Water-based bactericidal emulsion and preparation method thereof

Abstract

The invention relates to the technical field of bactericides, in particular to a water-based bactericidal emulsion and a preparation method thereof, and the water-based bactericidal emulsion is prepared from the following raw materials in parts by weight: alkenyl siloxy benzisothiazolinone ester; a monomer composition; a hydrophilic agent; an emulsifier; an initiator; a pH adjusting agent; deionized water; the structure of the alkenyl siloxy benzisothiazolinone ester is silane modified benzisothiazolinone ester containing double bonds. The water-based bactericidal emulsion has the beneficial effects that the water-based bactericidal emulsion can be slowly hydrolyzed in a water system and release a trace amount of benzisothiazolinone derivative with an efficient bactericidal structure, bacteria, fungi and the like possibly existing in the system are killed, and the performance and appearance stability of the emulsion are continuously maintained; the emulsion can be used as a film-forming substance independently or matched with other emulsions to be applied to the fields of coatings and adhesives, and the purposes of reducing the dosage of a bactericide and prolonging the quality guarantee period of the emulsions are achieved. The production amplification is easy, the compatibility is good, and the stability is good.

Description

Technical Field

[0001] The invention relates to the technical field of bactericides, and in particular to an aqueous bactericidal emulsion and a preparation method thereof. Background Art

[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 there are a small amount of bacterial nutrients in the emulsion, which makes it easy for water-based emulsions to breed bacteria and mold. During long-term storage and application, water-based emulsions or coatings are prone to corruption and mildew. For this problem, the conventional solution is to add fungicides.

[0003] There are various types of fungicides, such as formaldehyde, iodopropynylbutyl carbamate, zinc pyrithione, carbendazim, thiophanate-methyl, etc. They all have their own characteristics and have played an important role in a certain period of development. At the same time, they also have their own shortcomings, such as high toxicity, poor environmental protection, strong irritation, and great influence on system stability. In recent years, isothiazolinone fungicides have been widely used because of their low toxicity, broad-spectrum antibacterial effect, and good effect. However, isothiazolinone fungicides are still highly irritating to the human body and cannot be promoted in many fields.

[0004] CN111909631B discloses a bactericidal emulsion pressure-sensitive adhesive, a sticky mat and a preparation method thereof. The invention uses a quaternary ammonium salt surfactant, which can be used as an emulsifier to provide an emulsifying effect, improve the adhesion and stability of the pressure-sensitive adhesive, and can also be used as a bactericide to kill bacteria. However, quaternary ammonium salt surfactants belong to cationic surfactants, and conventional auxiliary agents such as thickeners are all developed based on anionic emulsions. The surfaces of pigments and fillers such as calcium carbonate are also negatively charged and have poor compatibility with quaternary ammonium salt surfactants. If a special thickener is used, the types that can be selected are limited, and the cost is greatly increased.

[0005] CN115340626A discloses an antifouling and bactericidal resin of a grafted phenol isothiazolinone acrylate monomer and a preparation method thereof, which are used in the field of marine antifouling and bactericidal materials. 2,4,6-triformyl pyrogallol is reduced to 2,4,6-trihydroxyformyl pyrogallol, and then reacted with solid phosgene, acryloyl chloride, and isothiazolinone compounds to obtain a grafted phenol isothiazolinone acrylate monomer, and the monomer is reacted with an acrylate tool to obtain a grafted phenol isothiazolinone acrylate antifouling and bactericidal resin, which has excellent algae inhibition, bactericidal, and self-polishing properties. The release of active substances is controlled by slow hydrolysis of the ester group to achieve the purpose of long-term antifouling and bactericidal, and effectively prolong the life of marine buildings, ships, and marine facilities. However, the grafted phenol isothiazolinone acrylate monomer disclosed in the invention has a complex structure, a high molecular weight, and a large amount of use; it is difficult to produce and has a high cost; the color is darker, and its application is limited in the production process of light-colored coatings or adhesives.

[0006] CN112279957A provides an aqueous polyacrylate antibacterial emulsion, which is prepared from isothiazolinone-containing monomers, acrylate monomers, nonylphenol polyoxyethylene ether ammonium sulfate, ammonium persulfate and deionized water. The isothiazolinone-containing monomer is obtained by reacting 1,2-benzisothiazolin-3-one, 2-bromoethanol and methacryloyl chloride. The aqueous polyacrylate emulsion is uniformly dispersed, has good particle size distribution, stable compatibility, good compatibility, and has good antibacterial and mildew resistance. The antibacterial rate is greater than 99.9%, and the mildew resistance grade is 0. It can be directly used as a bactericide in water-based coatings, and can also be used in combination with commonly used water-based coating emulsions such as polyacrylate, polyurethane or epoxy resin emulsions, greatly reducing the amount of bactericide added. However, the aqueous polyacrylate antibacterial emulsion uses non-environmentally friendly nonylphenol polyoxyethylene ether ammonium sulfate as an emulsifier, which has a greater impact on the environment. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide an aqueous bactericidal emulsion which can reduce the dosage of bactericide and can continuously sterilize and a preparation method thereof.

[0008] In order to solve the above technical problems, the technical solution adopted by the present invention is: to provide an aqueous bactericidal emulsion, wherein the aqueous bactericidal emulsion is prepared by including the following raw materials in parts by weight: 1-4 parts of alkenylsiloxybenzisothiazolinone ester; 40-49 parts of monomer composition; Hydrophilic agent 0.4-0.9 parts; 1-2 parts of emulsifier; Initiator 0.2-0.4 parts; 0.5-1.5 parts of pH regulator; 45-56 parts of deionized water; The structure of the alkenylsiloxybenzisothiazolinone ester is a silane-modified benzisothiazolinone ester containing a double bond.

