Aqueous bactericidal emulsion and method for its preparation

Abstract

The present application relates to the technical field of bactericides, in particular to a water-based bactericidal emulsion and a preparation method thereof, the water-based bactericidal emulsion is prepared from the following raw materials in parts by weight: alkenyl siloxyl benzisothiazolinone ester; monomer composition; hydrophilic agent; emulsifier; initiator; pH regulator; deionized water; the structure of the alkenyl siloxyl benzisothiazolinone ester is a silane-modified benzisothiazolinone ester containing a double bond. The present application has the beneficial effect that the water-based bactericidal emulsion can slowly hydrolyze in the water system and release a trace amount of benzisothiazolinone derivative with a high-efficiency bactericidal structure, kill bacteria, fungi and the like that may exist in the system, and continuously maintain the performance and appearance stability of the emulsion; the water-based bactericidal emulsion can be used alone as a film-forming material or in combination with other emulsions, applied in the fields of coatings and adhesives, and used to reduce the bactericide dosage and prolong the shelf life of the emulsion; the water-based bactericidal emulsion is easy to produce and scale up, has good compatibility and good stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of bactericides, in particular to a water-based bactericidal emulsion and a preparation method thereof. BACKGROUND

[0002] With the development of water-based technology, water-based emulsions have been widely used in various fields. Water-based emulsions use water as a carrier, and a small amount of bacterial nutrients exists in the emulsion, which leads to the easy breeding of bacteria and mold in water-based emulsions. In the long-term storage and application process, water-based emulsions or coatings are prone to spoilage, mold, and other problems. For this problem, the conventional solution is to add bactericides.

[0003] There are various types of bactericides, such as formaldehyde, iodopropynyl butylcarbamate, zinc pyrithione, carbendazim, chlorothalonil, and the like. Each of them has its own characteristics and has played an important role in a certain development period. At the same time, they also have their own shortcomings, such as high toxicity, poor environmental protection, strong irritation, and large influence on system stability. In recent years, isothiazolinone bactericides have been widely used because of their low toxicity, broad-spectrum bacteriostasis, and good effect. However, due to the still high irritation of isothiazolinone bactericides to the human body, they cannot be popularized in many fields.

[0004] CN111909631B discloses a bactericidal emulsion pressure-sensitive adhesive, dust pad, and a preparation method thereof. The invention uses a quaternary ammonium salt surfactant, which can not only provide emulsifying effect as an emulsifier to improve the adhesion and stability of the pressure-sensitive adhesive, but also kill bacteria as a bactericide. However, the quaternary ammonium salt surfactant belongs to a cationic surfactant, while conventional additives such as thickeners are based on anionic emulsions, and the surfaces of pigments and fillers such as calcium carbonate are also negatively charged, which has poor compatibility with the quaternary ammonium salt surfactant. If special thickeners are used, the selection of types is limited, and the cost is greatly increased.

[0005] CN115340626A discloses a pollution-resistant bactericidal resin grafted with phenol isothiazolinone acrylate monomer and a preparation method thereof, which is used in the field of marine pollution-resistant bactericidal materials. 2,4,6-triformylphloroglucinol is reduced to 2,4,6-trihydroxyformylphloroglucinol, which is then reacted with solid phosgene, acryloyl chloride, and isothiazolinone compounds to obtain a grafted phenol isothiazolinone acrylate monomer. The monomer is used with acrylate tools to obtain a grafted phenol isothiazolinone acrylate pollution-resistant bactericidal resin, which has excellent algae inhibition, bactericidal, and self-polishing properties. Through the slow hydrolysis of the ester group, the release of active substances is controlled, achieving the purpose of long-term pollution-resistant bactericidal, and effectively prolonging the service life of marine buildings, ships, and marine facilities. However, the grafted phenol isothiazolinone acrylate monomer disclosed in the invention has a complex structure and a high molecular weight, requiring a large amount of use; the production is difficult and the cost is high; and the color is deep, limiting its application in the production process of light-colored coatings or adhesives.

[0006] CN112279957A provides a kind of water-based polyacrylate antibacterial emulsion, and the emulsion is prepared by containing isothiazolinone-based monomer, acrylate monomer, nonylphenol polyoxyethylene ether ammonium sulfate, ammonium persulfate and deionized water.Containing isothiazolinone-based monomer is obtained by the reaction of 1,2-benzisothiazolin-3-one, 2-bromoethanol and methacryloyl chloride.The water-based polyacrylate emulsion is uniformly dispersed, and the particle size distribution is good and compatible, and has good antibacterial property and mildew resistance, antibacterial rate is greater than 99.9%, mildew resistance grade 0, can be directly used in water-based paint as fungicide, also can be used with commonly used water-based paint emulsion such as polyacrylate, polyurethane or epoxy resin emulsion, greatly reduce the addition amount of fungicide.But the water-based polyacrylate antibacterial emulsion uses nonylphenol polyoxyethylene ether ammonium sulfate as emulsifier, which is not environmentally friendly, and has greater impact on the environment. SUMMARY

[0007] The technical problem to be solved by the present application is to provide a water-based bactericidal emulsion that reduces the amount of bactericide and can continuously kill bacteria and a preparation method thereof.

[0008] To solve the above technical problems, the technical scheme adopted by the present application is to provide a water-based bactericidal emulsion prepared from the following raw materials in parts by weight:

[0009] Alkenyl siloxyl benzisothiazolinone ester 1-4 parts;

[0010] Monomer composition 40-49 parts;

[0011] Hydrophilic agent 0.4-0.9 parts;

[0012] Emulsifier 1-2 parts;

[0013] Initiator 0.2-0.4 parts;

[0014] pH adjuster 0.5-1.5 parts;

[0015] Deionized water 45-56 parts;

[0016] The structure of the alkenyl siloxyl benzisothiazolinone ester is a silane-modified benzisothiazolinone ester containing a double bond.

[0017] Further, in the above-mentioned water-based bactericidal emulsion, the monomer composition is a combination of at least two of styrene, methylstyrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, or stearyl methacrylate.

