A highly antibacterial Bola surfactant and its preparation method and application

Abstract

The present invention relates to a high antibacterial Bola surfactant and its preparation method and application, belonging to the field of surfactants. The preparation steps of the Bola surfactant are: (1) 1,12-dibromododecane is dissolved in acetonitrile to obtain a solution; (2) after diethanolamine is added dropwise while stirring to the solution obtained in step (1), an acid binding agent is added when heated to 75-85°C, and the temperature is kept for 8-12h; (3) after the heating reaction ends, the acid binding agent, acetonitrile and excess diethanolamine are removed in sequence, and then dissolved in ethyl acetate, washed with pure water, and ethyl acetate is removed to obtain an intermediate product; (4) the intermediate product obtained in step (3) is dissolved in anhydrous ethanol, ethylene dichloride is added thereto, after heating to reflux, anhydrous ethanol is removed, and vacuum drying after washing with a solvent is obtained to obtain a Bola surfactant. The preparation process in the present invention is simple, the synthesis efficiency of the Bola surfactant is high, and the prepared Bola surfactant has high water solubility and antibacterial effect.

Description

Technical Field

[0001] The invention belongs to the field of surfactants, and in particular relates to a Bola surfactant with high antibacterial property and a preparation method and application thereof. Background Art

[0002] Bola-type surfactants are a new type of functional surfactant. Different from traditional surfactants that are composed of a single hydrophobic chain and a monopolar head group, Bola-type surfactants are compounds composed of two hydrophilic polar groups connected and bonded by one or more hydrophobic chains, including single-chain, double-chain and semi-ring types. They not only have the good wetting, emulsification, antistatic and soft properties of traditional surfactants, but also because of their unique structural characteristics, Bola-type surfactants can form stable monolayer lipid membranes and vesicles. At present, the research on Bola-type surfactants is still in a relatively early stage, and the application and development of Bola-type surfactants still have broad prospects.

[0003] Patent CN 114181718 A discloses a Bola-type surfactant. The invention first mixes aliphatic polyetheramine with halogen-substituted alkyl sulfonate to react to obtain an intermediate product; then mixes the intermediate product with halogen-substituted methane or ethane to react to obtain a Bola-type surfactant. The invention applies this surfactant to nanoemulsions, which have high temperature resistance and high salt resistance, low nanoscale and ultra-low crude oil interfacial tension and high oil washing activity. Patent CN 105688741 A discloses a method for preparing an amino acid-type Bola surfactant. The invention uses alkyl diamine and tert-butyl hydroxyl-protected amino acid as raw materials, and prepares a new type of Bola-type surfactant through acylation reaction. Amide bonds are formed during the preparation process, making its properties in aqueous solution more stable.

[0004] However, the Bola surfactants in the existing invention patents are mainly used in the fields of heavy oil extraction, biological science, new materials, information science, printing and dyeing industry, etc., while the related research on Bola surfactants used in the field of disinfection is still relatively small. In modern society, there are mainly two types of surfactants used in disinfectants, namely cationic surfactants, such as disinfectants of traditional quaternary ammonium salt type surfactants, and amphoteric surfactants. Based on the problems existing in the prior art, the development of a Bola-type surfactant used in the field of medical disinfection has practical significance for expanding the application of Bola-type surfactants and enhancing the bactericidal effect of disinfectants. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a highly antibacterial Bola surfactant and a preparation method and application thereof. The preparation process of the present invention is simple, the synthesis efficiency of the Bola surfactant is high, and the prepared Bola surfactant has high water solubility and antibacterial effect.

[0006] The first aspect of the present invention provides a highly antibacterial Bola surfactant, and the synthesis steps of the highly antibacterial Bola surfactant are as follows:

[0007]

[0008] The second aspect of the present invention provides a method for preparing a highly antibacterial Bola surfactant, comprising the following preparation steps:

[0009] (1) dissolving 1,12-dibromododecane in acetonitrile to obtain a solution;

[0010] (2) adding diethanolamine dropwise to the solution obtained in step (1) while stirring, heating to 75-85° C., adding an acid binding agent, and keeping the temperature for 8-12 hours;

[0011] (3) After the heat preservation reaction is completed, the acid binding agent, acetonitrile and excess diethanolamine are removed in sequence, and then dissolved in ethyl acetate, washed with pure water, and then ethyl acetate is removed to obtain an intermediate product;

[0012] (4) dissolving the intermediate product obtained in step (3) in anhydrous ethanol, adding dichloroethane thereto, heating under reflux, removing the anhydrous ethanol, washing with a solvent and vacuum drying to obtain a highly antibacterial Bola surfactant.

