A kind of water-based environmentally friendly olefin structure antibacterial emulsion and preparation method

Abstract

The invention belongs to the technical field of acrylic resins, and discloses a water-based environmentally friendly alkenyl structure antibacterial emulsion and a preparation method, including 100 parts of alkenyl monomers, 1-7 parts of diquaternary ammonium salt styrene diphenyl sulfone monomers, 1.2-1.6 parts of initiators, 2-3 parts of emulsifiers, and 5.8-8.3 parts of neutralizers; the present invention introduces styrene structure monomers into the acrylic resin molecular chain, which is conducive to improving the hardness and impact resistance of the paint film, and showing good mechanical properties and heat resistance. The diquaternary ammonium salt styrene diphenyl sulfone monomer contains a unique diquaternary ammonium salt antibacterial group, which is grafted into the acrylic resin, giving the paint film excellent long-term antibacterial properties. Escherichia coli and Staphylococcus aureus show obvious antibacterial rates. There are broad application prospects in high-performance antibacterial coatings, adhesives and other materials.

Description

Technical Field

[0001] The invention belongs to the technical field of acrylic resins, and in particular relates to a water-based environmentally friendly olefin-structured antibacterial emulsion and a preparation method thereof. Background Art

[0002] Acrylic resin is a polymer resin obtained by free radical polymerization of monomers containing alkenyl groups such as acrylate and acrylic acid. It is widely used in coatings, inks, adhesives, etc. Modification of acrylic resin and its emulsion to improve its mechanical strength and heat resistance, give it antibacterial properties, and expand the application field of acrylic resin is a research hotspot.

[0003] Developing new polymer monomers and copolymerizing and modifying acrylic resins are common methods to improve their comprehensive performance. Adding styrene monomers during the polymerization process can improve the mechanical properties of acrylic resins; adding quaternary ammonium salt antibacterial monomers can give acrylic resins long-lasting antibacterial properties. The invention patent with announcement number CN115433498B discloses a method for preparing a waterproof and antibacterial acrylic resin wood paint and its application. Hydrophobic diperfluoroalkyl chains and antibacterial diquaternary ammonium salt groups are introduced into the main chain of acrylic resin, which improves the water resistance and waterproofness of acrylic resin, and at the same time gives acrylic resin excellent antibacterial and mildew-proof effects. However, this patent does not improve the mechanical and heat resistance of acrylic resins. Summary of the invention

[0004] The invention solves the problem that the acrylic resin solution has poor heat resistance and no antibacterial performance.

[0005] The technical scheme of the present invention is: an aqueous environmentally friendly olefin structure antibacterial emulsion, comprising the following raw materials in parts by weight: 100 parts of olefin monomer, 1-7 parts of diquaternary ammonium salt styrene diphenyl sulfone monomer, 1.2-1.6 parts of initiator, 2-3 parts of emulsifier, and 5.8-8.3 parts of neutralizer.

[0006] The diquaternary ammonium salt styryl diphenyl sulfone monomer has the structural formula described in the following formula (I):

[0007] Where n is any integer between 6 and 10.

[0008] Among them, the olefinic monomers include butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxypropyl acrylate.

[0009] Wherein, the initiator includes potassium persulfate or ammonium persulfate.

[0010] Among them, the emulsifiers include sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and OP-10.

[0011] Wherein, the neutralizing agent includes triethylamine and ammonia water.

[0012] Among them, the preparation method of the water-based environmentally friendly olefinic structure antibacterial emulsion includes: adding water, olefinic monomer, diquaternary ammonium salt styrene diphenyl sulfone monomer, and emulsifier into a reaction container, stirring evenly, heating to 60-80°C in a nitrogen atmosphere, dripping an aqueous solution containing an initiator, and reacting for 1-1.5 hours; then adding olefinic monomer and diquaternary ammonium salt styrene diphenyl sulfone monomer, dripping an aqueous solution containing an initiator, continuing to react for 3-5 hours, cooling, adding a neutralizer, mixing evenly, and obtaining a water-based environmentally friendly olefinic structure antibacterial emulsion.