[0018] Further, in the above-mentioned water-based bactericidal emulsion, the emulsifier is one or a combination of several of BASF Disponil BES-20, BASF FES-77, Solvay ABEX 8018R, Solvay RHODAFAC RS 710, ADEKA Reasoap SR-10, Shanghai Zhongcheng Chemical ONIST NRS-10, or ONIST M-30S.

[0019] Further, in the above-mentioned water-based bactericidal emulsion, the hydrophilic agent is one of methacrylic acid, acrylic acid, itaconic acid, or maleic acid; the initiator is one of potassium persulfate, sodium persulfate, or ammonium persulfate; and the pH adjuster is one of 25wt% ammonia water, N,N-dimethyl ethanolamine, or triethylamine.

[0020] Another technical solution of the present application is to provide a preparation method of the above-mentioned water-based bactericidal emulsion, comprising the following steps:

[0021] S1: Dissolve the emulsifier in deionized water, add the monomer composition dropwise, stir to obtain pre-emulsion A; dissolve the emulsifier in deionized water, add a composition composed of an alkenyl siloxyl benzisothiazolinone ester, a monomer composition, and a hydrophilic agent dropwise, and stir to obtain pre-emulsion B;

[0022] S2: Take deionized water, add the emulsifier, stir until uniform and heat, add 5wt% of the pre-emulsion A and the initiator, react for a period of time, and then simultaneously drop the remaining pre-emulsion A and the initiator aqueous solution; continue to simultaneously drop the pre-emulsion B and the initiator aqueous solution after the pre-emulsion A is completely added, continue to keep warm after the dropping is completed, then cool down, add the pH adjuster to adjust the pH, and filter to remove the gel with a 200-mesh filter screen to obtain the water-based bactericidal emulsion.

[0023] Further, the preparation method of the above-mentioned water-based bactericidal emulsion further comprises a preparation method of the alkenyl siloxyl benzisothiazolinone ester, comprising the following steps:

[0024] 1,2-Benzisothiazolin-3-one, a haloalcohol, a weak base, and 1,2-dichloroethane were added to a reaction vessel and heated to react. After cooling, the solid precipitate was removed by filtration. The solid precipitate was washed with 1,2-dichloroethane, and the 1,2-dichloroethane solutions were combined. Alkenylchlorosilane was slowly added dropwise to the 1,2-dichloroethane solution, and the reaction was carried out under a dry nitrogen atmosphere for a period of time. A small molecule alcohol was added dropwise, and the reaction was carried out under a dry nitrogen atmosphere for a period of time. After cooling, a dilute alkali solution was added dropwise to neutralize the mixture. The mixture was washed with deionized water, allowed to stand to remove the aqueous phase, and then the 1,2-dichloroethane, the remaining small molecule alcohol, and the remaining alcohol were removed by vacuum distillation to obtain a crude product. The crude product was recrystallized from a mixture of 1,2-dichloroethane and petroleum ether in a volume ratio of 2:1 to obtain alkenylsiloxybenzisisothiazolinone ester.

[0025] Furthermore, in the above-mentioned method for preparing the aqueous bactericidal emulsion, the general structural formula of the haloalcohol is XCH2(CH2). n CH2OH, where X = one of Cl, Br, and I, and n = a natural number from 4 to 12.

[0026] Furthermore, in the above-mentioned method for preparing the aqueous bactericidal emulsion, the haloalcohol is one of 6-chloro-1-hexanol, 6-bromo-1-hexanol, 6-iodo-1-hexanol, 8-chloro-1-octanol, 8-bromo-1-octanol, 8-iodo-1-octanol, 10-iodo-1-decanol, 12-bromo-1-dodecanol, and 14-bromo-1-tetradecanool.

[0027] Furthermore, in the above-mentioned method for preparing the aqueous bactericidal emulsion, the general structural formula of the alkenylchlorosilane is CH2=CH m (CH3) 1-m COOCH2CH2CH2Si(CH3) n Cl 3-n , where m = 0 or 1, n = an integer from 0 to 2; the small molecule alcohol is one of methanol or ethanol.

[0028] Furthermore, in the above-mentioned method for preparing the aqueous bactericidal emulsion, the weak alkali is one of sodium carbonate, sodium bicarbonate, potassium carbonate, or potassium bicarbonate; the dilute alkali solution is an aqueous solution of the weak alkali with a concentration of 3-8 wt%.

[0029] The beneficial effects of this invention are as follows:

[0030] a) The functional monomer alkenylsiloxybenzisothiazolinone ester in the aqueous bactericidal emulsion of the present invention has a structure of silane-modified benzisothiazolinone ester containing double bonds. The double bonds are highly reactive and can copolymerize with ordinary monomers. The siloxybenzisothiazolinone ester segments in the polymer are evenly distributed in the latex particle shell of the emulsion. Both the Si-OC bonds and ester groups can be slowly hydrolyzed in the aqueous system to release trace amounts of highly effective bactericidal benzisothiazolinone derivatives, killing bacteria and fungi that may be present in the system, and maintaining the long-term stability of the emulsion's performance and appearance. The presence of silane groups improves the adhesion of bacteria and fungi, resulting in rapid and effective sterilization.

[0031] b) The waterborne bactericidal emulsion obtained by this invention has excellent stability. As a film-forming substance in waterborne coatings, it has good compatibility with conventional waterborne resins, is stable, and can be used alone to extend the shelf life of the emulsion without the need for additional preservatives. In formulations using conventional waterborne resins as the main film-forming substance, adding a portion of the waterborne bactericidal emulsion described in this invention at any stage of paint mixing can significantly reduce the risk of spoilage of the waterborne emulsion, making it applicable to the fields of coatings and adhesives.

[0032] c) The preparation process of the functional monomer alkenylsiloxybenzisothiazolinone ester in the preparation method of the aqueous bactericidal emulsion of the present invention is simple, suitable for industrial scale-up production, and has a high yield, which is conducive to reducing the cost of aqueous bactericidal emulsion. Attached Figure Description

[0033] Figure 1 The infrared spectra of alkenylsiloxybenzisothiazolinone ester F1 and 1,2-benzisothiazolin-3 one BIT are from Example 1 of the specific embodiments of the present invention. Detailed Implementation

[0034] To explain in detail the technical content, objectives, and effects of the present invention, the following description is provided in conjunction with the embodiments and accompanying drawings.

