CN116655943A - Preparation method of antibacterial and antiviral water-based hydroxy acrylate emulsion - Google Patents

Preparation method of antibacterial and antiviral water-based hydroxy acrylate emulsion Download PDF

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CN116655943A
CN116655943A CN202310557674.0A CN202310557674A CN116655943A CN 116655943 A CN116655943 A CN 116655943A CN 202310557674 A CN202310557674 A CN 202310557674A CN 116655943 A CN116655943 A CN 116655943A
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CN116655943B (en
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戴国亮
初广成
廖华
黄钦龙
曹华庆
王�锋
林莉
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Shenzhen Giantechem Technology Co ltd
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Abstract

The invention relates to a preparation method of an antibacterial and antiviral water-based hydroxy acrylate emulsion, belonging to the technical field of special paint. The emulsion is prepared by polymerizing hydroxyl acrylic ester, methacrylic ester and a cross-linked antibacterial monomer serving as film forming materials and adding water for emulsification, wherein the cross-linked antibacterial monomer participates in polymerization, a double-long-chain quaternary ammonium structure is introduced into a side chain, a good antibacterial and antiviral effect is achieved, sulfur in the structure and adjacent oxygen elements can jointly form a coordination effect, the externally added nano titanium dioxide is effectively chelated, the anchoring nano titanium dioxide is achieved, the film damage and photocatalysis synergistic effect are achieved, the antibacterial and antiviral effect is improved, functional components are not easy to separate from a matrix, and the long-acting stable antibacterial and antiviral effect is achieved.

Description

Preparation method of antibacterial and antiviral water-based hydroxy acrylate emulsion
Technical Field
The invention belongs to the technical field of special paint, and particularly relates to a preparation method of an antibacterial and antiviral water-based hydroxy acrylate emulsion.
Background
Current studies indicate that 80% of common infections (e.g., cold, influenza, diarrhea, etc.) are actually transmitted by contact with the contaminated object surface. When touching the surface of an object, germs may adhere to the hands, and after touching the mouth, eyes and nose, the human body may be infected with the germs. In recent years, the importance of cutting the propagation chain has been increasingly realized. The existing coping method mainly kills public objects which are easy to contact through various sterilizing solutions, is large in workload and easy to form a killing dead angle, so that the coating material with the functions of resisting bacteria and viruses has profound research significance.
In the prior art, more reports about antibacterial and antiviral coatings exist, for example, chinese patent CN105968973A discloses that a traditional Chinese medicine extract is added into an aqueous emulsion, and the slow release of the traditional Chinese medicine extract achieves the antibacterial and antiviral effects of the surface, and CN111849266A discloses that a cuprous compound is added into a copolymerization emulsion to achieve the antiviral effect; however, these products generally suffer from the following problems: firstly, the doping amount of the antibacterial and antiviral auxiliary agent is large, the actual resistance effect is not obvious, and the antibacterial and antiviral effect is not obviously improved along with the increase of the dosage proportion of the antibacterial and antiviral auxiliary agent; secondly, the antibacterial and antiviral auxiliary agent is mainly added in an externally-added compound mode, functional components are easy to segregate and break away, and particularly for public medical and health areas, the functional auxiliary agent is generally killed for several times every day, such as sodium hypochlorite, medical alcohol and the like, so that the loss of the functional auxiliary agent can be accelerated, and the long-acting antibacterial and antiviral effects can not be achieved.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a preparation method of an antibacterial and antiviral water-based hydroxy acrylate emulsion.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the antibacterial and antiviral water-based hydroxy acrylate emulsion specifically comprises the following steps:
step S1: uniformly mixing methacrylate, a crosslinking antibacterial monomer, hydroxy acrylate and cyclobutanone, adding a free radical initiator, mixing, applying 80-120rpm mechanical stirring, heating to 62-68 ℃, carrying out heat preservation, stirring, reacting for 30-40min, and removing the cyclobutanone by decompression rotary evaporation to obtain a prepolymer;
further, the methacrylate is one or more of methyl methacrylate, ethyl methacrylate and butyl methacrylate.
Further, the hydroxy acrylic ester is one or more of hydroxy ethyl acrylate, hydroxy propyl acrylate and hydroxy butyl acrylate.