[0009] Further, in the above-mentioned aqueous bactericidal emulsion, the monomer composition is a combination of at least two of styrene, methyl styrene, 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, octadecyl acrylate or octadecyl methacrylate.

[0010] Furthermore, in the above-mentioned aqueous bactericidal emulsion, the emulsifier is one or a combination of BASF Disponil BES-20, BASF FES-77, Solvay ABEX 8018R, Solvay RHODAFAC RS 710, Idico Reasoap SR-10, Shanghai Zhongcheng Chemical ONIST NRS-10 or ONIST M-30S.

[0011] Furthermore, in the above-mentioned aqueous 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-dimethylethanolamine or triethylamine.

[0012] Another technical solution of the present invention is to provide a method for preparing the aqueous bactericidal emulsion, comprising the following steps: S1: dissolving an emulsifier in deionized water, adding a monomer composition dropwise, stirring, and obtaining a pre-emulsion A; dissolving an emulsifier in deionized water, adding a composition consisting of alkenylsiloxybenzisothiazolinone ester, a monomer composition, and a hydrophilic agent dropwise, stirring, and obtaining a pre-emulsion B; S2: Take deionized water, add emulsifier, stir evenly and heat up, add 5wt% of pre-emulsion A and initiator, react for a period of time, and then drop the remaining pre-emulsion A and initiator aqueous solution at the same time; after the addition of pre-emulsion A is completed, continue to drop pre-emulsion B and initiator aqueous solution at the same time, continue to keep warm after the addition is completed, then cool down, add pH adjuster to adjust pH, filter with 200 mesh filter to remove gel, and obtain aqueous bactericidal emulsion.

[0013] Furthermore, the preparation method of the above-mentioned aqueous bactericidal emulsion also includes a preparation method of alkenylsiloxybenzisothiazolinone ester, comprising the following steps: 1,2-Benzisothiazoline-3-one, halogenated alcohol, weak base and 1,2-dichloroethane are added into a reaction kettle, the temperature is raised for reaction, the temperature is lowered for filtering to remove solid precipitates, the solid precipitates are washed with 1,2-dichloroethane, and the 1,2-dichloroethane solution is combined; alkenyl chlorosilane is slowly dripped into the 1,2-dichloroethane solution, the temperature is raised for reaction for a period of time in a dry nitrogen atmosphere, a small molecule alcohol is dripped into the solution, the temperature is lowered after the temperature is raised for reaction for a period of time, a dilute alkali solution is dripped into the solution for neutralization, the solution is washed with deionized water, the aqueous phase is removed by standing, and the 1,2-dichloroethane and the remaining small molecule alcohol and the remaining alcohol are removed by reduced pressure distillation to obtain a crude product, and the crude product is recrystallized with a mixed solution of 1,2-dichloroethane and petroleum ether in a volume ratio of 2:1 to obtain alkenylsiloxybenzisothiazolinone ester.

[0014] Furthermore, in the preparation method of the aqueous bactericidal emulsion, the general structural formula of the halogenated alcohol is XCH2(CH2):n CH2OH, wherein X = one of Cl, Br, I, and n = a natural number from 4 to 12.

[0015] Furthermore, in the preparation method of the above-mentioned aqueous bactericidal emulsion, the halogenated alcohol 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-tetradecanol.

[0016] Furthermore, in the preparation method of the aqueous bactericidal emulsion, the structural formula of the alkenyl chlorosilane is CH2=CH m (CH3) 1-m COOCH2CH2CH2Si(CH3) n Cl 3-n , wherein m=0 or 1, n=an integer of 0-2; the small molecule alcohol is one of methanol or ethanol.

[0017] Furthermore, in the preparation method of the above-mentioned aqueous bactericidal emulsion, the weak base is one of sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate; the dilute alkali solution is an aqueous solution of the weak base with a concentration of 3-8wt%.

[0018] The beneficial effects of the present invention are: 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, and the double bonds are highly active and can be copolymerized and bonded with ordinary monomers. The siloxybenzisothiazolinone ester segments in the polymer are evenly distributed in the latex particle shell of the emulsion, and its Si-OC bond and ester group can be slowly hydrolyzed in the water system and release a trace amount of highly effective bactericidal benzisothiazolinone derivatives, which kill bacteria and fungi that may exist in the system, and maintain the performance and appearance of the emulsion for a long time. The presence of silane groups has better adhesion to bacteria and fungi, fast sterilization speed, and good effect; b) The water-based bactericidal emulsion obtained by the present invention has excellent stability. As a film-forming substance for water-based coatings, it has good compatibility with conventional water-based resins, is stable, and can be used alone. No additional preservatives are needed to extend the shelf life of the emulsion. In a formula with conventional water-based resins as the main film-forming substance, adding part of the water-based bactericidal emulsion of the present invention at any stage of paint mixing can significantly reduce the risk of corruption of the water-based emulsion, and can be applied to the fields of coatings and adhesives; c) The functional monomer alkenylsiloxybenzisothiazolinone ester in the preparation method of the aqueous bactericidal emulsion of the present invention has a simple preparation process, is suitable for industrial scale-up production, has a high yield, and is conducive to reducing the cost of the aqueous bactericidal emulsion. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is an infrared spectrum of alkenylsiloxybenzisothiazolinone ester F1 and 1,2-benzisothiazolin-3-one BIT of Example 1 according to a specific embodiment of the present invention. DETAILED DESCRIPTION

[0020] In order to explain the technical content, achieved objectives and effects of the present invention in detail, the following is an explanation in combination with the implementation modes and the accompanying drawings.