[0035] This invention provides a method for preparing an aqueous bactericidal emulsion, comprising the following steps:

[0036] S1: By weight, add 151 parts of 1,2-benzisothiazolin-3-one, 144-308 parts of haloalcohol, 120-160 parts of weak base, and 1000-1500 parts of 1,2-dichloroethane to a reaction vessel, heat to 60-80℃, react for 4-7 hours, cool to 20-30℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions; slowly add 231-275 parts of alkenylchlorosilane dropwise to the 1,2-dichloroethane solution, and heat to [temperature missing] under a dry nitrogen atmosphere. The mixture was kept at 50-70℃ for 4-10 hours, then cooled to 40-50℃. 10-65 parts of small molecule alcohol were added dropwise, the temperature was raised to 50-70℃, and the reaction was carried out for 1-2 hours. The temperature was then lowered to 20-30℃, and the mixture was neutralized to pH 6-8 by adding dilute alkali solution. The mixture was washed twice with 1000 parts of deionized water, allowed to stand to remove the aqueous phase, and then removed by vacuum distillation to remove 1,2-dichloroethane and the remaining small molecule alcohol and alcohol, yielding a crude product. The crude product was recrystallized with 1,2-dichloroethane:petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisisothiazolinone ester.

[0037] S2: By weight, dissolve 3-7 parts of emulsifier in 140-190 parts of deionized water, add dropwise a monomer composition consisting of 200-270 parts of monomer, and stir at 600 rpm for 1 hour to obtain pre-emulsion A; dissolve 5-12 parts of emulsifier in 160-250 parts of deionized water, add dropwise a monomer composition consisting of 10-50 parts of alkenylsiloxybenzisothiazolinone ester, 250-350 parts of monomer, and 5-12 parts of hydrophilic agent, and stir at 600 rpm for 1 hour to obtain pre-emulsion B;

[0038] S3: By weight, take 100-220 parts of deionized water, add 4-7 parts of emulsifier, stir evenly and heat to 70-90℃, add 5wt% of pre-emulsion A and 0.5-1 parts of initiator, react for 0.3-0.5 hours, then simultaneously add the remaining pre-emulsion A and 20 parts of aqueous solution containing 1-1.5 parts of initiator, and continue adding for 2-3 hours; after the addition of pre-emulsion A is complete, continue to simultaneously add pre-emulsion B and 20 parts of aqueous solution containing 0.8-1.5 parts of initiator, and continue adding for 1-2 hours. After the addition is complete, continue to keep warm for 1-3 hours, cool to 20-30℃, add an appropriate amount of pH adjuster to adjust pH to 7-9, filter through a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion M.

[0039] Example 1:

[0040] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0041] S1: Add 151g of 1,2-benzisothiazolin-3-one, 144g of 6-chloro-1-hexanol, 160g of potassium carbonate, and 1000g of 1,2-dichloroethane to a reaction vessel. Heat to 80℃ and react for 4 hours. Cool to 30℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions. Slowly add 275g of methacryloxypropyltrichlorosilane dropwise to the 1,2-dichloroethane solution. Heat to 50℃ under a dry nitrogen atmosphere and maintain the temperature for 10 hours. Cool to 40℃, add 65g of methanol dropwise, heat to 50℃, react for 2 hours, cool to 20℃, and add a 5wt% potassium carbonate aqueous solution dropwise. Neutralized to pH 8, washed twice with 1000g deionized water, allowed to stand to remove the aqueous phase, and then distilled under reduced pressure to remove 1,2-dichloroethane and the remaining methanol, yielding a crude product. The crude product was recrystallized from the crude product using 1,2-dichloroethane:petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F1; the yield was 78.21% and the purity was 95.68% based on 1,2-benzisothiazolin-3 one. The infrared spectra of alkenylsiloxybenzisothiazolinone ester F1 and 1,2-benzisothiazolin-3 one BIT are shown below. Figure 1 .from Figure 1 It can be seen that the characteristic absorption peak of the isothiazolinone heterocycle of BIT is at 1635 cm⁻¹. -1 Above, the characteristic absorption peak of the isothiazolinone heterocycle in F1 is at a higher wavenumber of 1664 cm⁻¹. -1 This indicates that the hydrogen atom on the heterocycle of isothiazolinone is replaced by a hydrocarbon group; 1735 cm -1 The absorption peak is a characteristic absorption peak of the ester group, at 1089 cm⁻¹. -1 The characteristic absorption peaks of the Si-OC bond indicate that F1 contains ester and siloxane groups. A comparison of the infrared spectra of the two substances shows that this step successfully prepared the alkenylsiloxybenzisothiazolinone ester F1.

[0042] S2: Dissolve 3g of emulsifier Disponil BES-20 in 180g of deionized water, and add dropwise a monomer composition consisting of 20g of styrene, 35g of methyl methacrylate, 75g of n-butyl acrylate and 70g of 2-ethylhexyl acrylate. Stir at 600rpm for 1 hour to obtain pre-emulsion A1. Dissolve 5g of emulsifier ABEX 8018R and 7g of emulsifier Reasoap SR-10 in 160g of deionized water, and add dropwise a monomer composition consisting of 10g of alkenylsiloxybenzisothiazolinone ester F1, 50g of styrene, 55g of methyl methacrylate, 75g of n-butyl acrylate and 70g of 2-ethylhexyl acrylate, and 8g of methacrylic acid. Stir at 600rpm for 1 hour to obtain pre-emulsion B1. S3: Take 100g of deionized water, add 4g of emulsifier Disponil BES-20, stir evenly and heat to 70℃, add 5wt% of pre-emulsion A1 and 0.5g of sodium persulfate, react for 0.5 hours, then simultaneously add the remaining pre-emulsion A1 and 20g of aqueous solution containing 1.5g of sodium persulfate, and continue adding for 3 hours; after the addition of pre-emulsion A1 is completed, continue to simultaneously add pre-emulsion B1 and 20g of aqueous solution containing 1.5g of sodium persulfate, and continue adding for 2 hours. After the addition is completed, continue to keep warm for 3 hours, cool to 20℃, add 25wt% ammonia water to adjust pH=7.5, filter with a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion M1.

