing with a dialysis bag with the molecular weight cutoff of 500Da for 20h, replacing the deionized water every 2h, after dialysis, freezing the obtained mixed solution at the temperature of 0 ℃ for 24h, and freeze-drying in a freeze dryer for 71h to obtain a product, namely the auxiliary agent.
Wherein, the molar ratio of guanidine hydrochloride to hexamethylene diamine in the step S11 is 1: 1.2; the amount ratio of the white powder to the dimethylsulfoxide in step S12 was 11 g: 30 mL; the mass ratio of the white powder to the methacrylic anhydride to the 4-dimethylaminopyridine is 1: 1.3: 0.1.
wherein the stabilizer is prepared by the following steps:
step S21, mixing deionized water, absolute ethyl alcohol and nano-silica, performing ultrasonic treatment for 35min under the condition of the frequency of 55kHz, adjusting the pH value to 3 by formic acid after the ultrasonic treatment is finished, adding a silane coupling agent, setting the temperature to be 95 ℃ and the rotating speed to be 300r/min, stirring for 11h, cooling to room temperature after the stirring is finished, performing reduced pressure suction filtration on reaction liquid to remove filtrate, and drying the obtained filter cake to constant weight at 95 ℃ to obtain modified silica micropowder;
and S22, adding carboxymethyl cellulose and hydroxyethyl cellulose into deionized water, dissolving at room temperature, setting the temperature to be 40 ℃ and the rotating speed to be 300r/min, dropwise adding an aluminum sulfate solution during stirring for 20min, adding the modified silica micropowder prepared in the step S21 after dropwise adding, continuously stirring for 55min to obtain a mixed solution, cooling the obtained mixed solution, performing vacuum filtration, removing filtrate, and drying the obtained filter cake at 95 ℃ to constant weight to obtain the stabilizer.
Wherein the silane coupling agent in the step S21 is gamma-aminopropyltriethoxysilane, and the mass ratio of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide is 5: 50: 9; the dosage of the silane coupling agent is 5 percent of the total mass of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide; in step S22, the molar concentration of the aluminum sulfate solution is 2.4mol/L, and the dosage ratio of the carboxymethyl cellulose, the hydroxyethyl cellulose, the aluminum sulfate solution, the deionized water and the modified silicon dioxide micropowder is 3 g: 1 g: 5mL of: 100mL of: 2g of the total weight.
Example 3
A water-based acrylic emulsion with lasting antibacterial function comprises the following raw materials in parts by weight:
120 parts of vinyl monomer, 5 parts of emulsifier, 0.9 part of initiator, 7 parts of assistant, 10 parts of stabilizer and 200 parts of deionized water;
the water-based acrylic emulsion with durable antibacterial property is prepared by the following steps:
firstly, adding 20% of emulsifier and 20% of initiator into 20% of deionized water, and adding vinyl monomer and 20% of auxiliary agent after dissolving to obtain pre-emulsion;
and secondly, adding the rest of the emulsifier into the rest of the deionized water, sequentially adding the rest of the initiator and the rest of the auxiliary agent, adding the stabilizer, heating the solution to raise the temperature to 90 ℃ under the protection of nitrogen, dropwise adding the pre-emulsion obtained in the first step, controlling the dropwise adding speed, keeping the dropwise adding time at 4h, continuing raising the temperature to 100 ℃ after the dropwise adding is finished, reacting for 4h, cooling the reactant to 50 ℃ after the reaction is finished, adjusting the pH value to 8, and finally filtering to obtain the water-based acrylic emulsion with the lasting antibacterial property.
Wherein the vinyl monomer is alkyl methacrylate; the emulsifier is sodium dodecyl sulfate; the initiator is azobiscyanovaleric acid.
The auxiliary agent is prepared by the following steps:
step S11, adding guanidine hydrochloride and hexamethylene diamine into a three-neck flask, setting the temperature at 150 ℃ and the rotating speed at 200r/min, starting stirring after reactants are melted, reducing the temperature to 120 ℃, reacting for 2 hours, then increasing the temperature to 160 ℃, continuing to react for 60 minutes, reducing the temperature to room temperature after the reaction is finished to obtain a solid, dissolving the obtained solid with deionized water to obtain a mixed solution, freezing the mixed solution at 0 ℃ for 24 hours, and then freeze-drying in a freeze dryer for 72 hours to obtain white powder;
step S12, adding white powder and dimethyl sulfoxide into a round-bottom flask, starting stirring until the white powder is completely dissolved at room temperature and the rotating speed of 300r/min, adding methacrylic anhydride and 4-dimethylaminopyridine, stirring at room temperature in the dark for 50h, adding dichloromethane into the obtained reaction liquid at the temperature of 5 ℃ to generate a precipitate, filtering, washing the obtained precipitate with dichloromethane three times, dissolving the washed precipitate with deionized water, dialyzing with a dialysis bag with the molecular weight cutoff of 500Da for 20h, replacing the deionized water every 2h, after dialysis, freezing the obtained mixed solution at the temperature of 0 ℃ for 24h, and freeze-drying in a freeze dryer for 72h to obtain a product, namely the auxiliary agent.
