Antibacterial deodorizing composition and preparation method thereof

Abstract

The present invention relates to the technical field of deodorant compositions, and more specifically, to an antibacterial deodorant composition and a preparation method thereof. The antibacterial deodorant composition comprises a fatty alcohol dimethacrylate, γ-cyclodextrin, an azacarbene silver ion complex, a pH regulator, and deionized water; wherein the mass concentration of the fatty alcohol dimethacrylate is 0.5%-1%, the mass concentration of the γ-cyclodextrin is 1%-2%, and the mass concentration of the azacarbene silver ion complex is 0.04%-0.1%. The present invention utilizes the synergistic effect of the fatty alcohol dimethacrylate, γ-cyclodextrin, and the azacarbene silver ion complex to not only have an excellent deodorizing effect but also significantly improve deodorizing efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of deodorant compositions, in particular to an antibacterial deodorant composition and a preparation method thereof. Background Art

[0002] As people's quality of life continues to improve and their awareness of health and environmental protection grows, the market demand for disinfection and deodorization products is becoming increasingly significant. Whether in daily living spaces such as homes, offices, and bathrooms, or in specialized areas such as industrial production, agricultural breeding, and healthcare, strict requirements are placed on environmental cleanliness, hygiene, and odor control.

[0003] At present, there are many products used for deodorization, which can be roughly divided into four categories: sensory deodorants, physical deodorants, biological deodorants and chemical deodorants. Sensory deodorants use some pleasant aromatic compounds to mask or offset odors to achieve sensory deodorization. However, after the aromatic compounds evaporate, the odor molecules still exist and cannot be eliminated. Physical deodorants mainly use some porous substances such as activated carbon and diatomaceous earth to adsorb odor molecules. The disadvantage of this method is that the adsorption is selective, and the adsorbent needs to be replaced or regenerated regularly, which is costly. Biological deodorants mainly include enzyme deodorants, plant deodorants and microbial deodorants. At present, due to limitations such as their durability and cost, the feasibility of large-scale production is not high. Chemical deodorants mainly use neutralization, oxidation, reduction, condensation, complexation, substitution and other reactions between active substances and odorous substances to convert odorous substances into new substances with no odor or less odor, thereby achieving the purpose of deodorization.

[0004] Existing chemical deodorants mostly use zinc ricinoleate and soybean ethyl sulfate morpholine as deodorizing components, but their deodorizing effect on hydrogen sulfide is poor. In addition, soybean ethyl sulfate morpholine has biosafety issues, which limits the increase in its usage. Bactericides mostly use cationic bactericides, which have environmental pollution and drug resistance issues. Although silver ion bactericides can effectively kill bacteria and have good drug resistance, the stability of silver ions in traditional silver ion bactericides has always been a difficult problem to solve. Traditional silver ion bactericides only have a bactericidal effect and have no promoting effect on deodorization.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The first objective of the present invention is to provide an antibacterial deodorizing composition to address the technical problems of existing chemical deodorizers being ineffective against hydrogen sulfide, and traditional silver ion fungicides being poorly stable and lacking a deodorizing effect. The present invention utilizes the synergistic effects of a fatty alcohol dimethacrylate, γ-cyclodextrin, and an azacarbene silver ion complex to not only effectively remove hydrogen sulfide-like odor molecules but also significantly improve deodorization efficiency. The azacarbene silver ion complex not only has the advantages of good stability and high sterilization efficiency as a fungicide, but also acts as a catalyst, increasing the reaction rate of the fatty alcohol dimethacrylate in eliminating hydrogen sulfide and other sulfides, thereby accelerating deodorization.

[0007] The second object of the present invention is to provide a method for preparing the antibacterial deodorizing composition as described above, which has a simple preparation process and is convenient for mass production.

[0008] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted:

[0009] An antibacterial and deodorizing composition comprises fatty alcohol dimethacrylate, γ-cyclodextrin, an azacarbene silver ion complex, a pH regulator, and deionized water; wherein the mass concentration of the fatty alcohol dimethacrylate is 0.5%-1%, the mass concentration of the γ-cyclodextrin is 1%-2%, and the mass concentration of the azacarbene silver ion complex is 0.04%-0.1%.

[0010] Preferably, the fatty alcohol dimethacrylate includes at least one of 1,12-dodecanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,14-tetradecanediol dimethacrylate.

[0011] Preferably, the preparation method of the azacarbene silver ion complex comprises the following steps:

[0012] S1. An imidazole salt, potassium hexafluorophosphate, water and dichloromethane are mixed and stirred for reaction; wherein the imidazole salt comprises at least one of 1,3-bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and 4,5-dihydro-1,3-bis(2-methylphenyl)-1H-imidazolium chloride;

[0013] S2. The reaction solution in step S1 is separated to obtain a first organic phase and an aqueous phase, the aqueous phase obtained after separation is extracted with an extractant to obtain a second organic phase, the first organic phase and the second organic phase are combined, the combined organic phases are dried, and the solvent and the extractant are evaporated to obtain an azacarbene precursor;

[0014] S3. The azacarbene precursor and the silver source are mixed with acetonitrile, and the mixture is refluxed under light shielding conditions. After cooling, the solvent is removed to obtain the azacarbene silver ion complex.