[0043] Example 2:

[0044] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0045] S1: Add 151g of 1,2-benzisothiazolin-3-one, 220g of 8-bromo-1-octanol, 120g of sodium carbonate, and 1500g of 1,2-dichloroethane to a reaction vessel. Heat to 60℃ and react for 7 hours. Cool to 20℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions. Slowly add 253g of methacryloxypropylmethyldichlorosilane dropwise to the 1,2-dichloroethane solution. Heat to 55℃ under a dry nitrogen atmosphere and maintain the temperature for 9 hours. Cool to 45℃, add 50g of ethanol dropwise, heat to 60℃, and react for 2 hours. The solution was cooled to 25°C, and neutralized to pH 7 by adding 3wt% dilute potassium carbonate aqueous solution. It was washed twice with 1000g deionized water, allowed to stand to remove the aqueous phase, and then removed by vacuum distillation to remove 1,2-dichloroethane and the remaining ethanol, yielding a crude product. The crude product was recrystallized from the crude product using 1,2-dichloroethane:petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F2. The yield was 81.94% and the purity was 96.31% based on 1,2-benzisothiazolin-3 one.

[0046] S2: Dissolve 4g of emulsifier ONIST NRS-10 in 180g of deionized water, and add dropwise a monomer composition consisting of 50g cyclohexyl acrylate, 60g methyl acrylate, 30g ethyl methacrylate, 45g n-butyl methacrylate, and 40g tridecyl methacrylate. Stir at 600rpm for 1 hour to obtain preemulsion A2. Dissolve 5g of emulsifier FES-77 in 250g of deionized water, and add dropwise a monomer composition consisting of 50g alkenylsiloxybenzisothiazolinone ester F2, 50g cyclohexyl acrylate, 110g methyl acrylate, 90g ethyl methacrylate, 40g n-butyl methacrylate, 60g tridecyl methacrylate, and 12g itaconic acid. Stir at 600rpm for 1 hour to obtain preemulsion B2.

[0047] S3: Take 220g of deionized water, add 5g of emulsifier ONIST NRS-10, stir evenly and heat to 90℃, add 5wt% of pre-emulsion A2 and 1g of ammonium persulfate, react for 0.3 hours, then simultaneously add the remaining pre-emulsion A2 and 20g of aqueous solution containing 1g of ammonium persulfate, and continue adding for 2 hours; after the addition of pre-emulsion A2 is completed, continue to simultaneously add pre-emulsion B2 and 20g of aqueous solution containing 0.8g of ammonium persulfate, and continue adding for 1 hour. After the addition is completed, continue to keep warm for 1 hour, cool to 30℃, add an appropriate amount of N,N-dimethylethanolamine to adjust pH=8.5, filter through a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion M2.

[0048] Example 3:

[0049] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0050] S1: Add 151g of 1,2-benzisothiazolin-3-one, 308g of 14-bromo-1-tetradecyl alcohol, 158g of potassium carbonate, and 1500g of 1,2-dichloroethane to a reaction vessel. Heat to 70℃ and react for 5 hours. Cool to 25℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions. Slowly heat 232g of methacryloxypropyl dimethylchlorosilane to 70℃ and maintain the temperature for 6 hours. Cool to 50℃, add 10g of ethanol dropwise, heat to 70℃, react for 1-2 hours, and then cool to... The solution was cooled to 25℃ at 20-30℃, and neutralized to pH 6 by adding 6wt% sodium carbonate aqueous solution. It was washed twice with 1000g deionized water, allowed to stand to remove the aqueous phase, and then distilled under reduced pressure to remove 1,2-dichloroethane and the remaining ethanol, yielding a crude product. The crude product was recrystallized from the crude product using 1,2-dichloroethane:petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F3; the yield was 74.69% and the purity was 97.17% based on 1,2-benzisothiazolin-3 one.

[0051] S2: Dissolve 7g of emulsifier ABEX 8018R in 183g of deionized water, and add dropwise a monomer composition consisting of 110g of n-butyl acrylate, 20g of n-butyl methacrylate, 35g of isobornyl acrylate and 40g of octadecyl methacrylate. Stir at 600rpm for 1 hour to obtain preemulsion A3; Dissolve 5g of emulsifier ABEX 8018R in 240g of deionized water, and add dropwise a monomer composition consisting of 25g of alkenylsiloxybenzisothiazolinone ester F3, 65g of methyl acrylate, 90g of n-butyl acrylate, 40g of lauryl acrylate, 55g of 2-ethylhexyl acrylate and 5g of acrylic acid. Stir at 600rpm for 1 hour to obtain preemulsion B3;

[0052] S3: Take 170g of deionized water, add 4g of emulsifier RHODAFAC RS 710, stir evenly and heat to 80℃, add 5wt% of pre-emulsion A3 and 0.5g of sodium persulfate, react for 0.3 hours, then simultaneously add the remaining pre-emulsion A3 and 20g of aqueous solution containing 1.5g of sodium persulfate, and continue adding for 3 hours; after the addition of pre-emulsion A3 is completed, continue to simultaneously add pre-emulsion B3 and 20g of aqueous solution containing 0.8g of sodium persulfate, and continue adding for 2 hours. After the addition is completed, continue to keep warm for 2 hours, cool to 25℃, add an appropriate amount of triethylamine to adjust pH=8.5, filter through a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion M3.

