Strong toilet cleaner capable of removing bacteria and odor and preparation method of powerful toilet cleaner

Abstract

The invention relates to the technical field of daily chemical products, and discloses a strong toilet cleaner for removing bacteria and odor and a preparation method thereof, the strong toilet cleaner comprises 3.8-6.5 parts by weight of a surfactant, 2.5-6 parts by weight of a cyclodextrin-based bacteria and odor removing agent, 4.6-6.8 parts by weight of an organic acid, 0.8-1.3 parts by weight of a chelating agent, and 0.3-0.8 part by weight of a thickening agent; the cyclodextrin-based degerming deodorant contains quaternary ammonium salt cation antibacterial groups and can form electrostatic interaction with cell membrane surfaces of bacteria and fungi, so that the cell membranes are destroyed, growth and reproduction of the bacteria and fungi are inhibited, and the cyclodextrin-based degerming deodorant shows very strong degerming and sterilizing performance. And the beta-cyclodextrin has a cavity structure, has specific inclusion and adsorption effects on ammonia, hydrogen sulfide, skatole and other substances and gas molecules, and can achieve a good deodorization effect.

Description

Technical Field

[0001] The present invention relates to the technical field of daily chemical products, in particular to a strong toilet cleaning liquid for sterilization and deodorization and a preparation method thereof. Background Art

[0002] In daily life, toilets, often lacking timely and effective cleaning, can emit foul odors and easily breed bacteria and fungi. This has led to the emergence of cleaning products such as toilet cleaners. Traditional toilet cleaners incorporate cationic surfactants such as cetyltrimethylammonium chloride, which offer effective bactericidal properties. However, these cationic surfactants are not readily biodegradable. Therefore, the development of bio-based antimicrobial agents is a hot topic.

[0003] β-cyclodextrin is a cyclic oligosaccharide that is inexpensive, readily available, biodegradable, and environmentally friendly. It also has a hydrophobic internal cavity structure that allows it to incorporate various substances, making it widely used in adsorbents, deodorants, and surfactants. Chinese patent CN109481713B discloses a liquid deodorant and its preparation method, combining β-cyclodextrin, malic acid, citric acid, and a polyoxyethylene nonionic surfactant to form a liquid deodorant with excellent deodorizing and antibacterial properties. However, conventional β-cyclodextrin has poor water solubility and lacks good antibacterial properties, significantly limiting its practical application in toilet cleaning solutions. Summary of the Invention

[0004] The invention solves the problem of poor water solubility and antibacterial performance of cyclodextrin, and at the same time gives the toilet cleaning liquid excellent deodorizing and antibacterial performance.

[0005] The technical solution of the present invention is a strong toilet cleaning liquid for debacterial and deodorizing and a preparation method thereof, comprising 3.8-6.5 parts by weight of a surfactant, 2.5-6 parts by weight of a cyclodextrin-based debacterial and deodorizing agent, 4.6-6.8 parts by weight of an organic acid, 0.8-1.3 parts by weight of a chelating agent, and 0.3-0.8 parts by weight of a thickener.

[0006] Furthermore, the preparation method includes: adding a surfactant, a cyclodextrin-based deodorizing agent, an organic acid, a chelating agent, and a thickener to water, stirring and mixing, and obtaining a strong toilet cleaning liquid with deodorizing and deodorizing properties.

[0007] Furthermore, the surfactant includes any one or a combination of fatty alcohol polyoxyethylene ether AEO-7, fatty alcohol polyoxyethylene ether AEO-9, fatty alcohol polyoxyethylene ether sodium sulfate AES, nonylphenol polyoxyethylene ether TX-10, and alkyl polyglycoside APG0810.

[0008] Furthermore, the thickener includes carboxymethyl cellulose, xanthan gum or polyvinyl alcohol.

[0009] Furthermore, the organic acid includes any one or a combination of maleic acid, citric acid, oxalic acid, and aminosulfonic acid.

[0010] Furthermore, the chelating agent is disodium ethylenediaminetetraacetic acid or trisodium nitrilotriacetic acid.

[0011] Furthermore, the preparation method of the cyclodextrin-based sterilizing and deodorizing agent includes:

[0012] (1) Add β-cyclodextrin, 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine to N,N-dimethylformamide, stir for reaction, and then distill under reduced pressure. The mixture is washed with water and acetone, and dried to obtain a cyclodextrin precursor.

[0013] (2) Adding a cyclodextrin precursor and an alkyl bromide compound to N,N-dimethylformamide, stirring for reaction, and then distilling under reduced pressure, washing with ethanol, and drying to obtain a cyclodextrin quaternary ammonium salt.