[0015] Preferably, in step S1, the molar ratio of the imidazole salt to the potassium hexafluorophosphate is 1:1-1.2.

[0016] Preferably, in step S1, the volume ratio of the water to the dichloromethane is 1:1-2.

[0017] Preferably, in step S1, the stirring reaction time is 3-5 hours.

[0018] Preferably, in step S2, the extractant comprises dichloromethane or ethyl acetate.

[0019] Preferably, in step S2, the organic phase is dried using anhydrous sodium sulfate.

[0020] Preferably, in step S3, the molar ratio of the azacarbene precursor to Ag in the silver source is 1.1-1.2:1.

[0021] Preferably, in step S3, the silver source includes silver acetate and / or silver oxide.

[0022] Preferably, in step S3, the reflux reaction time is not less than 12 hours.

[0023] Preferably, the antibacterial deodorizing composition further comprises glycerol, and the mass concentration of the glycerol is 5%-10%.

[0024] Preferably, the antibacterial deodorizing composition further comprises a plant extract, and the mass concentration of the plant extract is 0.1%-0.2%.

[0025] Preferably, the plant extract includes at least one of lavender essential oil, rose essential oil, jasmine essential oil, chamomile essential oil, and rosemary extract.

[0026] Preferably, the antibacterial deodorizing composition further comprises D1821, and the mass concentration of D1821 is 0.2%-0.5%.

[0027] Preferably, the antibacterial deodorant composition further comprises hydrogenated castor oil PEG-40, and the mass concentration of the hydrogenated castor oil PEG-40 is 3%-5%.

[0028] Preferably, the pH adjuster includes at least one of citric acid, sodium citrate, sodium bicarbonate, and sodium dihydrogen phosphate.

[0029] Preferably, the pH of the antibacterial deodorizing composition is 5-7.

[0030] A method for preparing the antibacterial deodorizing composition as described above comprises the following steps:

[0031] (1) Mix γ-cyclodextrin and fatty alcohol dimethacrylate with water, heat and stir to allow the two molecules to fully combine;

[0032] (2) adding the azacarbene silver ion complex to the solution obtained in step (1), stirring and dissolving while maintaining the temperature;

[0033] (3) At room temperature, the remaining components are added to the solution obtained in step (2), stirred and mixed, and finally a pH adjuster is added to adjust the pH value of the system.

[0034] Preferably, in step (1), the heating and stirring temperature is 50-65° C., and the stirring time is 20-40 min.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The present invention adopts the idea of combining physical deodorization with chemical deodorization, and uses fatty alcohol dimethacrylate and γ-cyclodextrin as deodorizing components. Compared with traditional lauryl methacrylate, fatty alcohol dimethacrylate has two reaction sites and has better hydrogen sulfide removal ability. At the same time, the larger inner cavity structure of γ-cyclodextrin is used to adsorb more odor molecules, providing a reaction site for fatty alcohol dimethacrylate to eliminate odor molecules. Compared with traditional silver ion fungicides, a nitrogen carbene silver ion complex is used as a bactericide. While having good stability and high sterilization efficiency compared with traditional silver ion fungicides, it can also serve as a catalyst to increase the reaction rate of fatty alcohol dimethacrylate in eliminating hydrogen sulfide and other sulfides, thereby accelerating deodorization. The three components can work together to achieve a synergistic effect, not only achieving a good deodorizing effect, but also significantly improving the deodorizing rate. DETAILED DESCRIPTION

[0037] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0038] The first aspect of the present invention provides an antibacterial and deodorizing composition, comprising fatty alcohol dimethacrylate, γ-cyclodextrin, an azacarbene silver ion complex, a pH regulator, and deionized water; wherein the mass concentration of the fatty alcohol dimethacrylate is 0.5%-1%, the mass concentration of the γ-cyclodextrin is 1%-2%, the mass concentration of the azacarbene silver ion complex is 0.04%-0.1%, and the amount of the pH regulator is determined according to the pH value of the system.

[0039] The formulation system of the present invention abandons the use of commonly used deodorizing raw materials such as zinc ricinoleate and soybean ethyl sulfate morpholine, and instead uses more efficient dimethacrylate fatty alcohol ester as the deodorizing component. At the same time, the idea of combining physical deodorization with chemical deodorization is adopted, and γ-cyclodextrin is introduced into the deodorizing system. The two synergistically achieve a better deodorizing effect. Compared with traditional lauryl methacrylate, dimethacrylate fatty alcohol ester has two reaction sites and therefore has a higher hydrogen sulfide scavenging ability. Currently, the cyclodextrin used in the combination of physical and chemical deodorization is mostly β-cyclodextrin, which has poor water solubility and the inner cavity formed by the spatial structure is not as good as γ-cyclodextrin. The present invention adopts γ-cyclodextrin in combination with dimethacrylate fatty alcohol ester, and utilizes the larger internal cavity structure of γ-cyclodextrin to adsorb more odor molecules. The larger internal cavity structure provides the dimethacrylate fatty alcohol ester with a reaction space to eliminate odor molecules, slows down the release of raw materials, prolongs the deodorization time, and achieves a better deodorization effect; in addition, the present invention adopts an azacarbene silver ion complex as a bactericide, which not only has high bactericidal efficiency but also has a catalytic effect, can enhance the reaction of dimethacrylate fatty alcohol ester to eliminate hydrogen sulfide and other sulfides, and accelerate the elimination of odor molecules; the combination of the three achieves a synergistic effect.