Wherein, the molar ratio of guanidine hydrochloride to hexamethylene diamine in the step S11 is 1: 1.3; the amount ratio of the white powder to the dimethylsulfoxide in step S12 was 12 g: 30 mL; the mass ratio of the white powder to the methacrylic anhydride to the 4-dimethylaminopyridine is 1: 1.4: 0.1.
wherein the stabilizer is prepared by the following steps:
step S21, mixing deionized water, absolute ethyl alcohol and nano-silica, performing ultrasonic treatment for 40min under the condition of frequency of 60kHz, adjusting the pH value to 4 by formic acid after the ultrasonic treatment is finished, adding a silane coupling agent, setting the temperature to be 100 ℃ and the rotating speed to be 300r/min, stirring for 12h, cooling to room temperature after the stirring is finished, performing reduced pressure suction filtration on reaction liquid to remove filtrate, and drying the obtained filter cake to constant weight at 100 ℃ to obtain modified silica micropowder;
and S22, adding carboxymethyl cellulose and hydroxyethyl cellulose into deionized water, dissolving at room temperature, setting the temperature to be 40 ℃ and the rotating speed to be 300r/min, dropwise adding an aluminum sulfate solution during stirring for 20min, adding the modified silica micropowder prepared in the step S21 after dropwise adding, continuously stirring for 60min to obtain a mixed solution, cooling the obtained mixed solution, performing vacuum filtration, removing filtrate, and drying the obtained filter cake at 100 ℃ to constant weight to obtain the stabilizer.
Wherein the silane coupling agent in the step S21 is gamma-aminopropyltriethoxysilane, and the mass ratio of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide is 5: 50: 10; the dosage of the silane coupling agent is 6 percent of the total mass of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide; in step S22, the molar concentration of the aluminum sulfate solution is 2.4mol/L, and the dosage ratio of the carboxymethyl cellulose, the hydroxyethyl cellulose, the aluminum sulfate solution, the deionized water and the modified silicon dioxide micropowder is 3 g: 1 g: 6mL of: 100mL of: 3g of the total weight.
Comparative example 1
The comparative example is a water-based acrylic emulsion which is common in the market and can resist bacteria for a long time.
The emulsions of examples 1 to 3 and comparative example 1 were subjected to the antibacterial property test, and the test results are as follows: and (3) carrying out an antibacterial performance test according to the standard of HG/T3950-2007 antibacterial paint, wherein the durability is an antibacterial property test after the coating is cleaned by ultrasonic waves for 2 hours.
TABLE 1
From the above table 1, it can be seen that the water-based acrylic emulsion prepared by the invention has better lasting antibacterial property, excellent performance after film formation and better storage stability.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. The water-based acrylic emulsion with durable antibacterial property is characterized by comprising the following raw materials in parts by weight: 100 portions of vinyl monomer, 3 to 5 portions of emulsifier, 0.3 to 0.9 portion of initiator, 5 to 7 portions of auxiliary agent, 6 to 10 portions of stabilizer and 100 portions of deionized water and 200 portions;
the water-based acrylic emulsion with durable antibacterial property is prepared by the following steps:
firstly, adding 20% of emulsifier and 10-20% of initiator into 20% of deionized water, and adding vinyl monomer and 20% of auxiliary agent after dissolving to obtain pre-emulsion;
and secondly, adding the rest of the emulsifier into the rest of the deionized water, sequentially adding the rest of the initiator and the rest of the auxiliary agent, adding the stabilizer, heating the solution to 70-90 ℃ under the protection of nitrogen, dripping the pre-emulsion obtained in the first step, controlling the dripping speed, keeping the dripping time at 2-4h, continuously heating to 80-100 ℃ after finishing dripping, reacting for 2-4h, cooling the reactant to 30-50 ℃ after the reaction is finished, adjusting the pH value to 7-8, and finally filtering to obtain the water-based acrylic emulsion with lasting antibacterial property.
2. The water-based acrylic emulsion with durable antibacterial property according to claim 1, wherein the vinyl monomer is one or more of methacrylic acid, alkyl methacrylate, hydroxyalkyl methacrylate and isobornyl methacrylate which are mixed in any proportion; the emulsifier is one or more of sodium dodecyl sulfate, nonylphenol polyoxyethylene ether and ethoxylated ammonium alkylphenol sulfate which are mixed in any proportion; the initiator is one of azobisisobutyronitrile hydrochloride and azobiscyanovaleric acid.