[0053] Example 4:

[0054] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0055] S1: Add 151g of 1,2-benzisothiazolin-3-one, 239g of 6-iodo-1-hexanol, 145g of sodium carbonate, and 1300g of 1,2-dichloroethane to a reaction vessel. Heat to 60℃ and react for 7 hours. Cool to 20℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions. Slowly add 260g of acryloyloxypropyltrichlorosilane dropwise to the 1,2-dichloroethane solution. Heat to 60℃ under a dry nitrogen atmosphere and maintain the temperature for 7 hours. Cool to 50℃, add 65g of methanol dropwise, heat to 55℃, react for 2 hours, and then cool to... The solution was neutralized to pH 6.5 by adding 8 wt% sodium carbonate aqueous solution at 25℃, washed twice with 1000 g deionized water, allowed to stand to remove the aqueous phase, and then removed by vacuum distillation to remove 1,2-dichloroethane and the remaining methanol, yielding a crude product. The crude product was recrystallized from the crude product using a 1,2-dichloroethane:petroleum ether ratio of 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F4; the yield was 80.93% and the purity was 95.78% based on 1,2-benzisothiazolin-3 one.

[0056] S2: Dissolve 5g of emulsifier Reasoap SR-10 in 190g of deionized water, and add dropwise a monomer composition consisting of 100g of methylstyrene, 25g of methyl acrylate, 30g of cyclohexyl methacrylate and 80g of n-butyl acrylate. Stir at 600rpm for 1 hour to obtain pre-emulsion A4; Dissolve 8g of emulsifier Reasoap SR-10 in 220g of deionized water, and add dropwise a monomer composition consisting of 40g of alkenylsiloxybenzisothiazolinone ester F4, 70g of cyclohexyl acrylate, 90g of cyclohexyl methacrylate, 25g of 2-ethylhexyl acrylate, 65g of octadecyl acrylate and 10g of maleic acid. Stir at 600rpm for 1 hour to obtain pre-emulsion B4.

[0057] S3: Take 170g of deionized water, add 6g of emulsifier Disponil BES-20, stir evenly and heat to 75℃, add 5wt% of pre-emulsion A4 and 1g of potassium persulfate, react for 0.4 hours, then simultaneously add the remaining pre-emulsion A4 and 20g of aqueous solution containing 1.2g of potassium persulfate, and continue adding for 2.5 hours; after the addition of pre-emulsion A4 is completed, continue to simultaneously add pre-emulsion B4 and 20g of aqueous solution containing 1.2g of potassium persulfate, and continue adding for 2 hours. After the addition is completed, continue to keep warm for 2 hours, cool to 25℃, add an appropriate amount of N,N-dimethylethanolamine to adjust pH=7, filter through a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion M4.

[0058] Example 5:

[0059] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0060] S1: Add 151g of 1,2-benzisothiazolin-3-one, 190g of 6-bromo-1-hexanol, 150g of potassium carbonate, and 1000g of 1,2-dichloroethane to a reaction vessel. Heat to 65℃ and react for 6 hours. Cool to 25℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions. Slowly add 239g of acryloyloxypropylmethyldichlorosilane dropwise to the 1,2-dichloroethane solution. Heat to 65℃ under a dry nitrogen atmosphere and maintain the temperature for 6 hours. Cool to 45℃, add 35g of methanol dropwise, heat to 50℃, react for 2 hours, and then cool to... At 20℃, the solution was neutralized to pH 7.5 by adding 7wt% potassium carbonate aqueous solution dropwise. The mixture was washed twice with 1000g deionized water, allowed to stand to remove the aqueous phase, and then subjected to vacuum distillation to remove 1,2-dichloroethane and the remaining small molecule alcohols, yielding a crude product. The crude product was recrystallized from the crude product using a 1,2-dichloroethane:petroleum ether ratio of 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F5; the yield was 78.06% and the purity was 94.52% based on 1,2-benzisothiazolin-3 one.

[0061] S2: Dissolve 6g of emulsifier ONIST NRS-10 in 170g of deionized water, and add dropwise a monomer composition consisting of 100g of methyl methacrylate, 90g of lauryl acrylate, and 80g of n-butyl methacrylate. Stir at 600rpm for 1 hour to obtain pre-emulsion A5; Dissolve 9g of emulsifier ONIST NRS-10 in 250g of deionized water, and add dropwise a monomer composition consisting of 20g of alkenylsiloxybenzisothiazolinone ester F5, 100g of n-butyl methacrylate, 40g of methyl methacrylate, 80g of 2-ethylhexyl acrylate, 70g of isobornyl methacrylate, and 7g of methacrylic acid. Stir at 600rpm for 1 hour to obtain pre-emulsion B5.

[0062] S3: Take 180g of deionized water, add 7g of emulsifier FES-77, stir evenly and heat to 85℃, add 5wt% of pre-emulsion A5 and 0.9g of sodium persulfate, react for 0.3 hours, then simultaneously add the remaining pre-emulsion A5 and 20g of aqueous solution containing 1.4g of sodium persulfate, and continue adding for 2 hours; after the addition of pre-emulsion A5 is completed, continue to simultaneously add pre-emulsion B5 and 20g of aqueous solution containing 1.3g of sodium persulfate, and continue adding for 1 hour. After the addition is completed, continue to keep warm for 1.5 hours, cool to 30℃, add 25wt% ammonia water to adjust pH=8, filter through a 200-mesh filter to remove the gel, and obtain the aqueous bactericidal emulsion M5.

[0063] Example 6:

[0064] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0065] S1: Add 151g of 1,2-benzisothiazolin-3-one, 278g of 12-bromo-1-dodecanool, 125g of sodium carbonate, and 1400g of 1,2-dichloroethane to a reaction vessel. Heat to 75℃ and react for 5 hours. Cool to 30℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions. Slowly add 235g of methacryloxypropyl dimethylchlorosilane dropwise to the 1,2-dichloroethane solution. Heat to 70℃ under a dry nitrogen atmosphere and maintain the temperature for 4 hours. Cool to 40-50℃, add 20g of ethanol dropwise, heat to 65℃, and react for 1 hour. The solution was cooled to 25°C, and neutralized to pH 7 by adding 6 wt% sodium bicarbonate aqueous solution. It was washed twice with 1000 g of deionized water, allowed to stand to remove the aqueous phase, and then distilled under reduced pressure to remove 1,2-dichloroethane and the remaining ethanol, yielding a crude product. The crude product was recrystallized from the crude product using a 1,2-dichloroethane:petroleum ether ratio of 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F6; the yield was 78.23% and the purity was 96.44% based on 1,2-benzisothiazolin-3 one.