[0021] The present invention provides a method for preparing an aqueous bactericidal emulsion, comprising the following steps: S1: In parts by weight, 151 parts of 1,2-benzisothiazolin-3-one, 144-308 parts of halogenated alcohol, 120-160 parts of weak base and 1000-1500 parts of 1,2-dichloroethane are added to a reaction kettle, the temperature is raised to 60-80°C, the reaction is carried out for 4-7 hours, the temperature is lowered to 20-30°C, the solid precipitate is filtered out, the solid precipitate is washed with a small amount of 1,2-dichloroethane, and the 1,2-dichloroethane solution is combined; 231-275 parts of alkenyl chlorosilane are slowly dripped into the 1,2-dichloroethane solution, the temperature is raised to 30°C in a dry nitrogen atmosphere, and the reaction is carried out. 50-70°C, keep warm for 4-10 hours, cool to 40-50°C, drop 10-65 parts of small molecule alcohol, heat to 50-70°C, react for 1-2 hours, cool to 20-30°C, drop dilute alkali solution to neutralize to pH=6-8, wash twice with 1000 parts of deionized water, stand to remove the water phase, remove 1,2-dichloroethane and the remaining small molecule alcohol and the remaining alcohol by vacuum distillation to obtain a crude product, recrystallize the crude product with 1,2-dichloroethane: petroleum ether=2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester; S2: In parts by weight, 3-7 parts of an emulsifier are dissolved in 140-190 parts of deionized water, and a monomer composition consisting of 200-270 parts of a monomer is added dropwise, and the mixture is stirred at 600 rpm for 1 hour to obtain a pre-emulsion A; 5-12 parts of an emulsifier are dissolved in 160-250 parts of deionized water, and a monomer composition consisting of 10-50 parts of alkenylsiloxybenzisothiazolinone ester, 250-350 parts of a monomer, and 5-12 parts of a hydrophilic agent is added dropwise, and the mixture is stirred at 600 rpm for 1 hour to obtain a pre-emulsion B; S3: In parts by weight, take 100-220 parts of deionized water, add 4-7 parts of emulsifier, stir evenly and heat to 70-90°C, add 5wt% of pre-emulsion A and 0.5-1 part of initiator, react for 0.3-0.5 hours, and then drip the remaining pre-emulsion A and 20 parts of aqueous solution containing 1-1.5 parts of initiator at the same time, and continue dripping for 2-3 hours; after the pre-emulsion A is dripped, continue to drip pre-emulsion B and 20 parts of aqueous solution containing 0.8-1.5 parts of initiator at the same time, and continue dripping for 1-2 hours. After the dripping is completed, continue to keep warm for 1-3 hours, cool to 20-30°C, add an appropriate amount of pH adjuster to adjust the pH to 7-9, filter with a 200-mesh filter to remove the gel, and obtain the aqueous bactericidal emulsion M.

[0022] Embodiment 1: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: 151 g 1,2-benzisothiazolin-3-one, 144 g 6-chloro-1-hexanol, 160 g potassium carbonate and 1000 g 1,2-dichloroethane were added to a reactor, heated to 80°C, reacted for 4 hours, cooled to 30°C, filtered to remove solid precipitate, washed solid precipitate with a small amount of 1,2-dichloroethane, and 1,2-dichloroethane solution was combined; 275 g methacryloxypropyltrichlorosilane was slowly dripped into the 1,2-dichloroethane solution, heated to 50°C in a dry nitrogen atmosphere, kept warm for 10 hours, cooled to 40°C, dripped 65 g methanol, heated to 50°C, reacted for 2 hours, cooled to 20°C, and dripped 5 wt% potassium carbonate aqueous solution The mixture was neutralized to pH=8, washed twice with 1000g of deionized water, allowed to stand to remove the aqueous phase, and 1,2-dichloroethane and the remaining methanol were removed by distillation under reduced pressure to obtain a crude product, which was recrystallized with 1,2-dichloroethane: petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F1; based on 1,2-benzisothiazolin-3-one, the yield was 78.21% and the purity was 95.68%; the infrared spectra of alkenylsiloxybenzisothiazolinone ester F1 and 1,2-benzisothiazolin-3-one BIT were shown in 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 The characteristic absorption peak of the isothiazolinone heterocyclic ring of F1 is at 1664 cm -1 , indicating that the H on the heterocyclic ring of isothiazolinone is replaced by a hydrocarbon group; 1735cm -1 The absorption peak is the characteristic absorption peak of ester group, 1089cm -1 It is a characteristic absorption peak of Si-OC bond, indicating that F1 contains ester group and siloxane group. From the comparison of infrared spectra of the two substances, it can be seen that the alkenylsiloxybenzisothiazolinone ester F1 is successfully prepared in this step.

[0023] S2: 3 g of emulsifier Disponil BES-20 was dissolved in 180 g of deionized water, and a monomer composition consisting of 20 g of styrene, 35 g of methyl methacrylate, 75 g of n-butyl acrylate and 70 g of 2-ethylhexyl acrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A1; 5 g of emulsifier ABEX 8018R and 7 g of emulsifier Reasoap SR-10 were dissolved in 160 g of deionized water, and a monomer composition consisting of 10 g of alkenylsiloxybenzisothiazolinone ester F1, 50 g of styrene, 55 g of methyl methacrylate, 75 g of n-butyl acrylate and 70 g of 2-ethylhexyl acrylate and 8 g of methacrylic acid was added dropwise, and the mixture was stirred at 600 rpm 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°C, add 5wt% of pre-emulsion A1 and 0.5g of sodium persulfate, react for 0.5 hour, and then drip the remaining pre-emulsion A1 and 20g of aqueous solution containing 1.5g of sodium persulfate at the same time, and continue dripping for 3 hours; after the pre-emulsion A1 is added, continue to drip the pre-emulsion B1 and 20g of aqueous solution containing 1.5g of sodium persulfate at the same time, and continue dripping for 2 hours. After the addition is completed, continue to keep warm for 3 hours, cool to 20°C, add 25wt% ammonia water to adjust the pH to 7.5, filter with a 200-mesh filter to remove the gel, and obtain the aqueous bactericidal emulsion M1.