[0013] Wherein, the preparation method of diquaternary ammonium salt styryl diphenyl sulfone monomer comprises:

[0014] Step (1), add a methanesulfonic acid solution of 7.5% by mass of phosphorus pentoxide, 4,4'-sulfonylbis(benzene-1,2-diamine), and 4-vinylbenzoic acid to a reaction vessel provided with a condenser reflux tube, heat to 115-130° C. in a nitrogen atmosphere for 1-3 hours to react, dilute with water, filter, wash the precipitate with water and methanol in turn, and dry to obtain a styryl imidazole diphenyl sulfone monomer. The reaction formula is:

[0015]

[0016] Step (2), add acetonitrile, styryl imidazole diphenyl sulfone monomer, chloroalkyl compound, potassium carbonate to a reaction vessel provided with a condenser reflux tube, heat to 80-85°C, react for 4-8h, then add chloroalkyl compound, continue to react for 6-12h, concentrate the solution, wash the precipitate with water, and then recrystallize in ethanol to obtain diquaternary ammonium salt styryl diphenyl sulfone monomer. The reaction formula is:

[0017]

[0018] Wherein, in step (1), the molar ratio of 4,4'-sulfonylbis(benzene-1,2-diamine) to 4-vinylbenzoic acid is 1:(1.8-2.4).

[0019] The molar ratio of the styrylimidazole diphenyl sulfone monomer, the chloroalkyl compound and potassium carbonate is 1:(4-4.8):(2-2.2). The structural formula of the chloroalkyl compound is CI-C n H 2n+1 , where n is any integer between 6 and 10.

[0020] The technical effect produced by the present invention is as follows: in the catalyst system of methanesulfonic acid solution of phosphorus pentoxide, 4,4'-sulfonylbis(benzene-1,2-diamine) and 4-vinylbenzoic acid are subjected to cyclization reaction to obtain a styryl imidazole diphenyl sulfone monomer, which is then subjected to substitution and quaternization reaction with a chloroalkyl compound to obtain a novel diquaternary ammonium salt styryl diphenyl sulfone monomer.

[0021] The present invention uses methyl methacrylate, methacrylic acid and other vinyl monomers to copolymerize with diquaternary ammonium salt styrene diphenyl sulfone monomers to obtain a water-based environmentally friendly acrylic resin emulsion. The introduction of styrene structural monomers into the acrylic resin molecular chain is beneficial to improving the hardness and impact resistance of the paint film, and has excellent mechanical properties.

[0022] The invention introduces a high temperature resistant diphenyl sulfone structure into the main molecular chain of acrylic resin, significantly improves the initial thermal decomposition temperature of the paint film, and exhibits good heat resistance.

[0023] The diquaternary ammonium salt styryl diphenyl sulfone monomer of the present invention contains a unique diquaternary ammonium salt antibacterial group, which is grafted into an acrylic resin to give the paint film excellent long-term antibacterial performance. It shows a significant antibacterial rate against Escherichia coli and Staphylococcus aureus. It has broad application prospects in high-performance antibacterial coatings, adhesives and other materials. DETAILED DESCRIPTION

[0024] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased through regular channels.

[0025] Example 1

[0026] Step (1), add 50mL of 7.5% methanesulfonic acid solution of phosphorus pentoxide by mass, 2mmol 4,4'-sulfonylbis(benzene-1,2-diamine) (CAS No. 13224-79-8), 4.8mmol 4-vinylbenzoic acid (CAS No. 1075-49-6) to a reaction container equipped with a condenser reflux tube, heat to 130°C in a nitrogen atmosphere for 1h to react, dilute with water, filter, wash the precipitate with water and methanol in turn, and dry to obtain a styryl imidazole diphenyl sulfone monomer. The structural formula is:

[0027]

[0028] Step (2), add acetonitrile, 2mmol styryl imidazole diphenyl sulfone monomer, 4mmol 1-chlorodecane, 4mmol potassium carbonate to a reaction vessel provided with a condenser reflux tube, heat to 85°C, react for 6h, then add 4.8mmol 1-chlorodecane, continue to react for 6h, concentrate the solution, wash the precipitate with water, and then recrystallize in ethanol to obtain a diquaternary ammonium salt styryl diphenyl sulfone monomer. The structural formula is:

[0029]

[0030] Step (3), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 0.2g of diquaternary ammonium salt styrene diphenyl sulfone monomer, 1.3g of sodium lauryl sulfate, and 0.7g of OP-10 to the reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of initiator potassium persulfate, and react for 1h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, and 0.8g of diquaternary ammonium salt styrene diphenyl sulfone monomer, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of neutralizer triethylamine, and mix well to obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0031] Example 2

[0032] Step (1), adding 60 mL of a 7.5% by mass phosphorus pentoxide methanesulfonic acid solution, 2 mmol 4,4'-sulfonylbis(benzene-1,2-diamine), and 4.8 mmol 4-vinylbenzoic acid into a reaction container provided with a condenser reflux tube, heating to 130° C. in a nitrogen atmosphere for 1 hour to react, adding water to dilute, filtering, washing the precipitate with water and methanol in turn, and drying to obtain a styryl imidazole diphenyl sulfone monomer.