[0013] The invention uses 1,12-dibromododecane, diethanolamine and dichloroethane as raw materials, and obtains a quaternary ammonium salt type Bola surfactant with a yield of more than 80% by controlling the molar ratio of the raw materials and the reaction conditions. The surfactant has good solubility in water and high-efficiency antibacterial property.

[0014] Preferably, the concentration of 1,12-dibromododecane in the solution of step (1) is 0.4-0.6 mol / L.

[0015] Further preferably, the concentration of 1,12-dibromododecane in the solution of step (1) is 0.5 mol / L.

[0016] Preferably, the molar ratio of the 1,12-dibromododecane, the acid binding agent and the diethanolamine is 1:(1.1-1.3):(2-2.7).

[0017] More preferably, the molar ratio of the 1,12-dibromododecane, the acid binding agent and the diethanolamine is 1:1.2:2.4.

[0018] The applicant found that strictly controlling the molar ratio of 1,12-dibromododecane, acid-binding agent and diethanolamine can improve the synthesis efficiency of the Bola surfactant intermediate. This is because, on the one hand, a moderate excess of diethanolamine can undergo a substitution reaction with the bromine at both ends of 1,12-dibromododecane to generate an intermediate; on the other hand, it can also avoid an increase in the loss of intermediate products due to excessive use of raw materials and too many washing times.

[0019] Preferably, the acid binding agent is anhydrous potassium carbonate.

[0020] In the present invention, anhydrous potassium carbonate is selected as the acid-binding agent. Anhydrous potassium carbonate has high alkalinity and relatively low cost. When it is heated to 75-85° C. and added into the reaction system, the synthesis reaction of the Bola surfactant can be accelerated.

[0021] Preferably, the molar ratio of the intermediate product to ethylene dichloride is 1:(1-1.3).

[0022] Further preferably, the molar ratio of the intermediate product to ethylene dichloride is 1:1.2.

[0023] The structural formula of the intermediate product is shown in the synthesis steps.

[0024] The applicant has found that strictly controlling the molar ratio of the intermediate product to ethylene dichloride in step (4) can save raw materials while ensuring a high synthesis efficiency of the Bola surfactant.

[0025] Preferably, the heating reflux temperature is 75-85° C., and the reflux time is 40-48 h.

[0026] More preferably, the heating reflux temperature is 80° C. and the reflux time is 42 h.

[0027] The applicant has found that strictly controlling the heating temperature and reflux time can ensure that the intermediate product fully reacts with ethylene dichloride, thereby improving the synthesis efficiency of the quaternary ammonium salt type Bola surfactant.

[0028] Preferably, the solvent in step (4) is acetone.

[0029] The applicant has found that using acetone as a solvent has a better washing effect on the Bola surfactant synthesized in the present invention without causing too much product loss.

[0030] Preferably, the yield of the Bola surfactant is ≥80%.

[0031] In the present invention, strictly controlling the above-mentioned raw material molar ratio, heating temperature and reflux time can keep the yield of the prepared Bola surfactant above 80%.

[0032] The third aspect of the present invention provides an application of a highly antibacterial Bola surfactant in the field of disinfection.

[0033] The Bola surfactant synthesized in the present invention is a quaternary ammonium salt type surfactant, which has good water solubility and antibacterial properties, and more hydroxyl groups in its structure can also produce complexation with other disinfectants in the disinfectant to enhance the bactericidal effect.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The invention synthesizes a quaternary ammonium salt type Bola surfactant which can be used in the field of disinfection. The preparation process is simple and easy to operate. By strictly controlling the preparation process, the yield of the quaternary ammonium salt type Bola surfactant can be maintained at more than 80%. The surfactant itself has good water solubility and antibacterial properties and can be used as an antibacterial agent. At the same time, since it also contains more hydroxyl groups in its structure, it can produce complexation with other disinfectants in the disinfectant to enhance the bactericidal effect. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment.It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.If not otherwise specified, the endpoints and any values ​​of the scope disclosed in this article are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values.For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between separate point values, one or more new numerical ranges can be combined with each other, and these numerical ranges should be considered to be specifically disclosed in this article.

[0037] The acid binding agent used in Examples 1-4 and 6-8 of the present invention is anhydrous potassium carbonate; the solvent used in Examples 1-7 is acetone.

[0038] Example 1

[0039] A method for preparing a highly antibacterial Bola surfactant comprises the following preparation steps:

[0040] (1) dissolving 0.1 mol of 1,12-dibromododecane in 200 mL of acetonitrile to obtain a solution;

[0041] (2) adding 0.2 mol of diethanolamine dropwise to the solution obtained in step (1) while stirring, adding 0.12 mol of an acid binding agent when heated to 75° C., and keeping the temperature for 12 h;

[0042] (3) After the reaction is completed, the acid-binding agent, acetonitrile and excess diethanolamine are removed by suction filtration and rotary evaporation, and then the mixture is dissolved in 100 mL of ethyl acetate, washed with pure water three times, and then the ethyl acetate is removed by rotary evaporation to obtain an intermediate product;

[0043] (4) 0.1 mol of the intermediate product obtained in step (3) was dissolved in 200 mL of anhydrous ethanol, to which 0.12 mol of dichloroethane was added. After refluxing at 80° C. for 42 h, the anhydrous ethanol was removed by rotary evaporation. The mixture was washed three times with 50 mL of solvent and then vacuum dried to obtain a highly antibacterial Bola surfactant.