[0014] (3) Add cyclodextrin quaternary ammonium salt, thioglycolic acid, and benzoin dimethyl ether to N,N-dimethylformamide, irradiate under ultraviolet light for reaction, distill under reduced pressure, wash with ethanol, and dry to obtain a cyclodextrin-based sterilizing and deodorizing agent. The reaction formula is:

[0015]

[0016] Furthermore, in (1), the amount of β-cyclodextrin is 100 parts by weight, 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid is 16-26 parts by weight, dicyclohexylcarbodiimide is 18-30 parts by weight, and 4-dimethylaminopyridine is 1.2-2 parts by weight.

[0017] Furthermore, the reaction temperature in (1) is 25-40°C, and the reaction time is 18-24h.

[0018] Furthermore, the amount of the cyclodextrin precursor in (2) is 100 parts by weight, and the amount of the alkyl bromide compound is 20-42 parts by weight; the structural formula of the alkyl bromide compound is Br-C n H 2n+1 , n is 10-16.

[0019] Furthermore, the reaction temperature in (2) is 100-120° C., and the reaction time is 24-48 h.

[0020] Furthermore, in (3), the amount of cyclodextrin quaternary ammonium salt is 100 parts by weight, the amount of thioglycolic acid is 7-12 parts by weight, and the amount of benzoin dimethyl ether is 0.4-0.7 parts by weight.

[0021] Furthermore, the power of the UV lamp in (3) is 600-1000W, the central wavelength is 365nm, and the irradiation reaction time is 1-2h.

[0022] The beneficial technical effects of the present invention are as follows: 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid is subjected to an esterification reaction with β-cyclodextrin, followed by a quaternization reaction with an alkyl bromide compound and a thiol-ene click reaction with thioglycolic acid to obtain a cyclodextrin-based antibacterial and deodorizing agent, which contains a hydrophilic carboxyl group, has good water solubility, and can be configured into a clear and transparent toilet cleaning liquid.

[0023] The present invention combines surfactants such as fatty alcohol polyoxyethylene ether, cyclodextrin-based antibacterial and deodorizing agents, organic acids such as citric acid, chelating agents such as disodium ethylenediaminetetraacetic acid, and carboxymethyl cellulose as thickeners to obtain a strong toilet cleaning liquid with antibacterial and deodorizing properties. The cyclodextrin-based antibacterial and deodorizing agent contains quaternary ammonium salt cationic antibacterial groups, which can form electrostatic interactions with the cell membrane surface of bacteria and fungi, thereby destroying the cell membrane and inhibiting the growth and reproduction of bacteria and fungi, showing strong bactericidal and sterilization properties.

[0024] The β-cyclodextrin in the cyclodextrin-based antibacterial and deodorizing agent of this invention has a cavity structure, which allows it to specifically incorporate and adsorb various substances and gas molecules, such as ammonia, hydrogen sulfide, and skatole, providing excellent deodorizing and odor removal effects. As an oligopolysaccharide, β-cyclodextrin is biodegradable, making it more environmentally friendly. DETAILED DESCRIPTION

[0025] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts should fall within the scope of protection of the present invention.

[0026] The preparation method of 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid is as follows: 3.98g of maleic anhydride is added to 10mL of toluene, 4.06g of 3-dimethylamino-1-propanol (structural formula: ), heated to 90 ° C, stirred for 5 hours, filtered, and the filtrate was distilled under reduced pressure. The product was recrystallized from methanol to obtain 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid, with the structural formula

[0027] Example 1:

[0028] (1) Add 5 g of β-cyclodextrin, 0.8 g of 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid, 0.9 g of dicyclohexylcarbodiimide, and 0.06 g of 4-dimethylaminopyridine to 40 mL of N,N-dimethylformamide, stir and react at 30°C for 18 h, evaporate under reduced pressure, wash with water and acetone, and dry to obtain a cyclodextrin precursor.

[0029] (2) Add 5 g of cyclodextrin precursor and 1 g of 1-bromodecane to 80 mL of N,N-dimethylformamide, heat to 120°C, stir and react for 24 h, distill under reduced pressure, wash with ethanol, and dry to obtain cyclodextrin quaternary ammonium salt.

[0030] (3) Add 20 g of cyclodextrin quaternary ammonium salt, 1.4 g of thioglycolic acid, and 0.04 g of benzoin dimethyl ether to 250 mL of N,N-dimethylformamide, irradiate under an ultraviolet lamp with a power of 800 W and a central wavelength of 365 nm for 1 h, distill under reduced pressure, wash with ethanol, and dry to obtain a cyclodextrin-based antibacterial and deodorizing agent.

[0031] (4) Add 31 g of fatty alcohol polyoxyethylene ether AEO-7, 9 g of nonylphenol polyoxyethylene ether TX-10, 8 g of alkyl glycoside APG0810, 25 g of cyclodextrin-based antibacterial and deodorizing agent, 51 g of citric acid, 17 g of oxalic acid, 9 g of chelating agent disodium ethylenediaminetetraacetic acid, and 8 g of thickener carboxymethyl cellulose to 842 mL of deionized water, stir and mix to obtain a strong toilet cleaning liquid with antibacterial and deodorizing properties.