Further, the dosage mass ratio of the hydroxy acrylic ester, the methyl acrylic ester and the crosslinking antibacterial monomer is 1:0.15-0.22:0.08-0.1.
Further, the free radical initiator was diisopropyl peroxydicarbonate in an amount of 0.1wt%.
Step S2: dispersing nano titanium dioxide, an emulsifying agent and deionized ultrasonic, adding the dispersion liquid into the prepolymer liquid, applying 600-800rpm high-speed stirring, heating to 50+/-5 ℃, preserving heat and curing for 1h, adding deionized water to adjust the solid content to 45+/-1%, and carrying out vacuum defoaming treatment to obtain the antibacterial and antiviral water-based hydroxy acrylate emulsion.
Further, the mass ratio of the prepolymerization solution to the nano titanium dioxide to the emulsifier is 100g:1.2-1.6g:0.7-1.1g.
The cross-linking antibacterial monomer is prepared by the following method:
step A1: adding acrylamide and triethylamine into the mixture, stirring and diluting the mixture by adding dioxane, adding a small amount of polymerization inhibitor, uniformly mixing the mixture, introducing nitrogen to replace air, mechanically stirring the mixture at 120-180rpm, heating the mixture to 50-60 ℃, uniformly adding chlorodecane, carrying out heat preservation and stirring reaction for 1.5-2h, introducing chloromethane to boost the pressure to 4.5-5.5bar, continuously heating the mixture to 88-95 ℃, carrying out pressure-maintaining reflux reaction for 3.5-4h, and removing low-boiling substances by rotary evaporation under reduced pressure after the reaction is finished to obtain an intermediate 1;
further, the ratio of the amounts of acrylamide, chlorodecane, triethylamine and dioxane was 0.1mol:0.2mol:1.4-1.8mL:80-110mL, DPPH as polymerization inhibitor, and 0.16-0.2wt%; and (3) performing substitution reaction on acrylamide and chlorodecane to generate a compound with a double long chain structure, and then performing quaternization treatment on the compound by chloromethane.
Step A2: mixing the intermediate 1, acetone and a small amount of photoinitiator, introducing nitrogen to replace air, keeping the temperature at 35-45 ℃, applying mechanical stirring at 300-420rpm, slowly adding thioglycollic acid under ultraviolet irradiation, carrying out irradiation stirring reaction for 1.2-1.8h, and removing acetone by rotary evaporation after the reaction is finished to obtain an intermediate 2;
further, the ratio of the amount of intermediate 1, thioglycollic acid and acetone was 0.1mol:0.1mol:200-260mL, wherein the photoinitiator is a photoinitiator 907T, and the dosage is 0.1-0.15%; under the conditions of photoinitiator promotion and ultraviolet irradiation, thioglycollic acid and double bonds in the intermediate 1 are subjected to click addition reaction, and carboxyl modification is introduced.
Step A3: mixing allyl glycidyl ether, an intermediate 2 and tetrahydrofuran, applying 120-240rpm mechanical stirring, heating to 40-50 ℃, stirring at constant temperature for reacting for 5-7h, and removing tetrahydrofuran by rotary evaporation after the reaction is finished to obtain a crosslinking antibacterial monomer;
further, the ratio of the amount of intermediate 2, allyl glycidyl ether and tetrahydrofuran was 0.1mol:0.11-0.13mol:100-140mL; the quaternary ammonium structure in the intermediate 2 molecule self-catalyzes the ring opening of epoxy groups, promotes the ring opening of the carboxyl of the intermediate 2 and the epoxy groups of allyl glycidyl ether, and introduces active double bond modification.