[0066] S2: Dissolve 5g of emulsifier FES-77 in 170g of deionized water, and add dropwise a monomer composition consisting of 80g of ethyl acrylate, 70g of styrene, 40g of cyclohexyl acrylate, and 45g of cyclohexyl methacrylate. Stir at 600rpm for 1 hour to obtain pre-emulsion A6; Dissolve 11g of emulsifier FES-77 in 240g of deionized water, and add dropwise a monomer composition consisting of 15g of alkenylsiloxybenzisothiazolinone ester F6, 75g of methylstyrene, 65g of ethyl methacrylate, 90g of methyl methacrylate, 45g of isobornyl methacrylate, and 11g of itaconic acid. Stir at 600rpm for 1 hour to obtain pre-emulsion B6;

[0067] S3: Take 160g of deionized water, add 4g of emulsifier FES-77, stir evenly and heat to 75℃, add 5wt% of pre-emulsion A6 and 0.6g of ammonium persulfate, react for 0.3 hours, then simultaneously add the remaining pre-emulsion A6 and 20g of aqueous solution containing 1g of ammonium persulfate, and continue adding for 3 hours; after the addition of pre-emulsion A6 is completed, continue to simultaneously add pre-emulsion B6 and 20g of aqueous solution containing 1.3g of ammonium persulfate, and continue adding for 2 hours; after the addition is completed, continue to keep warm for 2.5 hours, cool to 25℃, add an appropriate amount of triethylamine to adjust pH=9, filter through a 200-mesh filter to remove the gel, and obtain aqueous bactericidal emulsion M6.

[0068] Example 7:

[0069] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0070] S1: Add 151g of 1,2-benzisothiazolin-3-one, 298g of 10-iodo-1-decyl alcohol, 160g of sodium carbonate, and 1100g of 1,2-dichloroethane to a reaction vessel. Heat to 70℃ and react for 4 hours. Cool to 20℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions. Slowly add 270g of methacryloxypropyltrichlorosilane dropwise to the 1,2-dichloroethane solution. Under a dry nitrogen atmosphere, heat to 55℃ and maintain the temperature for 9 hours. Cool to 40℃, add 60g of methanol dropwise, heat to 60℃, and react for 2 hours. The solution was cooled to 20°C, neutralized to pH 8 by adding 4 wt% sodium carbonate aqueous solution, washed twice with 1000 g deionized water, allowed to stand to remove the aqueous phase, and then removed by vacuum distillation to remove 1,2-dichloroethane and the remaining methanol, yielding a crude product. The crude product was recrystallized from the crude product using a 1,2-dichloroethane:petroleum ether ratio of 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F7; the yield was 83.46% and the purity was 96.52% based on 1,2-benzisothiazolin-3 one.

[0071] S2: Dissolve 4g of emulsifier RHODAFAC RS 710 in 140g of deionized water, and add dropwise a monomer composition consisting of 30g of methyl acrylate, 65g of methyl methacrylate, 120g of n-butyl acrylate, and 55g of tridecyl acrylate. Stir at 600rpm for 1 hour to obtain pre-emulsion A7; Dissolve 5g of emulsifier RHODAFAC RS 710 and 2g of emulsifier ABEX 8018R in 183g of deionized water, and add dropwise a monomer composition consisting of 42g of alkenylsiloxybenzisothiazolinone ester F7, 50g of methyl acrylate, 50g of methyl methacrylate, 60g of n-butyl acrylate, 40g of tridecyl acrylate, 55g of 2-ethylhexyl acrylate, and 9g of acrylic acid. Stir at 600rpm for 1 hour to obtain pre-emulsion B7.

[0072] S3: Take 110g of deionized water, add 5g of emulsifier Reasoap SR-10, stir evenly and heat to 80℃, add 5wt% of pre-emulsion A7 and 1g of sodium persulfate, react for 0.4 hours, then simultaneously add the remaining pre-emulsion A7 and 20g of aqueous solution containing 1.5g of sodium persulfate, adding dropwise for 2.5 hours; after the addition of pre-emulsion A7 is complete, continue to simultaneously add pre-emulsion B7 and 20g of aqueous solution containing 1.5g of sodium persulfate, adding dropwise for 1.5 hours, and continue to keep warm for 2 hours after the addition is complete, cool to 20℃, add 25wt% ammonia water to adjust pH=8.5, filter through a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion M7.

[0073] Example 8:

[0074] A method for preparing an aqueous bactericidal emulsion includes the following steps:

[0075] S1: Add 151g of 1,2-benzisothiazolin-3-one, 269g of 8-iodo-1-octanol, 130g of sodium carbonate, and 1000g of 1,2-dichloroethane to a reaction vessel, heat to 65℃, react for 5 hours, cool to 25℃, filter to remove the solid precipitate, wash the solid precipitate with a small amount of 1,2-dichloroethane, and combine the 1,2-dichloroethane solutions; slowly add 248g of... Acryloyloxypropyltrichlorosilane was added dropwise to a solution of 1,2-dichloroethane. The mixture was heated to 65°C under a dry nitrogen atmosphere and held at this temperature for 6 hours. The temperature was then lowered to 45°C, and 62 g of methanol was added dropwise. The mixture was heated to 58°C and reacted for 2 hours. The temperature was then lowered to 20°C, and the mixture was neutralized to pH 6 by adding a 6 wt% potassium carbonate aqueous solution. The mixture was washed twice with 1000 g of deionized water, allowed to stand to remove the aqueous phase, and then subjected to vacuum distillation to remove 1,2-dichloroethane and the remaining methanol, yielding a crude product. The crude product was recrystallized from a 1,2-dichloroethane:petroleum ether ratio of 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F8. The yield was 79.38% and the purity was 95.56% based on 1,2-benzisothiazolin-3 one.