[0033] Step (2), add acetonitrile, 2mmol styryl imidazole diphenyl sulfone monomer, 4.8mmol 1-chlorohexane, 4.8mmol potassium carbonate to a reaction vessel provided with a condenser reflux tube, heat to 80°C, react for 8h, then add 4.8mmol 1-chlorohexane, continue to react for 12h, concentrate the solution, wash the precipitate with water, and then recrystallize in ethanol to obtain a diquaternary ammonium salt styryl diphenyl sulfone monomer. The structural formula is:

[0034]

[0035] Step (3), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 0.2g of diquaternary ammonium salt styrene diphenyl sulfone monomer, 2g of sodium dodecylbenzene sulfonate, and 1g of OP-10 to the reaction container, stir evenly, heat to 60°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.3g of initiator ammonium persulfate, and react for 1.5h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, 0.8g of diquaternary ammonium salt styrene diphenyl sulfone monomer, dropwise add an aqueous solution containing 1.3g of ammonium persulfate, continue to react for 5h, cool, add 8.9mL of neutralizing agent ammonia water (mass fraction 20%), mix evenly, and obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0036] Example 3

[0037] Step (1), adding 50 mL of a 7.5% by mass phosphorus pentoxide methanesulfonic acid solution, 2 mmol 4,4'-sulfonylbis(benzene-1,2-diamine), and 3.6 mmol 4-vinylbenzoic acid to a reaction vessel provided with a condenser reflux tube, heating to 115° C. in a nitrogen atmosphere for 3 hours to react, adding water to dilute, filtering, washing the precipitate with water and methanol in turn, and drying to obtain a styryl imidazole diphenyl sulfone monomer.

[0038] Step (2), add acetonitrile, 2mmol styryl imidazole diphenyl sulfone monomer, 4mmol 1-chlorooctane, 4.4mmol potassium carbonate to a reaction vessel provided with a condenser reflux tube, heat to 85°C, react for 4h, then add 4mmol 1-chlorooctane, continue to react for 10h, concentrate the solution, wash the precipitate with water, and then recrystallize in ethanol to obtain a diquaternary ammonium salt styryl diphenyl sulfone monomer. The structural formula is:

[0039]

[0040] Step (3), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 0.2g of diquaternary ammonium salt styrene diphenyl sulfone monomer, 1.6g of sodium lauryl sulfate, and 0.8g of OP-10 to the reaction container, stir evenly, heat to 80°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of initiator potassium persulfate, and react for 1.5h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, 0.8g of diquaternary ammonium salt styrene diphenyl sulfone monomer, dropwise add an aqueous solution containing 1g of potassium persulfate, continue to react for 3h, cool, add 8.9mL of neutralizing agent ammonia water (mass fraction 20%), mix evenly, and obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0041] Comparative Example 1

[0042] The difference between this comparative example and Example 1 is that no diquaternary ammonium salt styryl diphenyl sulfone monomer is added to the acrylic resin emulsion.

[0043] Step (1), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 1.3g of sodium lauryl sulfate, and 0.7g of OP-10 to a reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of an initiator potassium persulfate, and react for 1h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of a neutralizing agent triethylamine, mix well, and obtain an aqueous environmentally friendly acrylic resin emulsion.

[0044] Comparative Example 2

[0045] The difference between this comparative example and Example 1 is that the diquaternary ammonium salt styryl diphenyl sulfone monomer is not added to the acrylic resin emulsion, and styryl imidazole diphenyl sulfone monomer is added, and the structural formula is

[0046] Step (1), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 0.2g of styryl imidazole diphenyl sulfone monomer, 1.3g of sodium dodecyl sulfate, and 0.7g of OP-10 to a reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of an initiator potassium persulfate, and react for 1h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, and 0.8g of styryl imidazole diphenyl sulfone monomer, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of a neutralizing agent triethylamine, and mix well to obtain an aqueous environmentally friendly acrylic resin emulsion.