[0024] Embodiment 2: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: 151g 1,2-benzisothiazolin-3-one, 220g 8-bromo-1-octanol, 120g sodium carbonate and 1500g 1,2-dichloroethane were added to a reactor, heated to 60°C, reacted for 7 hours, cooled to 20°C, filtered to remove solid precipitate, washed with a small amount of 1,2-dichloroethane, and the 1,2-dichloroethane solution was combined; 253g methacryloyloxypropylmethyldichlorosilane was slowly dripped into the 1,2-dichloroethane solution, heated to 55°C in a dry nitrogen atmosphere, kept warm for 9 hours, cooled to 45°C, dripped with 50g ethanol, heated to 60°C, reacted for 2 hours, The temperature was lowered to 25°C, and a 3 wt % dilute potassium carbonate aqueous solution was added dropwise to neutralize to pH = 7. The mixture was washed twice with 1000 g of deionized water, and the aqueous phase was removed by standing. The 1,2-dichloroethane and the remaining ethanol were removed by reduced pressure distillation to obtain a crude product. The crude product was recrystallized with 1,2-dichloroethane: petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F2; based on 1,2-benzisothiazolin-3-one, the yield was 81.94% and the purity was 96.31%.

[0025] S2: 4 g of emulsifier ONIST NRS-10 was dissolved in 180 g of deionized water, and a monomer composition consisting of 50 g of cyclohexyl acrylate, 60 g of methyl acrylate, 30 g of ethyl methacrylate, 45 g of n-butyl methacrylate, and 40 g of tridecyl methacrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A2; 5 g of emulsifier FES-77 was dissolved in 250 g of deionized water, and a monomer composition consisting of 50 g of alkenylsiloxybenzisothiazolinone ester F2, 50 g of cyclohexyl acrylate, 110 g of methyl acrylate, 90 g of ethyl methacrylate, 40 g of n-butyl methacrylate, 60 g of tridecyl methacrylate, and 12 g of itaconic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B2.

[0026] 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, and then drip the remaining pre-emulsion A2 and 20g of aqueous solution containing 1g of ammonium persulfate at the same time, and continue dripping for 2 hours; after the addition of pre-emulsion A2 is completed, continue to drip pre-emulsion B2 and 20g of aqueous solution containing 0.8g of ammonium persulfate at the same time, and continue dripping for 1 hour. After the addition is completed, continue to keep warm for 1 hour, cool to 30℃, add appropriate amount of N,N-dimethylethanolamine to adjust pH=8.5, filter with a 200-mesh filter to remove the gel, and obtain aqueous bactericidal emulsion M2.

[0027] Embodiment 3: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: 151g 1,2-benzisothiazolin-3-one, 308g 14-bromo-1-tetradecanol, 158g potassium carbonate and 1500g 1,2-dichloroethane were added to a reactor, heated to 70°C, reacted for 5 hours, cooled to 25°C, filtered to remove solid precipitate, washed with a small amount of 1,2-dichloroethane, and the 1,2-dichloroethane solution was combined; 232g methacryloyloxypropyldimethylsilyl chloride was slowly heated to 70°C, kept warm for 6 hours, cooled to 50°C, 10g ethanol was added dropwise, heated to 70°C, reacted for 1-2 hours, cooled to 20-30°C, cool to 25°C, drop 6wt% sodium carbonate aqueous solution to neutralize to pH=6, wash twice with 1000g deionized water, stand to remove the water phase, remove 1,2-dichloroethane and remaining ethanol by vacuum distillation to obtain a crude product, recrystallize the crude product with 1,2-dichloroethane: petroleum ether=2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F3; based on 1,2-benzisothiazolin-3-one, the yield is 74.69% and the purity is 97.17%; S2: 7 g of emulsifier ABEX 8018R was dissolved in 183 g of deionized water, and a monomer composition consisting of 110 g of n-butyl acrylate, 20 g of n-butyl methacrylate, 35 g of isobornyl acrylate and 40 g of octadecyl methacrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A3; 5 g of emulsifier ABEX 8018R was dissolved in 240 g of deionized water, and a monomer composition consisting of 25 g of alkenylsiloxybenzisothiazolinone ester F3, 65 g of methyl acrylate, 90 g of n-butyl acrylate, 40 g of lauryl acrylate, 55 g of 2-ethylhexyl acrylate and 5 g of acrylic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B3; S3: Take 170g of deionized water, add 4g of emulsifier RHODAFAC RS 710, stir evenly and heat to 80°C, add 5wt% of pre-emulsion A3 and 0.5g of sodium persulfate, react for 0.3 hours, and then simultaneously drop the remaining pre-emulsion A3 and 20g of an aqueous solution containing 1.5g of sodium persulfate, and continue to drop for 3 hours; after the addition of pre-emulsion A3 is completed, continue to drop pre-emulsion B3 and 20g of an aqueous solution containing 0.8g of sodium persulfate, and continue to drop for 2 hours. After the addition is completed, continue to keep warm for 2 hours, cool to 25°C, add an appropriate amount of triethylamine to adjust the pH to 8.5, and filter with a 200-mesh filter to remove the gel to obtain an aqueous bactericidal emulsion M3.

