A long-acting bactericidal surfactant and its application in washing powder

Abstract

The present invention relates to the field of surfactant technology, and discloses a long-acting bactericidal surfactant and its application in washing powder. The present invention performs Schiff base condensation reaction on DL-tyrosine and glutaraldehyde, and then performs esterification reaction with alkyl acyl chloride compound, and then reduces with sodium borohydride, and undergoes epoxy ring-opening reaction in 2,3-epoxypropyltrimethylammonium chloride to obtain a novel long-acting bactericidal surfactant. The long-acting bactericidal surfactant contains a diquaternary ammonium salt antibacterial group, and the minimum inhibitory concentration MIC for bacteria such as Escherichia coli is only 0.391ug / mL. When the mass concentration of the long-acting bactericidal surfactant of the present invention is 0.2-2g / L, the surface tension of the solution is only 58.1-12.0mN / m, and the lower the surface tension, the better the wetting, emulsification and dispersibility, which is conducive to the practical application of surfactants in washing powder, laundry detergent, etc.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, in particular to a long-acting bactericidal surfactant and application thereof in washing powder. Background Art

[0002] Surfactants mainly include cationic surfactants, anionic surfactants, zwitterionic surfactants, etc., which can reduce the surface tension of the solution and have good emulsification, dispersion, wetting and other properties. They are important in washing powder, laundry liquid, dishwashing liquid and other cleaning products. Among them, cationic surfactants have good bactericidal properties and are widely used.

[0003] The development of surfactants with high surface performance, green and pollution-free, and good biocompatibility is a research hotspot. CN116286028B discloses a biodegradable amino acid surfactant, which is compounded with sodium cocoylaminopropionate, sodium lauroyl glutamate, etc., nanoparticle modifiers, and an interfacial liquid. The obtained amino acid surfactant has good detergency, biodegradability, and heat stability. However, the surfactant does not have antibacterial properties, which is not conducive to its practical application in sterilization and washing products. Summary of the invention

[0004] The invention solves the problem that the conventional surfactant used in washing powder has no antibacterial property.

[0005] The technical solution of the present invention is: a long-acting bactericidal surfactant, the structural formula of which is shown in formula (I):

[0006]

[0007] Further, the preparation method of the long-acting bactericidal surfactant is as follows:

[0008] Step (1), add ethanol, DL-tyrosine, glutaraldehyde, potassium hydroxide to a reaction flask, react at 50-70°C for 6-12h, add concentrated hydrochloric acid to acidify the solution to pH 5 after the reaction, rotary evaporate the solution, wash with water, and recrystallize the product in ethanol to obtain intermediate 1. The reaction formula is:

[0009]

[0010] Step (2), in an ice-water bath, add dichloromethane, toluene or tetrahydrofuran solvent, intermediate 1, alkyl acyl chloride compound, triethylamine to a reaction flask, stir and react at 20-35°C for 8-15h, rotary evaporate the solution, wash with deionized water, add the product to ethanol, then add sodium borohydride, react for 3-5h, concentrate the solution, wash with deionized water, and recrystallize the product in ethanol to obtain intermediate 2. The reaction formula is:

[0011]

[0012] Step (3), adding ethanol and the intermediate 2, 2, 3-epoxypropyltrimethylammonium chloride to a reaction bottle equipped with a condenser reflux tube, reacting at 70-80° C. for 36-72 hours, concentrating the solution after the reaction, washing with acetone, and drying to obtain a long-acting bactericidal surfactant.

[0013]

[0014] Furthermore, in step (1), the molar ratio of DL-tyrosine to glutaraldehyde is (2-2.2):1:(3.8-4.2).

[0015] Furthermore, in step (2), the molar ratio of intermediate 1, alkyl acyl chloride compound and triethylamine is 1:(2-2.6):(2-2.6).

[0016] Further, the structural formula of the alkyl acyl chloride compound is: n is any integer between 9 and 15.

[0017] Furthermore, in step (3), the molar ratio of the intermediate 2 to 2,3-epoxypropyltrimethylammonium chloride is 1:(2.4-3.2).

[0018] Furthermore, the application of long-lasting bactericidal surfactant in antibacterial laundry detergent; the antibacterial laundry detergent includes 72-75 parts by weight of industrial salt (the main component is sodium chloride), 4.5-5.5 parts by weight of alkaline protease blue particles, 1.2-1.8 parts by weight of protease (model Savinase 8.0T), 18-22 parts by weight of sodium carbonate, 0.5-2 parts by weight of long-lasting bactericidal surfactant, 2-3 parts by weight of fatty alcohol polyoxyethylene ether AEO-9, 2-3 parts by weight of sodium α-olefin sulfonate, and 1-1.5 parts by weight of fragrance.