The invention has the beneficial effects that:
the invention adds a self-made crosslinking antibacterial monomer into emulsion, which is prepared by substitution reaction of acrylamide and chlorodecane, through chloromethane quaternization treatment, a quaternary ammonium compound with a double-long chain structure and a double-bond structure is obtained, then thioglycollic acid is used for click addition, carboxyl end modification is introduced, and then allyl glycidyl ether ring opening reaction is carried out, and an active double bond is introduced; compared with the existing external antibacterial auxiliary agent, the antibacterial auxiliary agent has the following advantages:
1) The cross-linked antibacterial monomer contains a double long-chain quaternary ammonium structure in the molecular structure, and has good inhibition and killing effects on bacteria and viruses;
2) The terminal double bond of the crosslinking antibacterial monomer can participate in the polymerization chain of acrylic ester, so that the terminal double bond is not easy to separate from a matrix, and the stable antibacterial and antiviral effects can be exerted;
3) In the preparation process of the cross-linking antibacterial monomer, thioglycollic acid is used as a bridging material, sulfur element is introduced to molecules, the thioglycollic acid and adjacent oxygen elements can form a coordination effect together, the externally added nano titanium dioxide is effectively chelated, on one hand, an anchoring effect is formed on the nano titanium dioxide, so that the nano titanium dioxide is not easy to separate, on the other hand, the nano titanium dioxide is fixed on the periphery of a quaternary ammonium long chain, and an effective synergistic effect of membrane destruction and photocatalysis is generated, so that the cross-linking antibacterial monomer has high antibacterial and antiviral effects.
After the emulsion prepared by the invention is coated, the antibacterial rate of the surface to staphylococcus aureus and escherichia coli reaches more than 99.9%, the inactivating rate to H1N1 virus reaches more than 95.6%, and the effect is not greatly reduced after 60 times of medical alcohol washing, so that the emulsion can be used as a coating material in medical places.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The specific implementation process of the antibacterial and antiviral water-based hydroxyl acrylic emulsion is as follows;
1) Preparation of crosslinked antimicrobial monomers
1.1, taking acrylamide and triethylamine, adding dioxane, stirring and diluting, adding a small amount of polymerization inhibitor (DPPH, the same in the following examples), uniformly mixing, introducing nitrogen into a reaction system until stable airflow is discharged, displacing air in the reaction system, mechanically stirring at 180rpm, heating to 60 ℃, adding chlorodecane at a constant speed within 20min, and carrying out heat preservation stirring reaction for 1.5h, wherein the dosage ratio of the acrylamide, the chlorodecane, the triethylamine and the dioxane is 0.1mol:0.2mol:1.8mL:110mL, wherein the dosage of the polymerization inhibitor is 0.2wt% of the total amount of raw materials acrylamide and chlorodecane, then methyl chloride is introduced into a reaction system to be pressurized to 5.5bar, the temperature is continuously raised to 95 ℃, the pressure is maintained for reflux reaction for 3.5h, and low-boiling substances including dioxane are removed after the reaction is finished by decompression and rotary evaporation, so that an intermediate 1 is prepared;
1.2, mixing intermediate 1, acetone and a small amount of photoinitiator (907T, the same in the following examples), introducing nitrogen to replace air, keeping the temperature at 45 ℃, applying mechanical stirring at 420rpm, irradiating with a 600W UVA ultraviolet lamp tube, slowly adding thioglycollic acid within 40min, and controlling the total irradiation reaction time of adding the thioglycollic acid to be 1.2h, wherein the dosage ratio of the intermediate 1, the thioglycollic acid and the acetone is 0.1mol:0.1mol:260mL, wherein the photoinitiator is 0.15% of the total amount of the raw material intermediate 1 and thioglycollic acid, and the reaction is finished to remove the acetone by rotary evaporation, so as to obtain an intermediate 2.
1.3, mixing allyl glycidyl ether, an intermediate 2 and tetrahydrofuran, applying mechanical stirring at 240rpm, heating to 50 ℃, and stirring at constant temperature for reaction for 5 hours, wherein the dosage ratio of the intermediate 2 to the allyl glycidyl ether to the tetrahydrofuran is 0.1mol:0.13mol:140mL, and removing tetrahydrofuran after the reaction is finished by rotary evaporation, thus obtaining the crosslinked antibacterial monomer.
2) Preparation of antibacterial and antiviral aqueous hydroxy acrylic ester emulsion
2.1, methyl methacrylate and butyl methacrylate are taken according to the mole ratio of 1:3, mixing the mixture to be used as a methacrylate component, and mixing hydroxyethyl acrylate and hydroxypropyl acrylate according to a molar ratio of 1:1 to be used as a hydroxy acrylate component;
hydroxyl acrylic ester, methacrylic ester and crosslinking antibacterial monomer are mixed according to the mass ratio of 1:0.15:0.1, adding cyclobutanone which is 0.5 times of the total mass of the raw materials, uniformly mixing, adding a free radical initiator (diisopropyl peroxydicarbonate, the same in the following examples) which is 0.1 weight percent of the total mass of the raw materials, mixing, applying mechanical stirring at 120rpm, heating to 68 ℃, preserving heat, stirring and reacting for 30min, and removing the cyclobutanone by decompression and rotary evaporation to obtain a prepolymer.