[0028] Embodiment 4: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: 151 g of 1,2-benzisothiazolin-3-one, 239 g of 6-iodo-1-hexanol, 145 g of sodium carbonate and 1300 g of 1,2-dichloroethane were added to a reactor, heated to 60°C, reacted for 7 hours, cooled to 20°C, filtered to remove solid precipitates, washed with a small amount of 1,2-dichloroethane, and the 1,2-dichloroethane solution was combined; 260 g of acryloxypropyltrichlorosilane was slowly dripped into the 1,2-dichloroethane solution, heated to 60°C in a dry nitrogen atmosphere, kept warm for 7 hours, cooled to 50°C, dripped with 65 g of methanol, heated to 55°C, reacted for 2 hours, cooled to 25°C, dropwise add 8wt% sodium carbonate aqueous solution to neutralize to pH=6.5, wash twice with 1000g deionized water, let stand to remove the aqueous phase, remove 1,2-dichloroethane and remaining methanol by vacuum distillation to obtain a crude product, recrystallize the crude product with 1,2-dichloroethane: petroleum ether=2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F4; based on 1,2-benzisothiazolin-3-one, the yield is 80.93% and the purity is 95.78%; S2: 5 g of emulsifier Reasoap SR-10 was dissolved in 190 g of deionized water, and a monomer composition consisting of 100 g of methyl styrene, 25 g of methyl acrylate, 30 g of cyclohexyl methacrylate and 80 g of n-butyl acrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A4; 8 g of emulsifier Reasoap SR-10 was dissolved in 220 g of deionized water, and a monomer composition consisting of 40 g of alkenylsiloxybenzisothiazolinone ester F4, 70 g of cyclohexyl acrylate, 90 g of cyclohexyl methacrylate, 25 g of 2-ethylhexyl acrylate, 65 g of octadecyl acrylate and 10 g of maleic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B4; S3: Take 170g of deionized water, add 6g of emulsifier Disponil BES-20, stir evenly and heat to 75°C, add 5wt% of pre-emulsion A4 and 1g of potassium persulfate, react for 0.4 hours, and then drip the remaining pre-emulsion A4 and 20g of aqueous solution containing 1.2g of potassium persulfate at the same time, and continue dripping for 2.5 hours; after the pre-emulsion A4 is dripped, continue to drip pre-emulsion B4 and 20g of aqueous solution containing 1.2g of potassium persulfate at the same time, and continue dripping for 2 hours. After the dripping is completed, keep warm for 2 hours, cool to 25°C, add appropriate amount of N,N-dimethylethanolamine to adjust pH=7, filter with a 200-mesh filter to remove gel, and obtain aqueous bactericidal emulsion M4.

[0029] Embodiment 5: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: 151 g of 1,2-benzisothiazolin-3-one, 190 g of 6-bromo-1-hexanol, 150 g of potassium carbonate and 1000 g of 1,2-dichloroethane were added to a reactor, heated to 65°C, reacted for 6 hours, cooled to 25°C, filtered to remove solid precipitates, washed with a small amount of 1,2-dichloroethane, and the 1,2-dichloroethane solution was combined; 239 g of acryloxypropylmethyldichlorosilane was slowly dripped into the 1,2-dichloroethane solution, heated to 65°C in a dry nitrogen atmosphere, kept warm for 6 hours, cooled to 45°C, dripped with 35 g of methanol, heated to 50°C, reacted for 2 hours, cooled to 20°C, dropwise add 7wt% potassium carbonate aqueous solution to neutralize to pH=7.5, wash twice with 1000g deionized water, let stand to remove the aqueous phase, remove 1,2-dichloroethane and the remaining small molecular alcohols by vacuum distillation to obtain a crude product, and recrystallize the crude product with 1,2-dichloroethane: petroleum ether=2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F5; based on 1,2-benzisothiazolin-3-one, the yield is 78.06% and the purity is 94.52%; S2: 6 g of emulsifier ONIST NRS-10 was dissolved in 170 g of deionized water, and a monomer composition consisting of 100 g of methyl methacrylate, 90 g of lauryl acrylate, and 80 g of n-butyl methacrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A5; 9 g of emulsifier ONIST NRS-10 was dissolved in 250 g of deionized water, and a monomer composition consisting of 20 g of alkenylsiloxybenzisothiazolinone ester F5, 100 g of n-butyl methacrylate, 40 g of methyl methacrylate, 80 g of 2-ethylhexyl acrylate, 70 g of isobornyl methacrylate, and 7 g of methacrylic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B5; S3: Take 180g of deionized water, add 7g of emulsifier FES-77, stir evenly and heat to 85°C, add 5wt% of pre-emulsion A5 and 0.9g of sodium persulfate, react for 0.3 hours, and then drip the remaining pre-emulsion A5 and 20g of aqueous solution containing 1.4g of sodium persulfate at the same time, and continue dripping for 2 hours; after the pre-emulsion A5 is added, continue to drip pre-emulsion B5 and 20g of aqueous solution containing 1.3g of sodium persulfate at the same time, and continue dripping for 1 hour. After the addition is completed, continue to keep warm for 1.5 hours, cool to 30°C, add 25wt% ammonia water to adjust pH=8, filter with a 200-mesh filter to remove the gel, and obtain aqueous bactericidal emulsion M5.