[0044] Example 2

[0045] A method for preparing a highly antibacterial Bola surfactant comprises the following preparation steps:

[0046] (1) dissolving 0.1 mol of 1,12-dibromododecane in 182 mL of acetonitrile to obtain a solution;

[0047] (2) adding 0.24 mol of diethanolamine dropwise to the solution obtained in step (1) while stirring, adding 0.11 mol of an acid binding agent when heated to 80° C., and keeping the temperature for 10 h;

[0048] (3) After the reaction is completed, the acid-binding agent, acetonitrile and excess diethanolamine are removed by suction filtration and rotary evaporation, and then the mixture is dissolved in 100 mL of ethyl acetate, washed with pure water three times, and then the ethyl acetate is removed by rotary evaporation to obtain an intermediate product;

[0049] (4) 0.1 mol of the intermediate product obtained in step (3) was dissolved in 200 mL of anhydrous ethanol, 0.1 mol of dichloroethane was added thereto, and the mixture was refluxed at 75° C. for 48 h, and then the anhydrous ethanol was removed by rotary evaporation. The mixture was washed with a solvent for three times and then vacuum dried to obtain a highly antibacterial Bola surfactant.

[0050] Example 3

[0051] A method for preparing a highly antibacterial Bola surfactant comprises the following preparation steps:

[0052] (1) dissolving 0.1 mol of 1,12-dibromododecane in 208 mL of acetonitrile to obtain a solution;

[0053] (2) adding 0.27 mol of diethanolamine dropwise to the solution obtained in step (1) while stirring, adding 0.13 mol of an acid binding agent when heated to 85° C., and keeping the temperature for 8 h;

[0054] (3) After the reaction is completed, the acid-binding agent, acetonitrile and excess diethanolamine are removed by suction filtration and rotary evaporation, and then the mixture is dissolved in 100 mL of ethyl acetate, washed with pure water three times, and then the ethyl acetate is removed by rotary evaporation to obtain an intermediate product;

[0055] (4) 0.1 mol of the intermediate product obtained in step (3) was dissolved in 200 mL of anhydrous ethanol, to which 0.13 mol of dichloroethane was added. After refluxing at 85° C. for 40 h, the anhydrous ethanol was removed by rotary evaporation. The mixture was washed three times with a solvent and then dried in a vacuum to obtain a highly antibacterial Bola surfactant.

[0056] Example 4

[0057] A method for preparing a highly antibacterial Bola surfactant, the specific implementation method is the same as that of Example 1, except that the amount of diethanolamine used is 0.18 mol.

[0058] Example 5

[0059] A method for preparing a highly antibacterial Bola surfactant, the specific implementation method is the same as that of Example 1, except that the acid binding agent used is an equimolar amount of triethylamine.

[0060] Example 6

[0061] A method for preparing a highly antibacterial Bola surfactant, the specific implementation method is the same as that of Example 1, except that the amount of dichloroethane used is 0.9 mol.

[0062] Example 7

[0063] A method for preparing a highly antibacterial Bola surfactant, the specific implementation method is the same as that of Example 1, except that the heating reflux temperature is 70° C. and the reflux time is 35 hours.

[0064] Example 8

[0065] A method for preparing a highly antibacterial Bola surfactant, the specific implementation method is the same as that of Example 1, except that the solvent used is ethyl acetate.

[0066] Performance Test of Bola Surfactant

[0067] The Bola surfactant prepared in the examples was tested as follows:

[0068] 1. Yield of Bola surfactant: The yield of the Bola surfactant synthesized in Examples 1-8 was tested by high performance liquid chromatography (stationary phase: ZORBAX SB-C18 (4.6×150 mm, 5 μm); mobile phase composed of methanol and water in a volume ratio of 4:1; flow rate 0.5 mL / min; column temperature 25° C.; ultraviolet detection wavelength 232 nm), and the yield was calculated after quantitative analysis. The specific test results are shown in Table 1;

[0069] 2. Water solubility test: 0.2 g of the Bola surfactant synthesized in Examples 1-8 was taken and placed in equal volumes (10 mL) of water, anhydrous ethanol, methanol, n-hexane and petroleum ether, respectively, and the dissolution was observed. The specific test results are shown in Table 2;

[0070] 3. Antibacterial test: The Oxford cup method was used to measure the diameters of the inhibition zones of the Bola surfactant and benzalkonium chloride (control group) prepared in Example 1 against Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa. The larger the diameter of the inhibition zone, the better the antibacterial effect. The specific test results are shown in Table 3.