2.2, mixing nano titanium dioxide, an emulsifier (OP-10, the same in the following examples) and deionized water with the total mass of 8 times of the nano titanium dioxide and the emulsifier, applying 33kHz ultrasonic dispersion treatment for 10min, adding the dispersion liquid into a prepolymer liquid, applying 800rpm high-speed stirring, heating to 50+/-5 ℃ and preserving heat for 1h, wherein the dosage ratio of the prepolymer liquid, the nano titanium dioxide and the emulsifier is 100g:1.2g: and 0.7g, adding deionized water to adjust the solid content to 45+/-1%, and carrying out vacuum defoaming treatment to obtain the antibacterial and antiviral water-based hydroxy acrylate emulsion.
Example 2
The specific implementation process of the antibacterial and antiviral water-based hydroxyl acrylic emulsion is as follows;
1) Preparation of crosslinked antimicrobial monomers
1.1, taking acrylamide and triethylamine, adding dioxane, stirring and diluting, adding a small amount of polymerization inhibitor, uniformly mixing, introducing nitrogen into a reaction system until stable airflow is discharged, displacing air in the reaction system, applying 120rpm mechanical stirring, heating to 50 ℃, adding chlorodecane at a constant speed within 30min, and carrying out heat preservation stirring reaction for 2h, wherein the dosage ratio of the acrylamide to the chlorodecane to the triethylamine to the dioxane is 0.1mol:0.2mol:1.4mL:80mL, wherein the dosage of the polymerization inhibitor is 0.16wt% of the total amount of the raw materials of acrylamide and chlorodecane, then methyl chloride is introduced into the reaction system to be pressurized to 4.5bar, the temperature is continuously raised to 88 ℃, the pressure is maintained for reflux reaction for 4h, and low-boiling substances including dioxane are removed after the reaction is finished by decompression and rotary evaporation, so as to obtain an intermediate 1;
1.2, mixing the intermediate 1, acetone and a small amount of photoinitiator, introducing nitrogen to replace air, keeping the temperature at 35 ℃, applying mechanical stirring at 300rpm, adopting a 500W UVA ultraviolet lamp tube to irradiate, slowly adding thioglycollic acid within 60min, and controlling the total irradiation reaction time of adding the thioglycollic acid to be 1.8h, wherein the dosage ratio of the intermediate 1, the thioglycollic acid and the acetone is 0.1mol:0.1mol:200mL of photoinitiator is taken as a raw material intermediate 1 and 0.1% of the total amount of thioglycollic acid, and the reaction is finished, the rotary evaporation is carried out, and the acetone is removed, so that an intermediate 2 is prepared.
1.3, mixing allyl glycidyl ether, an intermediate 2 and tetrahydrofuran, applying 120rpm mechanical stirring, heating to 40 ℃, and stirring at constant temperature for 7 hours, wherein the dosage ratio of the intermediate 2 to the allyl glycidyl ether to the tetrahydrofuran is 0.1mol:0.11mol:100mL, and removing tetrahydrofuran by rotary evaporation after the reaction is finished, thus obtaining the crosslinked antibacterial monomer.
2) Preparation of antibacterial and antiviral aqueous hydroxy acrylic ester emulsion
2.1, methyl methacrylate, ethyl methacrylate and butyl methacrylate are taken according to the mole ratio of 1: mixing 1:2 as a methacrylate component, wherein hydroxy acrylic ester is hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate according to a molar ratio of 2:1:1 as a hydroxyacrylate component;
hydroxyl acrylic ester, methacrylic ester and crosslinking antibacterial monomer are mixed according to the mass ratio of 1:0.22: mixing 0.08, adding cyclobutanone with the total mass of 0.6 times of the raw materials, mixing, adding a free radical initiator with the total mass of 0.1wt% of the raw materials, mechanically stirring at 80rpm, heating to 62 ℃, preserving heat, stirring, reacting for 40min, and removing the cyclobutanone by decompression and rotary evaporation to obtain the prepolymer.