[0040] In some embodiments, typically but not limitatively, for example, the mass percentage of fatty alcohol dimethacrylate in the antibacterial deodorant composition can be any value among 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or a range consisting of any two values; the mass percentage of γ-cyclodextrin can be any value among 1%, 1.2%, 1.5%, 1.8%, 2%, or a range consisting of any two values; the mass percentage of azacarbene silver ion complex can be any value among 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, or a range consisting of any two values.

[0041] In some specific embodiments of the present invention, the fatty alcohol dimethacrylate used includes at least one of 1,12-dodecanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,14-tetradecanediol dimethacrylate; preferably 1,12-dodecanediol dimethacrylate.

[0042] In some specific embodiments of the present invention, the preparation method of the azacarbene silver ion complex used comprises the following steps:

[0043] S1. An imidazole salt, potassium hexafluorophosphate, water and dichloromethane are mixed and stirred for reaction; wherein the imidazole salt comprises at least one of 1,3-bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and 4,5-dihydro-1,3-bis(2-methylphenyl)-1H-imidazolium chloride;

[0044] S2. The reaction mixture in step S1 is separated to obtain a first organic phase and an aqueous phase, and the aqueous phase obtained after separation is extracted with an extractant to obtain a second organic phase, the first organic phase and the second organic phase are combined, the combined organic phase is dried, and the solvent and the extractant are evaporated to obtain an azacarbene precursor;

[0045] S3. Mixing an azacarbene precursor and a silver source with acetonitrile, performing a reflux reaction under light shielding, and removing the solvent after cooling to obtain an azacarbene silver ion complex.

[0046] The purpose of reacting potassium hexafluorophosphate with an imidazole salt in step S1 is to remove chloride ions by anion replacement. After the reaction is completed, separation is performed to obtain a first organic phase and an aqueous phase. The product is mainly located in the first organic phase. The aqueous phase is extracted with an extractant to obtain a second organic phase. The purpose is to extract the product remaining in the aqueous phase and improve the yield. The generated potassium chloride is left in the aqueous phase and removed, which can avoid the formation of silver chloride precipitate during the subsequent reaction with a silver source. The purpose of drying the organic phase in step S2 is to remove moisture therein, and then the dichloromethane solvent and the extractant are evaporated to obtain an azacarbene precursor. In step S3, compared with other organic solvents, acetonitrile is used as an organic solvent to prepare the azacarbene silver ion complex, which has a better catalytic effect on the deodorization reaction.

[0047] In some specific embodiments of the present invention, in step S1, the molar ratio of imidazole salt to potassium hexafluorophosphate is 1:1-1.2, for example, it can be any point value among 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, or a range value consisting of any two point values.

[0048] In some specific embodiments of the present invention, in step S1, the volume ratio of water to dichloromethane is 1:1-2, for example, it can be any value among 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, or a range value consisting of any two values.

[0049] In some specific embodiments of the present invention, in step S1, the stirring reaction is carried out at room temperature, and the stirring reaction time is 3-5 hours, for example, it can be any point value among 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or a range value consisting of any two point values.

[0050] In some specific embodiments of the present invention, in step S2, the extractant includes dichloromethane or ethyl acetate.

[0051] In some specific embodiments of the present invention, in step S2, the organic phase is dried with anhydrous sodium sulfate to remove moisture from the organic phase.

[0052] In some specific embodiments of the present invention, in step S3, the molar ratio of the azacarbene precursor to the Ag in the silver source is 1.1-1.2:1. For example, it can be any point value among 1.1:1, 1.12:1, 1.15:1, 1.18:1, 1.2:1 or a range value consisting of any two point values. If the amount of azacarbene precursor used is too small, the catalytic deodorization effect will decrease.

[0053] In some specific embodiments of the present invention, in step S3, the silver source used includes silver acetate and / or silver oxide.

[0054] In some specific embodiments of the present invention, in step S3, the reflux reaction time is not less than 12 hours, for example, it can be any point value among 12 hours, 16 hours, 20 hours, 24 hours, or a range value consisting of any two point values.

[0055] In some specific embodiments of the present invention, the antibacterial deodorant composition also includes glycerin, which mainly plays a soothing role. The mass concentration of glycerin in the antibacterial deodorant composition is 5%-10%. For example, it can be any point value among 5%, 6%, 7%, 8%, 9%, 10%, or a range value consisting of any two point values.