[0071] Preparation of Bola surfactant solution: 0.5 g of Bola surfactant in each example was added to a 10 mL centrifuge tube, and 10 mL of deionized water was added to fully dissolve to obtain a 50 mg / mL mother solution, and then diluted in multiples to obtain 25 mg / mL, 12.5 mg / mL, 6.5 mg / mL and 3 mg / mL test solutions respectively;

[0072] Benzalkonium chloride was used as a control, and the preparation of the benzalkonium chloride test solution was the same as above.

[0073] Table 1

[0074]

[0075] Table 2

[0076]

[0077] Table 3

[0078]

[0079] As can be seen from Table 1, the preparation process is strictly controlled in Examples 1-3, so that the yield of the prepared Bola surfactant reaches more than 80%, while the conditions of the preparation process, the raw material ratio, the type of acid binding agent, the heating temperature and reflux time, and the type of solvent are changed in Examples 4-8, so that the yield of the prepared Bola surfactant is lower and the comprehensive performance is also changed.

[0080] It can be seen from Table 2 that the Bola surfactant prepared in Examples 1-8 has good solubility in water, and can also be dissolved in anhydrous ethanol and methanol, but is insoluble in n-hexane and petroleum ether.

[0081] It can be seen from Table 3 that compared with the antibacterial property of benzalkonium chloride, the Bola surfactant in the present invention has a better antibacterial effect. When the concentrations of Bola surfactant and benzalkonium chloride are both 3 mg / mL, they have no antibacterial effect on Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa; when the concentration is 6.5 mg / mL, benzalkonium chloride only has an inhibitory effect on Staphylococcus aureus, while Bola surfactant has a good inhibitory effect on Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa; when the concentration is 12.5 mg / mL, the diameter of the inhibition zone of Bola surfactant for four bacteria is larger than that of benzalkonium chloride for four bacteria, indicating that the antibacterial effect of Bola surfactant is better; when the concentration is 25 mg / mL, the diameter of the inhibition zone of Bola surfactant and benzalkonium chloride for Bacillus subtilis is the same, but the diameter of the inhibition zone of Bola surfactant for Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa is larger than that of benzalkonium chloride for them. It can be seen from this that the Bola surfactant synthesized in the present invention has a higher antibacterial performance.

[0082] The above is only a preferred embodiment of the present invention and does not constitute any form of limitation to the present application. Although the present application is disclosed as above in the preferred embodiment, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A highly antibacterial Bola surfactant, characterized in that: The structural formula of the highly antibacterial Bola surfactant is as follows: 。 2. A method for preparing the highly antibacterial Bola surfactant according to claim 1, characterized in that: The method comprises the following preparation steps: (1) dissolving 1,12-dibromododecane in acetonitrile to obtain a solution; (2) adding diethanolamine dropwise to the solution obtained in step (1) while stirring, heating to 75-85°C, adding an acid binding agent, and keeping the temperature for 8-12 hours; (3) After the reaction is completed, the acid-binding agent, acetonitrile and excess diethanolamine are removed in sequence, and then dissolved in ethyl acetate. After washing with pure water, the ethyl acetate is removed to obtain an intermediate product; (4) The intermediate product obtained in step (3) is dissolved in anhydrous ethanol, dichloroethane is added thereto, the anhydrous ethanol is removed after heating under reflux, and the product is washed with a solvent and then dried under vacuum to obtain a highly antibacterial Bola surfactant.

3. The method for preparing a highly antibacterial Bola surfactant according to claim 2, characterized in that: The concentration of 1,12-dibromododecane in the solution of step (1) is 0.4-0.6 mol / L.

4. The method for preparing a highly antibacterial Bola surfactant according to claim 2, characterized in that: The molar ratio of the 1,12-dibromododecane, the acid binding agent and the diethanolamine is 1:(1.1-1.3):(2-2.7).

5. The method for preparing a highly antibacterial Bola surfactant according to claim 2, characterized in that: The acid binding agent is anhydrous potassium carbonate.

6. The method for preparing a highly antibacterial Bola surfactant according to claim 2, characterized in that: The molar ratio of the intermediate product to ethylene dichloride is 1:(1-1.3).

7. The method for preparing a highly antibacterial Bola surfactant according to claim 2, characterized in that: The heating reflux temperature in step (4) is 75-85° C., and the reflux time is 40-48 h.

8. The method for preparing a highly antibacterial Bola surfactant according to claim 2, characterized in that: The solvent in step (4) is acetone.

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