[0019] The technical effect of the present invention is as follows: the present invention conducts a Schiff base condensation reaction on DL-tyrosine and glutaraldehyde, then conducts an esterification reaction with an alkyl acyl chloride compound, then conducts a sodium borohydride reduction, and conducts an epoxy ring-opening reaction in 2,3-epoxypropyltrimethylammonium chloride to obtain a novel green and pollution-free amino acid-based long-acting bactericidal surfactant.

[0020] The long-acting bactericidal surfactant of the present invention contains a diquaternary ammonium salt antibacterial group, has a strong positive charge, can interact electrostatically with the negatively charged cell membrane of bacteria, thereby making the surfactant adhere to the cell membrane surface, improving the permeability of the cell membrane, making the genetic material such as enzymes in the cell membrane escape, destroying the normal metabolism and reproduction of bacteria, thereby achieving an excellent bactericidal effect. The minimum inhibitory concentration MIC of the surfactant to Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Candida albicans is only 0.391ug / mL, 0.391ug / mL, 25ug / mL and 3.125ug / mL.

[0021] The long-acting bactericidal surfactant of the present invention contains multiple hydrophilic carboxyl groups, quaternary ammonium salts, hydroxyl hydrophilic groups, and hydrophobic phenyl alkyl long chains, has a strong surface active effect, and significantly reduces the surface tension of the solution. When the mass concentration of the long-acting bactericidal surfactant in Example 3 is 0.2-2g / L, the surface tension of the solution is only 58.1-12.0mN / m. The lower the surface tension, the better the wetting, emulsification and dispersibility, which is conducive to the practical application of surfactants in washing powders, laundry liquids, etc. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0023] Antibacterial laundry detergent: composed of 720-750g industrial salt (the main component is sodium chloride), 45-55g alkaline protease blue particles, 12-18g protease (model Savinase 8.0T), 180-220g sodium carbonate, 5-20 parts by weight of long-acting bactericidal surfactant, 20-30g fatty alcohol polyoxyethylene ether AEO-9, 20-30g sodium α-olefin sulfonate, and 10-15g essence.

[0024] The preparation method of the long-acting bactericidal surfactant is shown in the following examples.

[0025] Example 1

[0026] Step (1), add 400mL ethanol, 63mmol DL-tyrosine, 30mmol glutaraldehyde, 120mmol potassium hydroxide to the reaction bottle, react at 60℃ for 12h, add concentrated hydrochloric acid to acidify the solution to pH 5 after the reaction, rotary evaporate the solution, wash with water, and recrystallize the product in ethanol to obtain intermediate 1 with a yield of 8.11g. The structural formula is as follows:

[0027]

[0028] Step (2), in an ice-water bath, add 200 mL of dichloromethane solvent, 20 mmol of intermediate 1, 56 mmol of decanoyl chloride (CAS No. 112-13-0), and 56 mmol of triethylamine to a reaction flask, stir and react at 30° C. for 15 h, rotary evaporate the solution, wash with deionized water, add the product to ethanol, then add 48 mmol of sodium borohydride, react for 5 h, concentrate the solution, wash with deionized water, and recrystallize the product in ethanol to obtain intermediate 2, with a yield of 11.89 g, and the structural formula is as follows:

[0029]

[0030] Step (3), add 300 mL of ethanol, 20 mmol of intermediate 2, and 64 mmol of 2,3-epoxypropyltrimethylammonium chloride to a reaction bottle equipped with a condenser reflux tube, react at 70°C for 48 hours, concentrate the solution, wash with acetone, and dry to obtain a long-acting bactericidal surfactant. The yield is 16.15 g, and the structural formula is as follows:

[0031]

[0032] Example 2

[0033] Step (1), add 400 mL of ethanol, 66 mmol of DL-tyrosine, 30 mmol of glutaraldehyde, and 126 mmol of potassium hydroxide to a reaction bottle, react at 70° C. for 6 h, add concentrated hydrochloric acid to acidify the solution to pH 5 after the reaction, rotary evaporate the solution, wash with water, and recrystallize the product in ethanol to obtain intermediate 1 with a yield of 8.38 g.