[0056] In some specific embodiments of the present invention, the antibacterial deodorizing composition further comprises a plant extract, the main function of which is to adjust the fragrance of the system to make the atmosphere pleasant. The mass concentration of the plant extract in the antibacterial deodorizing composition is 0.1%-0.2%. For example, it can be any point value among 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, or a range value consisting of any two point values.

[0057] In some specific embodiments of the present invention, the plant extract used includes at least one of lavender essential oil, rose essential oil, jasmine essential oil, chamomile essential oil, and rosemary extract; the plant extract is used to adjust the fragrance of the system.

[0058] In some specific embodiments of the present invention, the antibacterial deodorizing composition further comprises D1821. The functions of D1821 are fabric softening or hair softening and antistatic. When the antibacterial deodorizing composition is used for pet deodorization, D1821 can be added. The mass concentration of D1821 in the antibacterial deodorizing composition is 0.2%-0.5%. For example, it can be any point value among 0.2%, 0.3%, 0.4%, 0.5%, or a range value consisting of any two point values.

[0059] In some specific embodiments of the present invention, the antibacterial deodorant composition also includes hydrogenated castor oil PEG-40, which is used as a solubilizer to increase the volume of the flavor to make it more soluble. When a plant flavor is added to adjust the fragrance of the system, hydrogenated castor oil PEG-40 can be added for solubilization; the mass concentration of hydrogenated castor oil PEG-40 in the antibacterial deodorant composition is 3%-5%, for example, it can be any value among 3%, 3.5%, 4%, 4.5%, 5%, or a range value consisting of any two value values.

[0060] In some specific embodiments of the present invention, the pH adjuster used includes at least one of citric acid, sodium citrate, sodium bicarbonate, and sodium dihydrogen phosphate.

[0061] In some embodiments of the present invention, the pH of the antibacterial deodorant composition is 5-7.

[0062] A second aspect of the present invention provides a method for preparing the antibacterial deodorant composition according to any one of the aforementioned embodiments, comprising the following steps:

[0063] (1) Mix γ-cyclodextrin and fatty alcohol dimethacrylate with water, heat and stir to allow the two molecules to fully combine;

[0064] (2) adding the azacarbene silver ion complex to the solution obtained in step (1), stirring and dissolving while maintaining the temperature;

[0065] (3) At room temperature, glycerin, plant extract, D1821, and hydrogenated castor oil PEG-40 are added to the solution obtained in step (2), stirred and mixed, and finally a pH adjuster is added to adjust the pH value of the system.

[0066] The present invention first heats and stirs γ-cyclodextrin and fatty alcohol dimethacrylate in water to fully combine the two molecules and enhance their synergistic effect. The γ-cyclodextrin provides physical adsorption deodorization, and its larger internal cavity structure can absorb more odor molecules. The presence of the cavity also provides a reaction space for the fatty alcohol dimethacrylate to eliminate odor molecules, slowing the release of raw materials and prolonging the deodorization time. The method of the present invention has a simple preparation process, mild and controllable conditions, and is easy to mass produce.

[0067] In some specific embodiments of the present invention, in step (1), the heating and stirring temperature is 50-65°C, for example, it can be any point value among 50°C, 55°C, 60°C, and 65°C, or a range value consisting of any two points; the stirring time is 20-40 min, for example, it can be any point value among 20 min, 25 min, 30 min, 35 min, and 40 min, or a range value consisting of any two points.

[0068] The following describes some embodiments of the present invention in detail with reference to specific application examples. Unless otherwise specified, the raw materials used in the examples can be purchased from the market.

[0069] First, the deodorization effects of different deodorization raw materials and the synergistic deodorization effects between different components were evaluated; garlic juice was used as the odor source: garlic odor is mainly caused by thiols, sulfides and disulfides.

[0070] Experimental method: Fresh garlic was squeezed to extract the garlic juice and the juice was collected; an appropriate amount of garlic juice was weighed and added to a glass bottle, which was sealed in the glass bottle for 1 minute; then an appropriate amount of deodorant was added, the bottle was sealed after addition, and the mixture was stirred for the same amount of time (i.e., the action time); after stirring, 20 volunteers were asked to smell the odor in the bottle and give their evaluation.

[0071] The evaluation criteria for the presence or absence of garlic flavor in the present invention are as follows: if more than 18 of the test subjects evaluate it as having no flavor, it is considered to have no garlic flavor; if 2 or more test subjects evaluate it as having a garlic flavor, it is considered to have a garlic flavor.

[0072] (1) Evaluation of the removal effect of different deodorizing raw materials on garlic odor:

[0073] Zinc ricinoleate, ricinoleic acid ester, soybean ethyl sulfate morpholine, persimmon tannic acid, 1,12-dodecanol dimethacrylate, β-cyclodextrin, and lauryl methacrylate were prepared with deionized water to prepare sample solutions with a mass concentration of 0.1%. The solutions were used to evaluate the removal effect of garlic odor. The results are shown in Table 1.

[0074] Table 1

[0075]

[0076] The results in Table 1 show that after 30 seconds of treatment, only the garlic juice treated with 1,12-dodecanol dimethacrylate had no garlic smell in the bottle. Its garlic odor removal effect was better than that of traditional deodorizing raw materials such as zinc ricinoleate, ricinoleic acid ester, soybean ethyl sulfate morpholine, persimmon tannic acid, β-cyclodextrin and lauryl methacrylate.