[0032] Example 2:

[0033] (1) To 50 mL of N,N-dimethylformamide, 5 g of β-cyclodextrin, 1 g of 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid, 1.2 g of dicyclohexylcarbodiimide, and 0.08 g of 4-dimethylaminopyridine were added. The mixture was stirred at 25°C for 24 h, and then evaporated under reduced pressure. The mixture was washed with water and acetone, and dried to obtain a cyclodextrin precursor.

[0034] (2) Add 5 g of cyclodextrin precursor and 1.7 g of 1-bromohexadecane to 100 mL of N,N-dimethylformamide, heat to 100 °C, stir and react for 48 h, distill under reduced pressure, wash with ethanol, and dry to obtain cyclodextrin quaternary ammonium salt.

[0035] (3) Add 20 g of cyclodextrin quaternary ammonium salt, 1.9 g of thioglycolic acid, and 0.058 g of benzoin dimethyl ether to 300 mL of N,N-dimethylformamide, irradiate under ultraviolet light with a power of 600 W and a central wavelength of 365 nm for 2 h, distill under reduced pressure, wash with ethanol, and dry to obtain a cyclodextrin-based sterilization and deodorization agent.

[0036] (4) Add 30 g of fatty alcohol polyoxyethylene ether AEO-9, 5 g of nonylphenol polyoxyethylene ether TX-10, 3 g of alkyl glycoside APG0810, 40 g of cyclodextrin-based antibacterial and deodorizing agent, 51 g of citric acid, 8 g of maleic acid, 13 g of chelating agent trisodium salt of nitrilotriacetate, and 5 g of thickener polyvinyl alcohol to 845 mL of deionized water, stir and mix to obtain a strong toilet cleaning liquid with antibacterial and deodorizing properties.

[0037] Example 3:

[0038] (1) To 50 mL of N,N-dimethylformamide, 5 g of β-cyclodextrin, 1.3 g of 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid, 1.5 g of dicyclohexylcarbodiimide, and 0.1 g of 4-dimethylaminopyridine were added. The mixture was stirred at 40°C for 18 h, and then evaporated under reduced pressure. The mixture was washed with water and acetone, and dried to obtain a cyclodextrin precursor.

[0039] (2) Add 5 g of cyclodextrin precursor and 2.1 g of 1-bromododecane to 110 mL of N,N-dimethylformamide, heat to 120°C, stir and react for 36 h, distill under reduced pressure, wash with ethanol, and dry to obtain cyclodextrin quaternary ammonium salt.

[0040] (3) Add 20 g of cyclodextrin quaternary ammonium salt, 2.4 g of thioglycolic acid, and 0.07 g of benzoin dimethyl ether to 300 mL of N,N-dimethylformamide, irradiate under ultraviolet light with a power of 1000 W and a central wavelength of 365 nm for 1 h, distill under reduced pressure, wash with ethanol, and dry to obtain a cyclodextrin-based antibacterial and deodorizing agent.

[0041] (4) Add 45 g of sodium fatty alcohol polyoxyethylene ether sulfate AES, 12 g of nonylphenol polyoxyethylene ether TX-10, 8 g of alkyl glycoside APG0810, 60 g of cyclodextrin-based antibacterial and deodorizing agent, 42 g of citric acid, 4 g of aminosulfonic acid, 8 g of chelating agent disodium ethylenediaminetetraacetic acid, and 3 g of thickener xanthan gum to 818 mL of deionized water, stir and mix to obtain a strong toilet cleaning liquid with antibacterial and deodorizing properties.

[0042] Comparative Example 1:

[0043] (1) Add 31 g of fatty alcohol polyoxyethylene ether AEO-7, 9 g of nonylphenol polyoxyethylene ether TX-10, 8 g of alkyl glycoside APG0810, 51 g of citric acid, 17 g of oxalic acid, 9 g of chelating agent disodium ethylenediaminetetraacetic acid, and 8 g of thickener carboxymethyl cellulose to 842 mL of deionized water, stir and mix to obtain a toilet cleaning liquid.

[0044] Comparative Example 2:

[0045] (1) Add 31 g of fatty alcohol polyoxyethylene ether AEO-7, 9 g of nonylphenol polyoxyethylene ether TX-10, 8 g of alkyl glycoside APG0810, 25 g of β-cyclodextrin, 51 g of citric acid, 17 g of oxalic acid, 9 g of chelating agent disodium ethylenediaminetetraacetic acid, and 8 g of thickener carboxymethyl cellulose to 842 mL of deionized water, stir and mix to obtain a toilet cleaning liquid.