2.2, mixing nano titanium dioxide, an emulsifier and deionized water with the total mass of 6 times of the nano titanium dioxide and the emulsifier, applying 33kHz ultrasonic dispersion treatment for 10min, adding the dispersion liquid into a prepolymer, applying 600rpm high-speed stirring, heating to 50+/-5 ℃ and preserving heat and curing for 1h, wherein the dosage ratio of the prepolymer to the nano titanium dioxide to the emulsifier is 100g:1.6g:1.1g, then adding deionized water to adjust the solid content to 45+/-1%, and carrying out vacuum defoaming treatment to obtain the antibacterial and antiviral water-based hydroxy acrylate emulsion.
Example 3
The specific implementation process of the antibacterial and antiviral water-based hydroxyl acrylic emulsion is as follows;
1) Preparation of crosslinked antimicrobial monomers
1.1, taking acrylamide and triethylamine, adding dioxane, stirring and diluting, adding a small amount of polymerization inhibitor, uniformly mixing, introducing nitrogen into a reaction system until stable airflow is discharged, displacing air in the reaction system, applying 120rpm mechanical stirring, heating to 55 ℃, adding chlorodecane at a constant speed within 30min, and carrying out heat preservation stirring reaction for 1.8h, wherein the dosage ratio of the acrylamide to the chlorodecane to the triethylamine to the dioxane is 0.1mol:0.2mol:1.6mL:100mL, wherein the dosage of the polymerization inhibitor is 0.19wt% of the total amount of raw materials acrylamide and chlorodecane, then methyl chloride is introduced into a reaction system to be pressurized to 5bar, the temperature is continuously raised to 92 ℃, the pressure is maintained for reflux reaction for 4h, and low-boiling substances including dioxane are removed after the reaction is finished by decompression and rotary evaporation, so as to obtain an intermediate 1;
1.2, mixing the intermediate 1, acetone and a small amount of photoinitiator, introducing nitrogen to replace air, keeping the temperature at 42 ℃, applying mechanical stirring at 360rpm, irradiating by adopting a 600W UVA ultraviolet lamp tube, slowly adding thioglycollic acid within 50min, and controlling the total irradiation reaction time of adding the thioglycollic acid to be 1.5h, wherein the dosage ratio of the intermediate 1, the thioglycollic acid and the acetone is 0.1mol:0.1mol:240mL of photoinitiator is 0.12% of the total amount of the raw material intermediate 1 and thioglycollic acid, and the reaction is finished, the rotary evaporation is carried out, and the acetone is removed, so that the intermediate 2 is prepared.
1.3, mixing allyl glycidyl ether, an intermediate 2 and tetrahydrofuran, applying mechanical stirring at 240rpm, heating to 46 ℃, and stirring at constant temperature for reaction for 6.5 hours, wherein the dosage ratio of the intermediate 2 to the allyl glycidyl ether to the tetrahydrofuran is 0.1mol:0.11mol:120mL, and removing tetrahydrofuran by rotary evaporation after the reaction is finished, thus obtaining the cross-linking antibacterial monomer.
2) Preparation of antibacterial and antiviral aqueous hydroxy acrylic ester emulsion
2.1, methyl methacrylate, ethyl methacrylate and butyl methacrylate are taken according to the mole ratio of 1: mixing 1:2 as a methacrylate component, wherein hydroxy acrylic ester is hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate according to a molar ratio of 2:1:1 as a hydroxyacrylate component;
hydroxyl acrylic ester, methacrylic ester and crosslinking antibacterial monomer are mixed according to the mass ratio of 1:0.2:0.09, adding cyclobutanone with the total mass of 0.5 times of the raw materials, uniformly mixing, adding a free radical initiator with the total mass of 0.1wt% of the raw materials, mixing, applying mechanical stirring at 120rpm, heating to 65 ℃, keeping the temperature, stirring and reacting for 35min, and removing the cyclobutanone by decompression and rotary evaporation to obtain the prepolymer.