[0077] (2) Evaluation of garlic odor removal effects of different fatty alcohol dimethacrylates:

[0078] 1,12-dodecanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,14-tetradecanediol dimethacrylate were respectively prepared with deionized water to prepare sample solutions with a mass concentration of 0.1%, which were used to evaluate the removal effect of garlic odor. The results are shown in Table 2.

[0079] Table 2

[0080]

[0081] The results in Table 2 show that after 20 seconds of treatment, all three fatty alcohol dimethacrylates removed the garlic odor from the garlic juice jar. This demonstrates that the three fatty alcohol dimethacrylates employed in this invention are superior to traditional deodorizing ingredients such as zinc ricinoleate, ricinoleic acid ester, soybean ethyl sulfate morpholine, persimmon tannic acid, and lauryl methacrylate in removing garlic odor. After 15 seconds of treatment, only 1,12-dodecanediol dimethacrylate removed the garlic odor from the garlic juice jar, demonstrating that 1,12-dodecanediol dimethacrylate offers the best deodorizing effect among the three fatty alcohol dimethacrylates.

[0082] (3) Evaluation of the synergistic deodorizing effect of azacarbene silver ion complex prepared under different conditions and 1,12-dodecanediol dimethacrylate. The preparation method of azacarbene silver ion complex is as follows:

[0083] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at a molar ratio of 1:1.1 at room temperature for 3 hours. After the reaction, stirring was stopped and the mixture was separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to remove the dichloromethane to obtain an azacarbene precursor. The precursor and silver acetate were added in an acetonitrile solvent at a molar ratio of 1:1, and the mixture was refluxed for 12 hours under light-shielding conditions. The mixture was then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 1.

[0084] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred at a molar ratio of 1:1.1 in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at room temperature for 3 h. After the reaction, stirring was stopped and the mixture was separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to obtain an azacarbene precursor, which was added to an acetonitrile solvent with silver acetate at a molar ratio of 1.1:1. The mixture was refluxed under light-shielding conditions for 12 h, then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 2.

[0085] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred at a molar ratio of 1:1.1 in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at room temperature for 3 h. After the reaction, stirring was stopped and the mixture was separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to obtain an azacarbene precursor, which was added to an acetonitrile solvent with silver acetate at a molar ratio of 1.2:1. The mixture was refluxed under light-shielding conditions for 12 h. The mixture was then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 3.

[0086] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred at a molar ratio of 1:1.1 in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at room temperature for 3 h. After the reaction, stirring was stopped and the liquids were separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to remove the dichloromethane to obtain an azacarbene precursor. The azacarbene precursor and silver acetate were added to a methanol solvent at a molar ratio of 1.2:1. The mixture was refluxed under light-shielding conditions for 12 h. The mixture was then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 4.

[0087] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at a molar ratio of 1:1.1 at room temperature for 3 h. After the reaction, stirring was stopped and the mixture was separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to remove the dichloromethane to obtain an azacarbene precursor. The precursor was added to a tetrahydrofuran solvent with silver acetate at a molar ratio of 1.2:1, and the mixture was refluxed under light-shielding conditions for 12 h. The mixture was then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 5.

[0088] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred at a molar ratio of 1:1.1 in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at room temperature for 3 h. After the reaction, stirring was stopped and the liquids were separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to remove the dichloromethane to obtain an azacarbene precursor. The precursor and silver acetate were added to the dichloromethane solvent at a molar ratio of 1.2:1, and the mixture was refluxed under light-shielding conditions for 12 h. The mixture was then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 6.

[0089] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred at a molar ratio of 1:1.1 in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at room temperature for 3 h. After the reaction, stirring was stopped and the mixture was separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to remove the dichloromethane to obtain an azacarbene precursor. The precursor and silver oxide were added to the dichloromethane solvent at a molar ratio of 1.2:0.5. The mixture was refluxed under light-shielding conditions for 24 h. The mixture was then cooled to room temperature and the solvent was rotary evaporated. The obtained solid was dried under reduced pressure to obtain product 7.

[0090] 1,3-Bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and potassium hexafluorophosphate were stirred at a molar ratio of 1:1.1 in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at room temperature for 3 h. After the reaction, stirring was stopped and the liquids were separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first and second organic phases were collected and combined, and the organic phases were dried over anhydrous sodium sulfate. The dichloromethane was evaporated to remove the dichloromethane to obtain an azacarbene precursor. The precursor and silver oxide were added to an acetonitrile solvent at a molar ratio of 1.2:0.5, and the mixture was refluxed under light-shielding conditions for 24 h. The mixture was then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 8.