[0034] Step (2), in an ice-water bath, add 150 mL of tetrahydrofuran solvent, 20 mmol of intermediate 1, 40 mmol of tetradecanoyl chloride (CAS No. 112-64-1), and 40 mmol of triethylamine to a reaction bottle, stir and react at 35°C for 8 h, rotary evaporate the solution, wash with deionized water, add the product to ethanol, then add 48 mmol of sodium borohydride, react for 3 h, concentrate the solution, wash with deionized water, and recrystallize the product in ethanol to obtain intermediate 2. Yield 13.67 g. The structural formula is as follows:

[0035]

[0036] Step (3), add 200 mL of ethanol, 20 mmol of intermediate 2, and 48 mmol of 2,3-epoxypropyltrimethylammonium chloride to a reaction bottle equipped with a condenser reflux tube, react at 80°C for 36 hours, concentrate the solution, wash with acetone, and dry to obtain a long-acting bactericidal surfactant. The yield is 17.49 g, and the structural formula is as follows:

[0037]

[0038] Example 3

[0039] Step (1), add 300 mL of ethanol, 60 mmol of DL-tyrosine, 30 mmol of glutaraldehyde, and 114 mmol of potassium hydroxide to a reaction flask, react at 50 °C for 10 h, add concentrated hydrochloric acid to acidify the solution to pH 5 after the reaction, rotary evaporate the solution, wash with water, and recrystallize the product in ethanol to obtain intermediate 1 with a yield of 7.91 g.

[0040] Step (2), in an ice-water bath, add 150 mL of toluene solvent, 20 mmol of intermediate 1, 48 mmol of hexadecanoyl chloride (CAS No. 112-67-4), and 48 mmol of triethylamine to a reaction bottle, stir and react at 20° C. for 15 h, rotary evaporate the solution, wash with deionized water, add the product to ethanol, then add 48 mmol of sodium borohydride, react for 5 h, concentrate the solution, wash with deionized water, and recrystallize the product in ethanol to obtain intermediate 2. The yield is 13.80 g, and the structural formula is as follows:

[0041]

[0042] Step (3), add 300 mL of ethanol, 20 mmol of intermediate 2, and 56 mmol of 2,3-epoxypropyltrimethylammonium chloride to a reaction bottle equipped with a condenser reflux tube, react at 70°C for 72 hours, concentrate the solution, wash with acetone, and dry to obtain a long-acting bactericidal surfactant. The yield is 18.35 g, and the structural formula is as follows:

[0043]

[0044] Comparative Example 1: Intermediate 2 prepared in Example 1 is used as a surfactant, and its structural formula is

[0045]

[0046] Add the surfactant to the liquid agar culture medium to prepare a surfactant culture solution. Use the liquid culture medium dilution method to dilute the culture solution in sequence to concentrations of 100ug / mL, 50ug / mL, 25ug / mL, 12.5ug / mL, 6.25ug / mL, 3.125ug / mL, 1.563ug / mL, 0.781ug / mL, 0.391ug / mL, and 0.195ug / mL.

[0047] Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Candida albicans were used as test bacteria. 100 mL of activated test bacteria suspension (concentration of 10 6cfu / mL), placed in a surfactant culture medium, and then cultured in a constant temperature incubator at 37°C for 24 hours, and the bacterial growth results were observed after culture. The concentration of the culture medium with sterile growth is the minimum inhibitory concentration (MIC).

[0048] Table 1 Minimum inhibitory concentration test of surfactant

[0049]

[0050]

[0051] The surfactant was added to the liquid agar medium to prepare the surfactant culture solution, which was placed in a test tube and then heat-treated in boiling water at 100°C for 2 hours. After cooling to room temperature, the minimum inhibitory concentration MIC (ug / mL) of the test bacteria was tested.

[0052] Table 2 Minimum inhibitory concentration test of surfactant after heat treatment

[0053]

[0054] The surfactant was added into water to prepare a solution with a mass concentration of 0.2-2 g / L, and the surface tension of the solution was tested using a surface tension tester.