[0030] Embodiment 6: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: 151g 1,2-benzisothiazolin-3-one, 278g 12-bromo-1-dodecanol, 125g sodium carbonate and 1400g 1,2-dichloroethane were added to a reactor, heated to 75°C, reacted for 5 hours, cooled to 30°C, filtered to remove solid precipitate, washed with a small amount of 1,2-dichloroethane, and the 1,2-dichloroethane solution was combined; 235g methacryloxypropyldimethylsilyl chloride was slowly dripped into the 1,2-dichloroethane solution, heated to 70°C in a dry nitrogen atmosphere, kept warm for 4 hours, cooled to 40-50°C, dripped with 20g ethanol, heated to 65°C, and reacted for 1 hour , cooled to 25°C, dripped with 6wt% sodium bicarbonate aqueous solution to neutralize to pH=7, washed twice with 1000g deionized water, allowed to stand to remove the aqueous phase, and distilled under reduced pressure to remove 1,2-dichloroethane and remaining ethanol to obtain a crude product, which was recrystallized with 1,2-dichloroethane: petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F6; based on 1,2-benzisothiazolin-3-one, the yield was 78.23% and the purity was 96.44%; S2: 5 g of emulsifier FES-77 was dissolved in 170 g of deionized water, and a monomer composition consisting of 80 g of ethyl acrylate, 70 g of styrene, 40 g of cyclohexyl acrylate, and 45 g of cyclohexyl methacrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A6; 11 g of emulsifier FES-77 was dissolved in 240 g of deionized water, and a monomer composition consisting of 15 g of alkenylsiloxybenzisothiazolinone ester F6, 75 g of methylstyrene, 65 g of ethyl methacrylate, 90 g of methyl methacrylate, 45 g of isobornyl methacrylate, and 11 g of itaconic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B6; S3: Take 160g of deionized water, add 4g of emulsifier FES-77, stir evenly and heat to 75°C, add 5wt% of pre-emulsion A6 and 0.6g of ammonium persulfate, react for 0.3 hours, and then drip the remaining pre-emulsion A6 and 20g of aqueous solution containing 1g of ammonium persulfate at the same time, and continue dripping for 3 hours; after the addition of pre-emulsion A6 is completed, continue to drip pre-emulsion B6 and 20g of aqueous solution containing 1.3g of ammonium persulfate at the same time, and continue dripping for 2 hours. After the addition is completed, continue to keep warm for 2.5 hours, cool to 25°C, add appropriate amount of triethylamine to adjust pH=9, filter with a 200-mesh filter to remove the gel, and obtain aqueous bactericidal emulsion M6.

[0031] Embodiment 7: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: Add 151g 1,2-benzisothiazolin-3-one, 298g 10-iodo-1-decanol, 160g sodium carbonate and 1100g 1,2-dichloroethane into a reactor, heat to 70°C, react for 4 hours, cool to 20°C, filter to remove solid precipitate, wash solid precipitate with a small amount of 1,2-dichloroethane, and combine 1,2-dichloroethane solution; slowly drop 270g methacryloxypropyltrichlorosilane into 1,2-dichloroethane solution, heat to 55°C in a dry nitrogen atmosphere, keep warm for 9 hours, cool to 40°C, drop 60g methanol, heat to 60°C, react for 2 hours, The temperature was lowered to 20°C, 4 wt% sodium carbonate aqueous solution was added dropwise to neutralize to pH=8, the mixture was washed twice with 1000 g of deionized water, the aqueous phase was removed by standing, and 1,2-dichloroethane and the remaining methanol were removed by vacuum distillation to obtain a crude product, which was recrystallized with 1,2-dichloroethane: petroleum ether=2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F7; the yield was 83.46% based on 1,2-benzisothiazolin-3-one, and the purity was 96.52%; S2: 4 g of emulsifier RHODAFAC RS 710 was dissolved in 140 g of deionized water, and a monomer composition consisting of 30 g of methyl acrylate, 65 g of methyl methacrylate, 120 g of n-butyl acrylate, and 55 g of tridecyl acrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A7; 5 g of emulsifier RHODAFAC RS 710 and 2 g of emulsifier ABEX 8018R were dissolved in 183 g of deionized water, and a monomer composition consisting of 42 g of alkenylsiloxybenzisothiazolinone ester F7, 50 g of methyl acrylate, 50 g of methyl methacrylate, 60 g of n-butyl acrylate, 40 g of tridecyl acrylate, 55 g of 2-ethylhexyl acrylate, and 9 g of acrylic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B7; S3: Take 110g of deionized water, add 5g of emulsifier Reasoap SR-10, stir evenly and heat to 80°C, add 5wt% of pre-emulsion A7 and 1g of sodium persulfate, react for 0.4 hours, and then drip the remaining pre-emulsion A7 and 20g of aqueous solution containing 1.5g of sodium persulfate at the same time, and continue dripping for 2.5 hours; after the pre-emulsion A7 is added, continue to drip the pre-emulsion B7 and 20g of aqueous solution containing 1.5g of sodium persulfate at the same time, and continue dripping for 1.5 hours. After the addition is completed, continue to keep warm for 2 hours, cool to 20°C, add 25wt% ammonia water to adjust the pH to 8.5, and filter with a 200-mesh filter to remove the gel to obtain the aqueous bactericidal emulsion M7.