[0091] 4,5-Dihydro-1,3-bis(2-methylphenyl)-1H-imidazole chloride and potassium hexafluorophosphate were stirred at a molar ratio of 1:1.1 in a mixed solvent of water and dichloromethane (volume ratio of 1:1) at room temperature for 3 h. After the reaction, stirring was stopped and the mixture was separated to obtain a first organic phase and an aqueous phase. The aqueous phase was then extracted three times with dichloromethane to obtain a second organic phase. The first organic phase and the second organic phase were collected and combined, and the organic phase was dried over anhydrous sodium sulfate. The dichloromethane was evaporated to remove the dichloromethane to obtain an azacarbene precursor. The precursor and silver acetate were added to an acetonitrile solvent at a molar ratio of 1.2:1, and the mixture was refluxed under light-shielding conditions for 24 h. The mixture was then cooled to room temperature, the solvent was rotary evaporated, and the obtained solid was dried under reduced pressure to obtain product 9.

[0092] The sample solutions prepared under different conditions were prepared with azacarbene silver ion complexes, 1,12-dodecanediol dimethacrylate and deionized water. The concentration of 1,12-dodecanediol dimethacrylate was 0.1% and the concentration of azacarbene silver ion complex was 0.02%. The solutions were used to evaluate the removal effect of garlic juice odor. The results are shown in Table 3.

[0093] Table 3

[0094]

[0095] The results in Table 3 show that when the molar ratio of azacarbene precursor to Ag in the silver source is 1.1-1.2:1, the garlic juice odor removal effect is better after 20 seconds of action. Too low a ratio (such as 1:1) will lead to a decrease in the odor removal effect. Compared with methanol, tetrahydrofuran and dichloromethane, the azacarbene silver ion complex prepared by using acetonitrile as the organic solvent and combined with 1,12-dodecanediol dimethacrylate has a better garlic juice odor removal effect after 20 seconds of action. The azacarbene silver ion complex prepared by using silver acetate as the silver source has a better accelerating effect on the deodorization reaction. This shows that the ratio of azacarbene precursor to Ag in the silver source, the type of silver source and the choice of organic solvent will all affect the accelerating effect of the azacarbene silver ion complex on the deodorization reaction.

[0096] (4) Evaluation of the synergistic effect of cyclodextrin and fatty alcohol dimethacrylate:

[0097] 1,12-dodecanol dimethacrylate, cyclodextrin and water were prepared into a sample solution, and the garlic odor removal effect was evaluated. The results are shown in Table 4.

[0098] Table 4

[0099]

[0100] The results in Table 4 show that both β-cyclodextrin and γ-cyclodextrin can improve the garlic juice odor removal effect of 1,12-dodecanol dimethacrylate, but γ-cyclodextrin and 1,12-dodecanol dimethacrylate have a synergistic effect and a better odor removal effect.

[0101] (5) Evaluation of garlic juice odor removal effects of different deodorization systems:

[0102] Fatty alcohol dimethacrylate, γ-cyclodextrin, silver ion fungicide and deionized water were prepared into a sample solution for removing the odor of garlic juice. Among them, the fatty alcohol dimethacrylate was 1,12-dodecanol dimethacrylate, and the azacarbene silver ion complex was product 3 prepared by the present invention. The evaluation results are shown in Table 5.

[0103] Table 5

[0104]

[0105] As shown in Table 5, the samples without silver ion fungicide and the samples with traditional silver acetate (silver ion fungicide) both had a garlic smell in the bottle after being reacted with 0.5 g of garlic juice for 30 seconds. However, the sample with the azacarbene silver ion complex prepared by the present invention as a fungicide had no garlic smell in the bottle after being reacted with 0.7 g of garlic juice for 10 seconds. This indicates that the use of the azacarbene silver ion complex as a fungicide can significantly improve the odor removal efficiency of dimethacrylate fatty alcohol, while the traditional silver ion fungicide silver acetate does not have this effect.

[0106] (6) Effect of the dosage of azacarbene silver ion complex:

[0107] Fatty alcohol dimethacrylate, γ-cyclodextrin, azacarbene silver ion complex and deionized water were prepared into a sample solution for removing the odor of garlic juice. Among them, the fatty alcohol dimethacrylate was 1,12-dodecanol dimethacrylate with a mass concentration of 0.5%; the mass concentration of γ-cyclodextrin was 1%; the azacarbene silver ion complex was product 3 prepared by the present invention, and the mass concentrations were shown in Table 6 (0, 0.02%, 0.03%, 0.04% and 0.05% respectively); the evaluation results are shown in Table 6.

[0108] Table 6

[0109]

[0110] The results in Table 6 show that for 0.5 g of garlic juice, when the mass concentration of the azacarbene silver ion complex reaches 0.04%, the removal of odor molecules can be significantly accelerated, and the garlic smell is gone in the bottle after only 10 seconds.

[0111] In the following, an antibacterial and deodorizing composition product is prepared in conjunction with specific application examples, wherein the azacarbene silver ion complex adopts the product 3 prepared by the present invention.

[0112] Example 1

[0113] This embodiment provides an antibacterial deodorizing composition, which comprises the following components by weight percentage:

[0114] 1,12-dodecanol dimethacrylate 0.5%, γ-cyclodextrin 1%, azacarbene silver ion complex 0.05%, glycerin 5%, lavender essential oil 0.1%, D1821 0.2%, hydrogenated castor oil PEG-40 3%, pH adjuster 0.1% and the balance water.