[0076] S2: Dissolve 6g of emulsifier ONIST M-30S in 190g of deionized water, and add dropwise a monomer composition consisting of 120g of styrene, 60g of n-butyl acrylate, and 20g of 2-ethylhexyl acrylate. Stir at 600rpm for 1 hour to obtain pre-emulsion A8; Dissolve 8g of emulsifier ONIST M-30S in 210g of deionized water, and add dropwise a monomer composition consisting of 30g of alkenylsiloxybenzisothiazolinone ester F8, 120g of styrene, 60g of n-butyl acrylate, 20g of 2-ethylhexyl acrylate, 40g of lauryl acrylate, 75g of octadecyl methacrylate, and 6g of maleic acid. Stir at 600rpm for 1 hour to obtain pre-emulsion B8.

[0077] S3: Take 140g of deionized water, add 5g of emulsifier ONIST M-30S, stir evenly and heat to 90℃, add 5wt% of pre-emulsion A8 and 0.5g of potassium persulfate, react for 0.3 hours, then simultaneously add the remaining pre-emulsion A8 and 20g of aqueous solution containing 1g of potassium persulfate, and continue adding for 2 hours; after the addition of pre-emulsion A8 is completed, continue to simultaneously add pre-emulsion B8 and 20g of aqueous solution containing 1.5g of potassium persulfate, and continue adding for 2 hours. After the addition is completed, continue to keep warm for 2 hours, cool to 25℃, add an appropriate amount of N,N-dimethylethanolamine to adjust pH=7, filter through a 200-mesh filter to remove the gel, and obtain aqueous bactericidal emulsion M8.

[0078] Comparative Example 1:

[0079] A method for preparing an emulsion includes the following steps:

[0080] Comparative Example 1: The emulsion preparation process is the same as in Example 1, except that 10g of styrene is used instead of alkenylsiloxybenzisothiazolinone ester F1. The preparation steps are described below:

[0081] S1: Dissolve 3g of emulsifier Disponil BES-20 in 180g of deionized water, and add dropwise a monomer composition consisting of 20g of styrene, 35g of methyl methacrylate, 75g of n-butyl acrylate and 70g of 2-ethylhexyl acrylate. Stir at 600rpm for 1 hour to obtain preemulsion A9; Dissolve 5g of emulsifier ABEX 8018R and 7g of emulsifier Reasoap SR-10 in 160g of deionized water, and add dropwise a monomer composition consisting of 60g of styrene, 55g of methyl methacrylate, 75g of n-butyl acrylate and 70g of 2-ethylhexyl acrylate and 8g of methacrylic acid. Stir at 600rpm for 1 hour to obtain preemulsion B9;

[0082] S2: Take 100g of deionized water, add 4g of emulsifier Disponil BES-20, stir evenly and heat to 70℃, add 5wt% of pre-emulsion A9 and 0.5g of sodium persulfate, react for 0.5 hours, then simultaneously add the remaining pre-emulsion A9 and 20g of aqueous solution containing 1.5g of sodium persulfate, and continue adding for 3 hours; after the addition of pre-emulsion A9 is complete, continue to simultaneously add pre-emulsion B9 and 20g of aqueous solution containing 1.5g of sodium persulfate, and continue adding for 2 hours; after the addition is complete, continue to keep warm for 3 hours, cool to 20℃, add 25wt% ammonia to adjust pH=7.5, filter through a 200-mesh filter to remove gel, and obtain aqueous emulsion M9.

[0083] Comparative Example 2:

[0084] A method for preparing an emulsion includes the following steps:

[0085] Comparative Example 2 emulsion preparation is the same as Example 2, except that 50g of ethyl methacrylate is used instead of alkenylsiloxybenzisothiazolinone ester F2. The preparation steps are described below:

[0086] S1: Dissolve 4g of emulsifier ONIST NRS-10 in 180g of deionized water, and add dropwise a monomer composition consisting of 50g cyclohexyl acrylate, 60g methyl acrylate, 30g ethyl methacrylate, 45g n-butyl methacrylate, and 40g tridecyl methacrylate. Stir at 600rpm for 1 hour to obtain preemulsion A10; Dissolve 5g of emulsifier FES-77 in 250g of deionized water, and add dropwise a monomer composition consisting of 50g cyclohexyl acrylate, 110g methyl acrylate, 140g ethyl methacrylate, 40g n-butyl methacrylate, 60g tridecyl methacrylate, and 12g itaconic acid. Stir at 600rpm for 1 hour to obtain preemulsion B10.

[0087] S2: Take 220g of deionized water, add 5g of emulsifier ONIST NRS-10, stir evenly and heat to 90℃, add 5wt% of pre-emulsion A10 and 1g of ammonium persulfate, react for 0.3 hours, then simultaneously add the remaining pre-emulsion A10 and 20g of aqueous solution containing 1g of ammonium persulfate, and continue adding for 2 hours; after the addition of pre-emulsion A10 is completed, continue to simultaneously add pre-emulsion B10 and 20g of aqueous solution containing 0.8g of ammonium persulfate, and continue adding for 1 hour. After the addition is completed, continue to keep warm for 1 hour, cool to 30℃, add an appropriate amount of N,N-dimethylethanolamine to adjust pH=8.5, filter through a 200-mesh filter to remove gel, and obtain aqueous emulsion M10.

[0088] Example 9:

[0089] The aqueous bactericidal emulsions M1-M8 described in this invention, the aqueous emulsions M9-M10 obtained in the comparative examples, the Wantipro® 0625 emulsion produced by Wanhua Chemical, and the emulsions obtained by mixing aqueous bactericidal emulsions M1 and M10 at a volume ratio of 1:4 and M1 and M10 at a volume ratio of 1:10 were subjected to stability tests under routine non-sterilization conditions. The bactericidal content of Wantipro® 0625 was approximately 49 mg / kg CMIT / MIT (3:1) and approximately 240 mg / kg MIT. The test results are shown in Table 1 - Storage tests of M1-M10, M1+M10 mixed emulsions, and Wantipro® 0625 under routine non-sterilization conditions.