2.2, mixing nano titanium dioxide, an emulsifier and deionized water which is 8 times of the total mass of the nano titanium dioxide and the emulsifier, applying 33kHz ultrasonic dispersion treatment for 10min, adding the dispersion liquid into a prepolymer, applying 800rpm high-speed stirring, heating to 50+/-5 ℃ and preserving heat and curing for 1h, wherein the dosage ratio of the prepolymer to the nano titanium dioxide to the emulsifier is 100g:1.4g: and 0.9g, adding deionized water to adjust the solid content to 45+/-1%, and carrying out vacuum defoaming treatment to obtain the antibacterial and antiviral water-based hydroxy acrylate emulsion.
Comparative example
This comparative example was prepared from a commercially available aqueous modified polyacrylate emulsion (supplied by Instroy technology (Guangdong) Co., ltd.), nano titanium dioxide and didecyl dimethyl ammonium chloride in an amount ratio of 100g:1.4g:0.25g of the mixture is mixed, and then the solid content is adjusted to 45+/-1% by deionized water, so as to prepare the antibacterial and antiviral emulsion.
The emulsions prepared in examples 1-3 and comparative examples were repeatedly brushed and dried on the surface of a sterile glass slide, the thickness of the coating layer was controlled to be 0.8mm, and samples were prepared and respectively subjected to antibacterial and antiviral tests by the following specific test methods:
antibacterial test: taking staphylococcus aureus (ATCC 25923) and escherichia coli (ATCC 25922) as test strains, inoculating the test strains into a broth culture medium for culturing for 24 hours, and diluting with sterile physiological saline to prepare bacterial liquid; sterilizing both the sample and the blank slide by ultraviolet irradiation for 30min, transferring 0.2mL of bacterial liquid, respectively spreading the sample and the blank slide, and placing in saturated humidity,Culturing in a incubator with the temperature of 37 ℃ and the illumination of 500lx for 5 hours; washing the surface of the coating with 5mL of sterile physiological saline, respectively taking 0.5mL of washing liquid to inoculate into an agar culture medium, placing the agar culture medium into an incubator to culture for 24 hours, and respectively counting colony numbers;
antiviral test: in a sterile operation cabinet, plaque forming unit concentration is 1×10 4 Taking 0.1mL of pfu H1N1 type influenza virus-PBS buffer solution by a pipette, respectively fully paving a sample and a blank slide, then coating a sterile slide to ensure that the virus solution is uniformly and fully contacted with the test piece, placing the test piece in the incubator for culturing for 30min, and firstly washing the virus solution contact surfaces of the two slides by 5mL of PBS buffer solution to be marked as test stock solution; diluting the test stock solution with PBS buffer solution continuously for 10 times to obtain diluted samples, adding 100uL of each diluted solution into a Corning 12-well plate hole containing 50 mu LMDCK cell suspension, culturing for 1 hour, adding MDCK cells into a plaque culture medium, culturing for 3 days at 35 ℃, removing culture medium supernatant, fixing MDCK cells with formaldehyde solution at room temperature, removing agar coating, counting plaques after staining cells with crystal violet, and calculating TCID50 by using a Reed-Muench method to obtain the virus inactivation rate.
The specific test data are shown in table 1:
TABLE 1
As shown in the data of Table 1, the emulsion prepared by the invention has excellent antibacterial effect on staphylococcus aureus and escherichia coli, and also has good inactivating effect on H1N1 influenza virus.
To explore the lasting antibacterial and antiviral effects of the coating, the above samples were taken, rinsed with 10mL of medical alcohol spray, dried in a 50 ℃ oven for 2 hours, repeatedly treated for 60 times, and subjected to antibacterial and antiviral tests again according to the above test method, and specific test data are shown in table 2:
TABLE 2
As shown in the data of Table 2, the emulsion prepared by the invention has excellent lasting antibacterial effect on staphylococcus aureus and escherichia coli, the inactivation rate of H1N1 type influenza virus is still kept above 91.5%, the antibacterial effect of the comparative example is reduced to a certain extent, and the inactivation of the virus is obviously reduced.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (10)

1. The preparation method of the antibacterial and antiviral water-based hydroxy acrylate emulsion is characterized by comprising the following steps of:
step S1: uniformly mixing methacrylate, a crosslinking antibacterial monomer, hydroxy acrylate and cyclobutanone, adding a free radical initiator, mixing, stirring and heating to 62-68 ℃, preserving heat and stirring for reaction for 30-40min, and removing the cyclobutanone by decompression and rotary evaporation to obtain a prepolymer;
step S2: dispersing nano titanium dioxide, an emulsifying agent and deionized ultrasonic, adding the dispersion liquid into the prepolymer liquid, stirring at a high speed, heating to 50+/-5 ℃, preserving heat and curing for 1h, adding deionized water to adjust the solid content to 45+/-1%, and carrying out vacuum defoaming treatment to obtain the antibacterial and antiviral water-based hydroxy acrylate emulsion.