[0115] The preparation method comprises the following steps:

[0116] (1) Weigh the raw materials according to the formula ratio, mix γ-cyclodextrin and 1,12-dodecanol dimethacrylate with water, heat to 60°C and stir for 30 minutes to allow the two molecules to fully combine;

[0117] (2) adding the azacarbene silver ion complex to the solution obtained in step (1), stirring and dissolving at the same temperature for 30 minutes;

[0118] (3) At room temperature, glycerin, plant extract, D1821, and hydrogenated castor oil PEG-40 are added to the solution obtained in step (2), stirred and mixed, and finally a pH regulator is added to adjust the pH value of the system to 5-7.

[0119] Example 2

[0120] This embodiment provides an antibacterial deodorizing composition, which comprises the following components by weight percentage:

[0121] 1,12-dodecanol dimethacrylate 0.5%, γ-cyclodextrin 1.5%, azacarbene silver ion complex 0.05%, glycerin 5%, lavender essential oil 0.1%, D1821 0.2%, hydrogenated castor oil PEG-40 3%, pH adjuster 0.1% and the balance water.

[0122] The preparation method is similar to that of Example 1, with the only difference being the composition formula.

[0123] Example 3

[0124] This embodiment provides an antibacterial deodorizing composition, which comprises the following components by weight percentage:

[0125] 1,12-dodecanol dimethacrylate 1%, γ-cyclodextrin 2%, azacarbene silver ion complex 0.1%, glycerin 10%, lavender essential oil 0.1%, D1821 0.2%, hydrogenated castor oil PEG-40 3%, pH adjuster 0.1% and the balance water.

[0126] The preparation method is similar to that of Example 1, with the only difference being the composition formula.

[0127] Comparative Example 1

[0128] This comparative example provides an antibacterial deodorizing composition, which comprises the following components by weight percentage:

[0129] 1,12-dodecanol dimethacrylate 0.5%, γ-cyclodextrin 1%, silver acetate 0.05%, glycerin 5%, lavender essential oil 0.1%, D1821 0.2%, hydrogenated castor oil PEG-40 3%, pH adjuster 0.1% and the balance water.

[0130] The preparation method is similar to that of Example 1, with the only difference being the composition formula.

[0131] Test example

[0132] (1) Effect of antibacterial deodorizing composition on removing odor of garlic juice

[0133] Experimental method: Fresh garlic was squeezed to extract the garlic juice, and the juice was collected; 0.5 g of the garlic juice was weighed and added to a glass bottle, which was sealed in the glass bottle for 1 minute; then 0.1 g of the antibacterial and deodorizing composition was added, the bottle was sealed after addition, and the mixture was stirred for a certain time (5 seconds in Example 3 and 10 seconds in the others); after stirring, 20 professional volunteers were asked to smell the odor in the bottle and give their evaluation. The evaluation results are shown in Table 7.

[0134] Table 7

[0135]

[0136] The results in Table 7 show that the antibacterial deodorizing composition prepared by the present invention can remove the odor of 0.5 g of garlic juice within 5-10 seconds. The garlic odor is mainly caused by thiols, sulfides and disulfides. It can be seen that the antibacterial deodorizing composition provided by the present invention has an excellent deodorizing effect on sulfides. In addition, the results of Example 1 and Comparative Example 1 show that the azacarbene silver ion complex can significantly improve the odor removal efficiency, while the traditional silver ion fungicide silver acetate does not have this effect.

[0137] (2) Removal effect of antibacterial deodorizing composition on hydrogen sulfide and methyl mercaptan gas

[0138] To test hydrogen sulfide removal, at 25±1°C, weigh 0.1g of solid sodium sulfide nonahydrate and add deionized water to a 0.1% aqueous solution. Then, add 2g of the sodium sulfide aqueous solution to 100µL of 5% H₂SO₄. The solution was placed in a 25L sealed glassware and the hydrogen sulfide concentration was measured using a PTM-600 composite gas analyzer until the concentration stabilized. Repeat the experiment three times, recording the average of the results as the blank (X0). Under the same conditions, spray 10g of the deodorant sample into the glassware after the hydrogen sulfide concentration stabilized. The change in hydrogen sulfide concentration was then measured using a PTM-600 composite gas analyzer, recording the result as X. Repeat the experiment three times, taking the average of the results as X1. Removal efficiency was calculated as: Removal efficiency = (X0 - X1) / X0 × 100%. The hydrogen sulfide removal efficiency test results are shown in Table 8.