[0032] Embodiment 8: A method for preparing an aqueous bactericidal emulsion comprises the following steps: S1: 151g 1,2-benzisothiazolin-3-one, 269g 8-iodo-1-octanol, 130g sodium carbonate and 1000g 1,2-dichloroethane were added to a reaction kettle, the temperature was raised to 65°C, the reaction was carried out for 5 hours, the temperature was lowered to 25°C, the solid precipitate was filtered out, the solid precipitate was washed with a small amount of 1,2-dichloroethane, and the 1,2-dichloroethane solution was combined; 248g Acryloxypropyltrichlorosilane was dropped into 1,2-dichloroethane solution, heated to 65°C in a dry nitrogen atmosphere, kept warm for 6 hours, cooled to 45°C, 62g methanol was dropped, heated to 58°C, reacted for 2 hours, cooled to 20°C, and 6wt% potassium carbonate aqueous solution was dropped to neutralize to pH=6, washed twice with 1000g deionized water, allowed to stand to remove the water phase, and 1,2-dichloroethane and remaining methanol were removed by vacuum distillation to obtain a crude product, which was recrystallized with 1,2-dichloroethane: petroleum ether = 2:1 (volume ratio) to obtain alkenylsiloxybenzisothiazolinone ester F8; based on 1,2-benzisothiazolin-3-one, the yield was 79.38% and the purity was 95.56%; S2: 6 g of emulsifier ONIST M-30S was dissolved in 190 g of deionized water, and a monomer composition consisting of 120 g of styrene, 60 g of n-butyl acrylate, and 20 g of 2-ethylhexyl acrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A8; 8 g of emulsifier ONIST M-30S was dissolved in 210 g of deionized water, and a monomer composition consisting of 30 g of alkenylsiloxybenzisothiazolinone ester F8, 120 g of styrene, 60 g of n-butyl acrylate, 20 g of 2-ethylhexyl acrylate, 40 g of lauryl acrylate, 75 g of octadecyl methacrylate, and 6 g of maleic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B8; S3: Take 140g of deionized water, add 5g of emulsifier ONIST M-30S, stir evenly and heat to 90°C, add 5wt% of pre-emulsion A8 and 0.5g of potassium persulfate, react for 0.3 hours, and then drip the remaining pre-emulsion A8 and 20g of aqueous solution containing 1g of potassium persulfate at the same time, and continue dripping for 2 hours; after the pre-emulsion A8 is added, continue to drip pre-emulsion B8 and 20g of aqueous solution containing 1.5g of potassium persulfate at the same time, and continue dripping for 2 hours. After the addition is completed, continue to keep warm for 2 hours, cool to 25°C, add appropriate amount of N,N-dimethylethanolamine to adjust pH=7, and filter with a 200-mesh filter to remove the gel to obtain aqueous bactericidal emulsion M8.

[0033] Comparative Example 1: A method for preparing an emulsion comprises the following steps: Comparative Example 1 The emulsion was prepared in the same manner as in Example 1, except that 10 g of styrene was used instead of alkenylsiloxybenzisothiazolinone ester F1. The preparation steps are described as follows: S1: 3 g of emulsifier Disponil BES-20 was dissolved in 180 g of deionized water, and a monomer composition consisting of 20 g of styrene, 35 g of methyl methacrylate, 75 g of n-butyl acrylate and 70 g of 2-ethylhexyl acrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A9; 5 g of emulsifier ABEX 8018R and 7 g of emulsifier Reasoap SR-10 were dissolved in 160 g of deionized water, and a monomer composition consisting of 60 g of styrene, 55 g of methyl methacrylate, 75 g of n-butyl acrylate and 70 g of 2-ethylhexyl acrylate and 8 g of methacrylic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B9; S2: Take 100g of deionized water, add 4g of emulsifier Disponil BES-20, stir evenly and heat to 70°C, add 5wt% of pre-emulsion A9 and 0.5g of sodium persulfate, react for 0.5 hour, and then simultaneously drop the remaining pre-emulsion A9 and 20g of aqueous solution containing 1.5g of sodium persulfate, and continue to drop for 3 hours; after the addition of pre-emulsion A9 is completed, continue to drop pre-emulsion B9 and 20g of aqueous solution containing 1.5g of sodium persulfate, and continue to drop for 2 hours. After the addition is completed, continue to keep warm for 3 hours, cool to 20°C, add 25wt% ammonia water to adjust the pH to 7.5, filter with a 200-mesh filter to remove the gel, and obtain aqueous emulsion M9.

[0034] Comparative Example 2: A method for preparing an emulsion comprises the following steps: The preparation process of the emulsion of Comparative Example 2 is the same as that of Example 2, except that 50 g of ethyl methacrylate is used instead of alkenylsiloxybenzisothiazolinone ester F2. The preparation steps are described as follows: S1: 4 g of emulsifier ONIST NRS-10 was dissolved in 180 g of deionized water, and a monomer composition consisting of 50 g of cyclohexyl acrylate, 60 g of methyl acrylate, 30 g of ethyl methacrylate, 45 g of n-butyl methacrylate, and 40 g of tridecyl methacrylate was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion A10; 5 g of emulsifier FES-77 was dissolved in 250 g of deionized water, and a monomer composition consisting of 50 g of cyclohexyl acrylate, 110 g of methyl acrylate, 140 g of ethyl methacrylate, 40 g of n-butyl methacrylate, 60 g of tridecyl methacrylate, and 12 g of itaconic acid was added dropwise, and the mixture was stirred at 600 rpm for 1 hour to obtain pre-emulsion B10; 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, and then drip the remaining pre-emulsion A10 and 20g of aqueous solution containing 1g of ammonium persulfate at the same time, and continue dripping for 2 hours; after the addition of pre-emulsion A10 is completed, continue to drip pre-emulsion B10 and 20g of aqueous solution containing 0.8g of ammonium persulfate at the same time, and continue dripping for 1 hour. After the addition is completed, continue to keep warm for 1 hour, cool to 30℃, add appropriate amount of N,N-dimethylethanolamine to adjust pH=8.5, filter with a 200-mesh filter to remove the gel, and obtain aqueous emulsion M10.