[0047] Comparative Example 3

[0048] The difference between this comparative example and Example 1 is that the diquaternary ammonium salt styryl diphenyl sulfone monomer is not added to the antibacterial emulsion, but styryl imidazole quaternary ammonium salt is added.

[0049] Step (1), add acetonitrile, N-methylimidazole, and 4-chloromethylstyrene to a reaction vessel, heat to 40°C, react for 48 hours, concentrate the solution, wash with ether, and dry to obtain styrene imidazole quaternary ammonium salt. The reaction formula is:

[0050]

[0051] Step (2), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 0.2g of styrene imidazole quaternary ammonium salt, 1.3g of sodium lauryl sulfate, and 0.7g of OP-10 to a reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of initiator potassium persulfate, and react for 1h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, and 0.8g of styrene imidazole quaternary ammonium salt, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of neutralizer triethylamine, and mix well to obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0052] Pour the emulsion onto the mold surface and dry and cure it in an oven at 60°C for 8 hours to form a paint film. The hardness of the paint film is tested according to the GB / T6739-2022 method. The impact resistance is tested according to the GB / T 1732-2020 method.

[0053] The paint film was subjected to a thermogravimetric performance test in a thermogravimetric analyzer, with a nitrogen range, a test temperature of 20-700°C, and a heating rate of 20°C / min. The test results are shown in Table 1.

[0054] Table 1 Emulsion paint film performance test

[0055]

[0056] Escherichia coli and Staphylococcus aureus were cultured and activated respectively, and 10 7 cfu / mL bacterial suspension. Pipette 0.5mL of bacterial suspension and drop it on the surface of the latex paint film (5cm×5cm), then cover the surface of the latex paint film with a sterilized polyethylene film, place it in a constant temperature and humidity incubator, and culture it at 37℃ for 24h. Elute the bacteria on the surface of the latex paint film and polyethylene film with a 0.8% mass fraction of sodium chloride solution, transfer 1mL of the eluate, apply it on the surface of the nutrient agar culture medium, place it in a constant temperature and humidity incubator, culture it at 37℃ for 24h, and count the colonies. Calculate the antibacterial rate R.

[0057] R = (BC) / B × 100%. B is the average number of recovered bacteria (cfu / piece) of the blank control sample after 24 hours of culture, and the blank control sample is the emulsion paint film of comparative example 1. C is the average number of recovered bacteria (cfu / piece) of the test group after 24 hours of culture. The test results are shown in Table 2.

[0058] Table 2 Antibacterial performance test of latex paint film

[0059] Escherichia coli inhibition rate (%) Staphylococcus aureus inhibition rate (%) Example 1 88.3 83.9 Example 2 86.7 82.4 Example 3 88.1 83.5 Comparative Example 2 15.3 10.8 Comparative Example 3 79.2 74.6

[0060] As shown in Table 1 and Table 2, Examples 1, 2 and 3 utilize methyl methacrylate, methacrylic acid and other alkenyl monomers to copolymerize with diquaternary ammonium salt styrene diphenyl sulfone monomers to introduce styrene structure monomers into the acrylic resin molecular chain, and the hardness of the paint film reaches 3H, and the impact resistance reaches 45-50cm, with excellent mechanical properties; and the high temperature resistant diphenyl sulfone structure is introduced into the molecular main chain of the acrylic resin, and the initial thermal decomposition temperature of 5% mass loss reaches 286.2-287.8°C, showing good heat resistance.

[0061] The diquaternary ammonium styryl diphenyl sulfone monomer contains a unique diquaternary ammonium antibacterial group, which is grafted into the acrylic resin, giving the paint film excellent long-term antibacterial properties. It shows a significant inhibition rate against Escherichia coli and Staphylococcus aureus.

[0062] The acrylic resin emulsion of Comparative Example 1 does not contain diquaternary ammonium salt styrene diphenyl sulfone monomer, and the acrylic resin molecular chain does not contain styrene structure monomer and high temperature resistant diphenyl sulfone structure. The hardness of the paint film is 1H, the impact resistance is 30cm, the mechanical properties are not good, the initial thermal decomposition temperature is 272.4°C, and the heat resistance is not good. In addition, the molecular chain does not contain diquaternary ammonium salt groups, and the antibacterial property is very poor.