2. The method for preparing the antibacterial and antiviral aqueous hydroxyacrylate emulsion according to claim 1, wherein the crosslinked antibacterial monomer is prepared by the following method:
step A1: adding acrylamide and triethylamine into the mixture, stirring and diluting the mixture by adding dioxane, adding a polymerization inhibitor, uniformly mixing the mixture, introducing nitrogen to replace air, stirring and heating the mixture to 50-60 ℃, uniformly adding chlorodecane, carrying out heat preservation and stirring reaction for 1.5-2h, introducing chloromethane to boost the pressure to 4.5-5.5bar, continuously heating the mixture to 88-95 ℃, carrying out pressure-holding reflux reaction for 3.5-4h, and carrying out reduced pressure rotary evaporation to remove low-boiling substances after the reaction is finished to obtain an intermediate 1;
step A2: mixing the intermediate 1, acetone and a photoinitiator, introducing nitrogen to replace air, keeping the temperature at 35-45 ℃, applying mechanical stirring and ultraviolet irradiation, slowly adding thioglycollic acid, carrying out irradiation stirring reaction for 1.2-1.8 hours, and removing the acetone by rotary evaporation after the reaction is finished to obtain an intermediate 2;
step A3: mixing allyl glycidyl ether, an intermediate 2 and tetrahydrofuran, stirring and heating to 40-50 ℃, stirring and reacting for 5-7h at constant temperature, and removing tetrahydrofuran by rotary evaporation after the reaction is finished to obtain the cross-linking antibacterial monomer.
3. The method for preparing the antibacterial and antiviral aqueous hydroxyacrylate emulsion according to claim 2, wherein the dosage ratio of acrylamide, chlorodecane, triethylamine and dioxane is 0.1mol:0.2mol:1.4-1.8mL:80-110mL, DPPH as polymerization inhibitor, and 0.16-0.2wt%.
4. The method for preparing the antibacterial and antiviral aqueous hydroxyacrylate emulsion according to claim 3, wherein the dosage ratio of the intermediate 1, thioglycollic acid and acetone is 0.1mol:0.1mol:200-260mL, wherein the photoinitiator is 907T, and the dosage is 0.1-0.15%.
5. The method for preparing the antibacterial and antiviral aqueous hydroxyacrylate emulsion according to claim 4, wherein the ratio of the amount of the intermediate 2, allyl glycidyl ether and tetrahydrofuran is 0.1mol:0.11-0.13mol:100-140mL.
6. The method for preparing the antibacterial and antiviral aqueous hydroxy acrylate emulsion according to claim 5, wherein the mass ratio of the hydroxy acrylate to the methacrylate to the crosslinking antibacterial monomer is 1:0.15-0.22:0.08-0.1.
7. The method for preparing an antibacterial and antiviral aqueous hydroxyacrylate emulsion according to claim 6, wherein the hydroxyacrylate is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate.
8. The method for preparing the antibacterial and antiviral aqueous hydroxy acrylate emulsion according to claim 6, wherein the methacrylate is one or more of methyl methacrylate, ethyl methacrylate and butyl methacrylate.
9. The method for preparing the antibacterial and antiviral aqueous hydroxy acrylic ester emulsion according to claim 6, wherein the free radical initiator is diisopropyl peroxydicarbonate, and the amount is 0.1wt%.
10. The preparation method of the antibacterial and antiviral water-based hydroxyl acrylic emulsion according to claim 6, wherein the mass ratio of the pre-polymerization solution to the nano titanium dioxide to the emulsifier is 100g:1.2-1.6g:0.7-1.1g.
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