[0035] Embodiment 9: The aqueous bactericidal emulsions M1-M8 of the present invention, the aqueous emulsions M9-M10 obtained in the comparative examples, the emulsion Wantipro® 0625 produced by Wanhua Chemical, and the emulsions of the aqueous bactericide emulsions M1 and M10 mixed uniformly at a volume ratio of 1:4, and the emulsions of M1 and M10 mixed uniformly at a volume ratio of 1:10 were subjected to stability tests in a daily non-sterilized environment. The bactericide content of Wantipro® 0625 is: CMIT / MIT (3:1) is about 49 mg / kg, and MIT is about 240 mg / kg. The test results are shown in Table 1 - Storage test of M1-M10, M1+M10 mixed emulsions and Wantipro® 0625 in a daily non-sterilized environment.

[0036] Table 1 As can be seen from Table 1, the aqueous bactericidal emulsions M1-M8 and Wantipro® 0625 of the present invention can continue to sterilize in a daily non-sterilized environment, and are in good condition. During the 12-month storage period, the antibacterial properties are comparable to those of conventional emulsions with bactericides added, and can meet daily conditions for use. The bactericide-free emulsions M9 and M10 described in the comparative example were slightly corrupted after 1 month of storage, and the odor was normal; after 3 months of storage, obvious corruption and abnormal odor occurred; after 6 months of storage, the emulsions were seriously corrupted and smelled bad, and the emulsions settled and could not be used. The emulsions of M1 and M10 mixed in a volume ratio of 1:4 maintained a good appearance during the 12-month storage period. The emulsions of M1 and M10 mixed in a volume ratio of 1:10 maintained a good appearance during the 6-month storage period, and only slightly corrupted after 12 months of storage, and the odor was normal, which was similar to the degree of corruption of M10 stored alone for 1 month. This fully demonstrates that the addition of a small amount of aqueous bactericidal emulsion M1 can greatly delay the corruption of M10, and also demonstrates that the aqueous bactericidal emulsion of the present invention has good compatibility with other emulsions.

[0037] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention's specification and drawings, or directly or indirectly applied in related technical fields, are also included in 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 alkenylsiloxybenzisothiazolinone ester; 40-49 parts of monomer composition; Hydrophilic agent 0.4-0.9 parts; 1-2 parts of emulsifier; Initiator 0.2-0.4 parts; 0.5-1.5 parts of pH regulator; 45-56 parts of deionized water; The structure of the alkenylsiloxybenzisothiazolinone ester is 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 composition 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, 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 BASF Disponil BES-20, BASF FES-77, Solvay ABEX 8018R, Solvay RHODAFAC RS 710, Aidico 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; the pH adjuster is one of 25wt% ammonia water, N,N-dimethylethanolamine or triethylamine.

5. A method for preparing the aqueous bactericidal emulsion according to any one of claims 1 to 4, characterized in that: The steps include: S1: dissolving an emulsifier in deionized water, adding a monomer composition dropwise, stirring, and obtaining a pre-emulsion A; dissolving an emulsifier in deionized water, adding a composition consisting of alkenylsiloxybenzisothiazolinone ester, a monomer composition, and a hydrophilic agent dropwise, stirring, and obtaining a pre-emulsion B; S2: Take deionized water, add emulsifier, stir evenly and heat up, add 5wt% of pre-emulsion A and initiator, react for a period of time, and then drop the remaining pre-emulsion A and initiator aqueous solution at the same time; after the addition of pre-emulsion A is completed, continue to drop pre-emulsion B and initiator aqueous solution at the same time, continue to keep warm after the addition is completed, then cool down, add pH adjuster to adjust pH, filter with 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: Also included is a method for preparing alkenylsiloxybenzisothiazolinone ester, comprising the following steps: 1,2-Benzisothiazoline-3-one, halogenated alcohol, weak base and 1,2-dichloroethane are added into a reaction kettle, the temperature is raised for reaction, the temperature is lowered for filtering to remove solid precipitates, the solid precipitates are washed with 1,2-dichloroethane, and the 1,2-dichloroethane solution is combined; alkenyl chlorosilane is slowly dripped into the 1,2-dichloroethane solution, the temperature is raised for reaction for a period of time in a dry nitrogen atmosphere, a small molecule alcohol is dripped into the solution, the temperature is lowered after the temperature is raised for reaction for a period of time, a dilute alkali solution is dripped into the solution for neutralization, the solution is washed with deionized water, the aqueous phase is removed by standing, and the 1,2-dichloroethane and the remaining small molecule alcohol and the remaining alcohol are removed by reduced pressure distillation to obtain a crude product, and the crude product is recrystallized with a mixed solution of 1,2-dichloroethane and petroleum ether in a volume ratio of 2:1 to obtain alkenylsiloxybenzisothiazolinone ester.

7. The method for preparing the aqueous bactericidal emulsion according to claim 6, characterized in that: The general structural formula of the halogenated alcohol is XCH2(CH2) n CH2OH, wherein X = one of Cl, Br, 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 halogenated alcohol 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-tetradecanol.

9. The method for preparing the aqueous bactericidal emulsion according to claim 6, characterized in that: The general structural formula of the alkenyl chlorosilane is CH2=CH m (CH3) 1-m COOCH2CH2CH2Si(CH3) n Cl 3-n , wherein m=0 or 1, n=an integer of 0-2; 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 alkali solution is an aqueous solution of the weak base with a concentration of 3-8wt%.

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