[0090] Table 1

[0091]

[0092] As shown in Table 1, the aqueous bactericidal emulsions M1-M8 and Wantipro® 0625 described in this invention can maintain bactericidal activity under normal, unsterilized conditions, and their antibacterial performance is comparable to that of conventional emulsions with added bactericides within a 12-month storage period, meeting the requirements for daily use. In contrast, the bactericide-free emulsions M9 and M10 described in the comparative examples showed slight spoilage after one month of storage, with a normal odor; significant spoilage and an abnormal odor appeared after three months; and after six months, the emulsions exhibited severe spoilage, foul odor, and sedimentation, rendering them unusable. The emulsion obtained by mixing M1 and M10 at a volume ratio of 1:4 maintained a good appearance within a 12-month storage period. The emulsion obtained by mixing M1 and M10 at a volume ratio of 1:10 maintained a good appearance within a 6-month storage period, and only showed slight spoilage after 12 months, with a normal odor, similar to the degree of spoilage of M10 stored alone for one month. This fully demonstrates that the addition of a small amount of aqueous bactericidal emulsion M1 can greatly delay the spoilage of M10, and also shows that the aqueous bactericidal emulsion described in this invention has good compatibility with other emulsions.

[0093] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification and drawings, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. An aqueous bactericidal emulsion, characterized in that, The aqueous bactericidal emulsion is prepared from the following raw materials in parts by weight: 1-4 parts of alkenylsiloxybenzoisothiazolinone ester; 40-49 parts of monomer composition; 0.4-0.9 parts of hydrophilic agent; 1-2 parts emulsifier; Initiator 0.2-0.4 parts; pH adjuster 0.5-1.5 parts; 45-56 parts deionized water; The alkenylsiloxybenzisothiazolinone ester has the structure of a silane-modified benzisothiazolinone ester containing a double bond.

2. The aqueous bactericidal emulsion according to claim 1, characterized in that, The monomer composition is a combination of at least two of styrene, methyl methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, or octadecyl methacrylate.

3. The aqueous bactericidal emulsion according to claim 1, characterized in that, The emulsifier is one or a combination of several of the following: BASF Disponil BES-20, BASF FES-77, Solvay ABEX 8018R, Solvay RHODAFAC RS 710, Idicco Reasoap SR-10, Shanghai Zhongcheng Chemical ONIST NRS-10, or ONIST M-30S.

4. The aqueous bactericidal emulsion according to claim 1, characterized in that, The hydrophilic agent is one of methacrylic acid, acrylic acid, itaconic acid, or maleic acid; the initiator is one of potassium persulfate, sodium persulfate, or ammonium persulfate; and the pH adjuster is one of 25wt% ammonia, N,N-dimethylethanolamine, or triethylamine.

5. A method for preparing the aqueous bactericidal emulsion according to any one of claims 1-4, characterized in that, Includes the following steps: S1: Dissolve the emulsifier in deionized water, add the monomer composition dropwise, and stir to obtain pre-emulsion A; dissolve the emulsifier in deionized water, add the composition composed of alkenylsiloxybenzisothiazolinone ester, monomer composition, and hydrophilic agent dropwise, and stir to obtain pre-emulsion B; S2: Take deionized water, add emulsifier, stir evenly and heat, add 5wt% of pre-emulsion A and initiator, react for a period of time, and then simultaneously add the remaining pre-emulsion A and initiator aqueous solution; after the pre-emulsion A is added, continue to add pre-emulsion B and initiator aqueous solution simultaneously, continue to keep warm after the addition is completed, then cool down, add pH adjuster to adjust pH, filter with a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion.

6. The method for preparing the aqueous bactericidal emulsion according to claim 5, characterized in that, It also includes a method for preparing alkenylsiloxybenzisothiazolinone esters, comprising the following steps: 1,2-Benzisothiazolin-3-one, a haloalcohol, a weak base, and 1,2-dichloroethane were added to a reaction vessel and heated to react. After cooling, the solid precipitate was removed by filtration. The solid precipitate was washed with 1,2-dichloroethane, and the 1,2-dichloroethane solutions were combined. Alkenylchlorosilane was slowly added dropwise to the 1,2-dichloroethane solution, and the reaction was carried out under a dry nitrogen atmosphere for a period of time. A small molecule alcohol was added dropwise, and the reaction was carried out under a dry nitrogen atmosphere for a period of time. After cooling, a dilute alkali solution was added dropwise to neutralize the mixture. The mixture was washed with deionized water, allowed to stand to remove the aqueous phase, and then the 1,2-dichloroethane, the remaining small molecule alcohol, and the remaining alcohol were removed by vacuum distillation to obtain a crude product. The crude product was recrystallized from a mixture of 1,2-dichloroethane and petroleum ether in a volume ratio of 2:1 to obtain alkenylsiloxybenzisisothiazolinone ester.

7. The method for preparing the aqueous bactericidal emulsion according to claim 6, characterized in that, The general structural formula of the haloalcohol is XCH2(CH2). n CH2OH, where X = one of Cl, Br, and I, and n = a natural number from 4 to 12.

8. The method for preparing the aqueous bactericidal emulsion according to claim 6, characterized in that, The haloalcohol is one of 6-chloro-1-hexanol, 6-bromo-1-hexanol, 6-iodo-1-hexanol, 8-chloro-1-octanol, 8-bromo-1-octanol, 8-iodo-1-octanol, 10-iodo-1-decanol, 12-bromo-1-dodecanol, and 14-bromo-1-tetradecanool.

9. The method for preparing the aqueous bactericidal emulsion according to claim 6, characterized in that, The general structural formula of the alkenylchlorosilane is CH2=CH m (CH3) 1-m COOCH2CH2CH2Si(CH3) n Cl 3-n , where m = 0 or 1, n = an integer from 0 to 2; the small molecule alcohol is one of methanol or ethanol.

10. The method for preparing the aqueous bactericidal emulsion according to claim 6, characterized in that, The weak base is one of sodium carbonate, sodium bicarbonate, potassium carbonate, or potassium bicarbonate; the dilute alkaline solution is an aqueous solution of the weak base with a concentration of 3-8 wt%.

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