[0063] Comparative Example 2 added styrylimidazole diphenyl sulfone monomer during the polymerization process, introduced styrene structure monomer and high temperature resistant diphenyl sulfone structure into the acrylic resin molecular chain, endowed the paint film with good mechanical properties and heat resistance, the hardness of the paint film reached 3H, the impact resistance reached 45cm, and the initial thermal decomposition temperature reached 286.9° C. However, the styrylimidazole diphenyl sulfone monomer does not contain a diquaternary ammonium salt antibacterial group, and the antibacterial rate of the paint film against Escherichia coli and Staphylococcus aureus is very low.

[0064] Comparative Example 3 uses styrene imidazole quaternary ammonium salt and olefinic monomer for polymerization reaction. The diphenyl sulfone structural unit is not resistant to high temperatures, resulting in the thermal decomposition temperature of the paint film being significantly lower than that of Example 1.

[0065] Example 4

[0066] The difference between this embodiment and embodiment 1 is that the total amount of diquaternary ammonium salt styryl diphenyl sulfone monomer used is 2.5 g.

[0067] Step (1), add 200mL water, 9.8g butyl acrylate, 13.5g methyl methacrylate, 1.2g methacrylic acid, 1.5g hydroxypropyl acrylate, 0.6g diquaternary ammonium salt styrene diphenyl sulfone monomer, 1.3g sodium lauryl sulfate, 0.7g OP-10 to a reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of initiator potassium persulfate, and react for 1h; then add 28.9g butyl acrylate, 38.8g methyl methacrylate, 2.8g methacrylic acid, 3.5g hydroxypropyl acrylate, 1.9g diquaternary ammonium salt styrene diphenyl sulfone monomer, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of neutralizer triethylamine, mix well, and obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0068] Example 5

[0069] The difference between this embodiment and embodiment 1 is that the total amount of diquaternary ammonium salt styryl diphenyl sulfone monomer used is 4 g.

[0070] Step (1), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 0.9g of diquaternary ammonium salt styrene diphenyl sulfone monomer, 1.3g of sodium lauryl sulfate, and 0.7g of OP-10 to a reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of initiator potassium persulfate, and react for 1h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, and 3.1g of diquaternary ammonium salt styrene diphenyl sulfone monomer, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of neutralizer triethylamine, and mix well to obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0071] Example 6

[0072] The difference between this embodiment and embodiment 1 is that the total amount of diquaternary ammonium salt styryl diphenyl sulfone monomer used is 5.5 g.

[0073] Step (1), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 1.1g of diquaternary ammonium salt styryl diphenyl sulfone monomer, 1.3g of sodium lauryl sulfate, and 0.7g of OP-10 to a reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of an initiator potassium persulfate, and react for 1h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, and 4.3g of diquaternary ammonium salt styryl diphenyl sulfone monomer, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of a neutralizing agent triethylamine, and mix well to obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0074] Example 7

[0075] The difference between this embodiment and embodiment 1 is that the total amount of diquaternary ammonium salt styryl diphenyl sulfone monomer used is 7 g.

[0076] Step (1), add 200mL of water, 9.8g of butyl acrylate, 13.5g of methyl methacrylate, 1.2g of methacrylic acid, 1.5g of hydroxypropyl acrylate, 1.4g of diquaternary ammonium salt styryl diphenyl sulfone monomer, 1.3g of sodium lauryl sulfate, and 0.7g of OP-10 to a reaction container, stir evenly, heat to 70°C in a nitrogen atmosphere, dropwise add an aqueous solution containing 0.2g of initiator potassium persulfate, and react for 1h; then add 28.9g of butyl acrylate, 38.8g of methyl methacrylate, 2.8g of methacrylic acid, 3.5g of hydroxypropyl acrylate, and 5.6g of diquaternary ammonium salt styryl diphenyl sulfone monomer, dropwise add an aqueous solution containing 1.3g of potassium persulfate, continue to react for 4h, cool, add 5.8g of neutralizer triethylamine, and mix well to obtain an aqueous environmentally friendly olefin structure antibacterial emulsion.

[0077] The emulsion was poured onto the mold surface and dried and cured in an oven at 60°C for 8 hours to form a paint film. The hardness, impact resistance, thermogravimetric properties and antibacterial properties of the paint film were tested according to the above method. The test results are shown in Table 3.