3. The water-based acrylic emulsion with durable antibacterial property as claimed in claim 1, wherein the auxiliary agent is prepared by the following steps:
step S11, adding guanidine hydrochloride and hexamethylene diamine into a three-neck flask, setting the temperature at 150 ℃ and the rotating speed at 200r/min, starting stirring after reactants are melted, reducing the temperature to 120 ℃, reacting for 1-2h, then increasing the temperature to 160 ℃, continuing to react for 40-60min, reducing the temperature to room temperature after the reaction is finished to obtain a solid, dissolving the obtained solid with deionized water to obtain a mixed solution, freezing the mixed solution at 0 ℃ for 24h, and then freeze-drying in a freeze dryer for 70-72h to obtain white powder;
step S12, adding white powder and dimethyl sulfoxide into a round-bottom flask, starting stirring until the white powder is completely dissolved at room temperature and the rotating speed of 300r/min, adding methacrylic anhydride and 4-dimethylaminopyridine, stirring at room temperature in the dark for 48-50h, adding dichloromethane into the obtained reaction solution at 0-5 ℃ to generate a precipitate, filtering, washing the obtained precipitate with dichloromethane three times, dissolving the washed precipitate with deionized water, dialyzing for 20h with a dialysis bag with the molecular weight cutoff of 500Da, replacing the deionized water every 2h, freezing the obtained mixed solution for 24h at 0 ℃ after the dialysis is finished, and freeze-drying in a freeze dryer for 70-72h to obtain a product, namely the auxiliary agent.
4. The durable antibacterial aqueous acrylic emulsion according to claim 3, wherein the molar ratio of guanidine hydrochloride to hexamethylenediamine in step S11 is 1: 1-1.3; the dosage ratio of the white powder to the dimethyl sulfoxide in the step S12 is 10-12 g: 30 mL; the mass ratio of the white powder to the methacrylic anhydride to the 4-dimethylaminopyridine is 1: 1.2-1.4: 0.1.
5. the water-based acrylic emulsion with durable antibacterial property of claim 1, wherein the stabilizer is prepared by the following steps:
step S21, mixing deionized water, absolute ethyl alcohol and nano silicon dioxide, performing ultrasonic treatment for 30-40min under the condition of the frequency of 50-60kHz, adjusting the pH value to 3-4 by formic acid after the ultrasonic treatment is finished, adding a silane coupling agent, setting the temperature to 90-100 ℃ and the rotating speed to 300r/min, stirring for 10-12h, cooling to room temperature after the stirring is finished, performing vacuum filtration on reaction liquid to remove filtrate, and drying the obtained filter cake to constant weight under the condition of 90-100 ℃ to obtain modified silicon dioxide micropowder;
and S22, adding carboxymethyl cellulose and hydroxyethyl cellulose into deionized water, dissolving at room temperature, setting the temperature to be 40 ℃ and the rotating speed to be 300r/min, dropwise adding an aluminum sulfate solution during stirring for 20min, adding the modified silica micropowder prepared in the step S21 after dropwise adding, continuously stirring for 50-60min to obtain a mixed solution, cooling the obtained mixed solution, carrying out vacuum filtration, removing filtrate, and drying the obtained filter cake at 90-100 ℃ to constant weight to obtain the stabilizer.
6. The durable antibacterial aqueous acrylic emulsion according to claim 5, wherein the silane coupling agent in step S21 is γ -aminopropyltriethoxysilane, and the mass ratio of deionized water, absolute ethanol and nano silica is 5: 50: 8-10; the dosage of the silane coupling agent is 4-6% of the total mass of the deionized water, the absolute ethyl alcohol and the nano silicon dioxide; in step S22, the molar concentration of the aluminum sulfate solution is 2.4mol/L, and the dosage ratio of the carboxymethyl cellulose, the hydroxyethyl cellulose, the aluminum sulfate solution, the deionized water and the modified silicon dioxide micropowder is 3 g: 1 g: 4-6 mL: 100mL of: 1-3 g.
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| CN113233995A (en) * | 2021-04-13 | 2021-08-10 | 华南理工大学 | Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof |
| CN113415861A (en) * | 2021-08-24 | 2021-09-21 | 深圳市板明科技股份有限公司 | Water purificant and preparation method and use method thereof |
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| CN113233995A (en) * | 2021-04-13 | 2021-08-10 | 华南理工大学 | Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof |
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| CN113462251A (en) * | 2021-08-06 | 2021-10-01 | 海南赛诺实业有限公司 | Antibacterial coating, preparation method thereof and antibacterial coating film |
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