[0139] Table 8

[0140]

[0141] Methyl mercaptan gas removal test: At 25±1°C, 0.1g of sodium methyl mercaptan was weighed and added to deionized water to prepare a 0.1% aqueous solution. Then, 2g of the sodium methyl mercaptan solution was added to 100µL of 5% H₂SO₄. The solution was placed in a 25L sealed glassware and the methyl mercaptan concentration was measured using a PTM-600 composite gas analyzer until the concentration stabilized. This experiment was repeated three times, and the average of the results was recorded as the blank value (X0). Under the same conditions, 10g of the deodorant sample was sprayed into the glassware after the methyl mercaptan concentration stabilized. The change in methyl mercaptan concentration was then measured using the PTM-600 composite gas analyzer, and the result was recorded as X. This experiment was repeated three times, and the average of the results was recorded as X1. The removal rate was calculated as: Removal rate = (X0 - X1) / X0 × 100%. The methyl mercaptan gas removal rate results are shown in Table 9.

[0142] Table 9

[0143]

[0144] Although the present invention has been illustrated and described using specific embodiments, it should be appreciated that the above embodiments are merely intended to illustrate the technical solutions of the present invention rather than to limit them. Those skilled in the art should understand that the technical solutions described in the above embodiments may be modified, or some or all of the technical features thereof may be replaced by equivalents, without departing from the spirit and scope of the present invention. However, these modifications or replacements do not deviate from the essence of the corresponding technical solutions within the scope of the technical solutions of the embodiments of the present invention. Therefore, this means that all such replacements and modifications within the scope of the present invention are included in the appended claims.

Claims

1. An antibacterial deodorizing composition, characterized in that: The invention comprises fatty alcohol dimethacrylate, γ-cyclodextrin, azacarbene silver ion complex, a pH regulator and deionized water; wherein the mass concentration of the fatty alcohol dimethacrylate is 0.5%-1%, the mass concentration of the γ-cyclodextrin is 1%-2%, and the mass concentration of the azacarbene silver ion complex is 0.04%-0.1%.

2. The antibacterial deodorizing composition according to claim 1, characterized in that The fatty alcohol dimethacrylate includes at least one of 1,12-dodecanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,14-tetradecanediol dimethacrylate.

3. The antibacterial deodorizing composition according to claim 1, characterized in that The preparation method of the azacarbene silver ion complex comprises the following steps: S1. An imidazole salt, potassium hexafluorophosphate, water and dichloromethane are mixed and stirred for reaction; wherein the imidazole salt comprises at least one of 1,3-bis((s)-1-phenylethyl)-1H-imidazol-3-ium chloride and 4,5-dihydro-1,3-bis(2-methylphenyl)-1H-imidazolium chloride; S2. The reaction solution in step S1 is separated to obtain a first organic phase and an aqueous phase, the aqueous phase obtained after separation is extracted with an extractant to obtain a second organic phase, the first organic phase and the second organic phase are combined, the combined organic phases are dried, and the solvent and the extractant are evaporated to obtain an azacarbene precursor; S3. The azacarbene precursor and the silver source are mixed with acetonitrile, and the mixture is refluxed under light shielding conditions. After cooling, the solvent is removed to obtain the azacarbene silver ion complex.

4. The antibacterial deodorizing composition according to claim 3, characterized in that In step S1, the molar ratio of the imidazole salt to the potassium hexafluorophosphate is 1:1-1.2; and the stirring reaction time is 3-5 hours.

5. The antibacterial deodorizing composition according to claim 3, characterized in that In step S2, the extractant includes dichloromethane or ethyl acetate; and / or the organic phase is dried using anhydrous sodium sulfate.

6. The antibacterial deodorizing composition according to claim 3, characterized in that In step S3, at least one of the following characteristics is met: (1) The molar ratio of the azacarbene precursor to the Ag in the silver source is 1.1-1.2:1; (2) The silver source includes silver acetate and / or silver oxide; (3) The reflux reaction time is not less than 12 hours.

7. The antibacterial deodorizing composition according to claim 1, characterized in that Meet at least one of the following characteristics: (1) further comprising glycerol, wherein the mass concentration of the glycerol is 5%-10%; (2) Also includes plant extracts, wherein the mass concentration of the plant extracts is 0.1%-0.2%; (3) also including D1821, wherein the mass concentration of D1821 is 0.2%-0.5%; (4) further comprising hydrogenated castor oil PEG-40, wherein the mass concentration of the hydrogenated castor oil PEG-40 is 3%-5%; (5) The pH adjuster includes at least one of citric acid, sodium citrate, sodium bicarbonate, and sodium dihydrogen phosphate; (6) The pH of the antibacterial deodorizing composition is 5-7.

8. The antibacterial deodorizing composition according to claim 7, characterized in that The plant extract comprises at least one of lavender essential oil, rose essential oil, jasmine essential oil, chamomile essential oil and rosemary extract.

9. The method for preparing the antibacterial deodorizing composition according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Mix γ-cyclodextrin and fatty alcohol dimethacrylate with water, heat and stir to allow the two molecules to fully combine; (2) adding the azacarbene silver ion complex to the solution obtained in step (1), stirring and dissolving while maintaining the temperature; (3) At room temperature, the remaining components are added to the solution obtained in step (2), stirred and mixed, and finally a pH adjuster is added to adjust the pH value of the system.

10. The method for preparing the antibacterial deodorizing composition according to claim 9, characterized in that: In step (1), the heating and stirring temperature is 50-65° C., and the stirring time is 20-40 min.

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