[0078] Table 3 Performance test of latex paint film

[0079]

[0080] It can be seen from Table 3 that with the increasing amount of diquaternary ammonium salt styrene diphenyl sulfone monomer, the initial thermal decomposition temperature of the paint film becomes higher and higher, reaching 294.8°C, the heat resistance is also good, the antibacterial rate against Escherichia coli and Staphylococcus aureus is also getting higher and higher, both reaching 99.9%, the hardness and impact resistance are significantly increased, but when the dosage is too large, the hardness and impact resistance tend to decrease.

[0081] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A water-based environmentally friendly alkenyl structure antibacterial emulsion, characterized in that: The method comprises the following raw materials in parts by weight: 100 parts of olefin monomer, 1-7 parts of diquaternary ammonium salt styrene diphenyl sulfone monomer, 1.2-1.6 parts of initiator, 2-3 parts of emulsifier, and 5.8-8.3 parts of neutralizer; The diquaternary ammonium salt styryl diphenyl sulfone monomer has the structural formula described in the following formula (I): Formula (I), wherein n is any integer between 6 and 10.

2. The water-based environmentally friendly alkenyl structured antibacterial emulsion according to claim 1, characterized in that: The ethylenic monomer includes any one of butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxypropyl acrylate.

3. The water-based environmentally friendly alkenyl structured antibacterial emulsion according to claim 1, characterized in that: The initiator is potassium persulfate or ammonium persulfate.

4. The water-based environmentally friendly alkenyl structured antibacterial emulsion according to claim 1, characterized in that: The emulsifier is a combination of sodium dodecyl sulfate and OP-10, or a combination of sodium dodecylbenzene sulfonate and OP-10.

5. The water-based environmentally friendly alkenyl structured antibacterial emulsion according to claim 1, characterized in that: The neutralizing agent is triethylamine or ammonia water.

6. A method for preparing the water-based environmentally friendly alkenyl structured antibacterial emulsion according to any one of claims 1 to 5, characterized in that: The preparation method comprises: adding water, olefin monomer, diquaternary ammonium salt styryl diphenyl sulfone monomer and emulsifier into a reaction container, stirring evenly, heating to 60-80°C in a nitrogen atmosphere, dripping an aqueous solution containing an initiator, and reacting for 1-1.5 hours; then adding olefin monomer and diquaternary ammonium salt styryl diphenyl sulfone monomer, dripping an aqueous solution containing an initiator, continuing to react for 3-5 hours, cooling, adding a neutralizer, mixing evenly, and obtaining a water-based environmentally friendly olefin structure antibacterial emulsion.

7. The method for preparing the water-based environmentally friendly alkenyl structured antibacterial emulsion according to claim 6, characterized in that: The preparation method of the diquaternary ammonium salt styryl diphenyl sulfone monomer comprises: Step (1), adding a methanesulfonic acid solution of phosphorus pentoxide, 4,4'-sulfonylbis(benzene-1,2-diamine) and 4-vinylbenzoic acid into a reaction container, reacting in a nitrogen atmosphere, diluting with water, filtering, washing the precipitate with water and methanol in sequence, and drying to obtain a styryl imidazole diphenyl sulfone monomer; Step (2), adding acetonitrile, styryl imidazole diphenyl sulfone monomer, chloroalkyl compound and potassium carbonate into a reaction container, heating to 80-85° C., reacting for 4-8 hours, then adding the chloroalkyl compound, continuing the reaction for 6-12 hours, concentrating the solution, washing the precipitate with water, and then recrystallizing in ethanol to obtain a diquaternary ammonium salt styryl diphenyl sulfone monomer.

8. The method for preparing the water-based environmentally friendly alkenyl structured antibacterial emulsion according to claim 7, characterized in that: In the step (1), the molar ratio of 4,4'-sulfonylbis(benzene-1,2-diamine) to 4-vinylbenzoic acid is 1:(1.8-2.4).

9. The method for preparing the water-based environmentally friendly alkenyl structured antibacterial emulsion according to claim 7, characterized in that: In the step (1), the reaction is carried out at 115-130° C. for 1-3 hours.

10. The method for preparing the water-based environmentally friendly alkenyl structure antibacterial emulsion according to claim 7, characterized in that: The molar ratio of the styrylimidazole diphenyl sulfone monomer, the chloroalkyl compound and potassium carbonate is 1:(4-4.8):(2-2.2); the structural formula of the chloroalkyl compound is Cl-CnH2n+1, wherein n is any integer between 6 and 10.

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