[0055] Table 3 Surface tension test

[0056]

[0057] The long-acting bactericidal surfactant prepared by testing Examples 1-3 contains a diquaternary ammonium salt antibacterial group, which has a strong positive charge and can electrostatically interact with the negatively charged cell membrane of bacteria, so that the surfactant is attached to the cell membrane surface, improves the permeability of the cell membrane, and allows the genetic material such as enzymes in the cell membrane to escape, destroying the normal metabolism and reproduction of bacteria, thereby achieving an excellent bactericidal effect. The minimum inhibitory concentration MIC of the surfactant in Example 2 for Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Candida albicans is only 0.391ug / mL, 0.391ug / mL, 25ug / mL, and 3.125ug / mL. And the long-acting bactericidal surfactant has good heat resistance. After 100°C heat treatment, it still has a very low minimum inhibitory concentration for Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Candida albicans, showing long-acting antibacterial performance.

[0058] The long-acting bactericidal surfactant contains multiple hydrophilic carboxyl groups, quaternary ammonium salts, hydroxyl hydrophilic groups, and hydrophobic phenyl alkyl long chains. It has a strong surface active effect and significantly reduces the surface tension of the solution. When the mass concentration of the long-acting bactericidal surfactant in Example 3 is 0.2-2g / L, the surface tension of the solution is only 58.1-12.0mN / m. The lower the surface tension, the better the wetting, emulsification and dispersibility, which is conducive to the practical application of surfactants in washing powder, laundry liquid, etc.

[0059] The intermediate 2 of comparative example 1 does not have a diquaternary ammonium salt antibacterial group, has no antibacterial effect on bacteria such as Escherichia coli, and has no minimum inhibitory concentration. It also does not contain hydroxyl groups or diquaternary ammonium salt hydrophilic groups, and its solution surface tension and surface activity are lower than those of the examples.

[0060] The above are only preferred embodiments of the present invention and are not intended to limit the present invention in other forms. Any technician familiar with the profession may use the technical contents disclosed above to change or modify them into equivalent embodiments with equivalent changes and apply them to other fields. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A long-acting bactericidal surfactant, characterized in that: The structural formula of the long-acting bactericidal surfactant is shown in formula (I): In formula (I), n is any integer between 9 and 15.

2. A method for preparing the long-acting bactericidal surfactant according to claim 1, wherein the preparation method is as follows: Step (1), add ethanol, DL-tyrosine, glutaraldehyde, and potassium hydroxide to a reaction flask, add concentrated hydrochloric acid to acidify after the reaction, rotary evaporate the solution, wash with water, and recrystallize the product in ethanol to obtain intermediate 1; the structural formula is ； Step (2), in an ice-water bath, add a solvent, intermediate 1, an alkyl acyl chloride compound, and triethylamine to a reaction flask, stir, react at 20-35° C. for 8-15 hours, rotary evaporate the solution, wash with deionized water, add the product to ethanol, then add sodium borohydride, react for 3-5 hours, concentrate the solution, wash with deionized water, and recrystallize the product in ethanol to obtain intermediate 2; the structural formula is: , n is any integer between 9 and 15; Step (3), adding ethanol and the intermediate 2,2,3-epoxypropyltrimethylammonium chloride to a reaction bottle equipped with a condenser reflux tube, concentrating the solution after the reaction, washing with acetone, and drying to obtain a long-acting bactericidal surfactant.

3. The method for preparing a long-acting bactericidal surfactant according to claim 2, wherein in step (1), the molar ratio of DL-tyrosine to glutaraldehyde is (2-2.2):1:(3.8-4.2).

4. The method for preparing a long-acting bactericidal surfactant according to claim 2, wherein in step (1), the reaction temperature is 50-70°C and the reaction time is 6-12 hours.

5. The method for preparing a long-acting bactericidal surfactant according to claim 2, wherein in step (2), the solvent is dichloromethane, toluene or tetrahydrofuran.

6. The method for preparing a long-acting bactericidal surfactant according to claim 2, wherein in step (2), the molar ratio of the intermediate 1, the alkyl acyl chloride compound, and triethylamine is 1:(2-2.6):(2-2.6).

7. The method for preparing a long-acting bactericidal surfactant according to claim 6, wherein the structural formula of the alkyl acyl chloride compound is: , n is any integer between 9 and 15.

8. The method for preparing a long-acting bactericidal surfactant according to claim 2, wherein in step (3), the molar ratio of the intermediate 2 to 2,3-epoxypropyltrimethylammonium chloride is 1:(2.4-3.2).

9. The method for preparing a long-acting bactericidal surfactant according to claim 2, wherein in step (3), the reaction temperature is 70-80°C and the reaction time is 36-72h.

10. Use of the long-acting bactericidal surfactant obtained by the preparation method according to any one of claims 2 to 9 in antibacterial laundry detergent.

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