[0046] Comparative Example 3:

[0047] (1) To 842 mL of deionized water, 31 g of fatty alcohol polyoxyethylene ether AEO-7, 9 g of nonylphenol polyoxyethylene ether TX-10, 8 g of alkyl glycoside APG0810, 25 g of cyclodextrin precursor (prepared in Example 1), 51 g of citric acid, 17 g of oxalic acid, 9 g of chelating agent disodium ethylenediaminetetraacetic acid, and 8 g of thickener carboxymethyl cellulose were added and stirred to obtain a toilet cleaning liquid.

[0048] Comparative Example 4:

[0049] (1) To 842 mL of deionized water, 31 g of fatty alcohol polyoxyethylene ether AEO-7, 9 g of nonylphenol polyoxyethylene ether TX-10, 8 g of alkyl glycoside APG0810, 25 g of cyclodextrin quaternary ammonium salt (prepared in Example 1), 51 g of citric acid, 17 g of oxalic acid, 9 g of chelating agent disodium ethylenediaminetetraacetic acid, and 8 g of thickener carboxymethyl cellulose were added and stirred to obtain a toilet cleaning liquid.

[0050] To 1 L of deionized water, cyclodextrin-based sterilizing and deodorizing agents (prepared respectively by Examples 1-3), β-cyclodextrin (Comparative Example 2), cyclodextrin precursor (Comparative Example 3), and cyclodextrin quaternary ammonium salt (Comparative Example 3) were added, respectively, and stirred for 30 minutes to prepare a cyclodextrin aqueous solution. The mixture was placed at room temperature for 48 hours and the state of the solution was observed.

[0051] Place the toilet cleaning liquid at room temperature for 48 hours and observe the status of the toilet cleaning liquid.

[0052] Table 1 Toilet cleaning liquid status test

[0053] Cyclodextrin aqueous solution state Toilet cleaning liquid status Example 1 Clear and transparent, no sediment Clear and transparent, no sediment Example 2 Clear and transparent, no sediment Clear and transparent, no sediment Example 3 Clear and transparent, no sediment Clear and transparent, no sediment Comparative Example 1 - Clear and transparent, no sediment Comparative Example 2 There is obvious sediment There is obvious sediment Comparative Example 3 There is obvious sediment There is obvious sediment Comparative Example 4 The solution is turbid with suspended matter The solution is turbid with suspended matter

[0054] Testing revealed that aqueous solutions and toilet cleaning liquids formulated with the cyclodextrin-based antibacterial and deodorizing agents prepared in Examples 1-3 were clear and transparent, with no precipitate. This is primarily because the cyclodextrin-based antibacterial and deodorizing agents contain hydrophilic carboxyl groups, significantly improving the water solubility and dispersibility of β-cyclodextrin. The β-cyclodextrin, cyclodextrin precursor, and cyclodextrin quaternary ammonium salt prepared in Comparative Examples 2-4 lack hydrophilic carboxyl groups and exhibit poor water solubility, resulting in suspended matter and precipitate in the resulting toilet cleaning liquids.

[0055] The antibacterial properties of toilet cleaning liquids were tested according to the method in GB 15979-2002. Bactericidal rate = (AB) / A × 100%. A is the average colony count of the control sample (the toilet cleaning liquid in Comparative Example 1); B is the average colony count of the test sample. The test strains were Candida albicans ATCC 10231, Escherichia coli ATCC 25922, and Staphylococcus aureus ATC 6538.

[0056] Table 2 Antibacterial performance test of toilet cleaning liquid

[0057]

[0058]

[0059] After testing, the toilet cleaning liquids of Examples 1-3 were added with cyclodextrin-based antibacterial and deodorizing agents, which contained quaternary ammonium salt cationic antibacterial groups, which could form electrostatic interactions with the cell membrane surfaces of bacteria and fungi, thereby destroying the cell membranes and inhibiting the growth of bacteria and fungi, showing strong bactericidal and sterilization properties.

[0060] The β-cyclodextrin and cyclodextrin precursor added in Comparative Examples 2 and 3 do not contain quaternary ammonium salt cationic antibacterial groups, and their antibacterial properties are very poor.

[0061] The cyclodextrin quaternary ammonium salt in Comparative Example 4 has very poor solubility, which makes it difficult for the cyclodextrin quaternary ammonium salt to be completely dissolved in the toilet cleaning liquid. The antibacterial agent has poor dispersibility and it is difficult to completely and effectively expose the antibacterial sites, resulting in the sterilization rate of the toilet cleaning liquid being lower than that of the various embodiments.

[0062] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A strong toilet cleaning liquid for sterilization and deodorization, characterized in that: The strong toilet cleaning liquid for sterilization and deodorization comprises 3.8-6.5 parts by weight of a surfactant, 2.5-6 parts by weight of a cyclodextrin-based sterilization and deodorization agent, 4.6-6.8 parts by weight of an organic acid, 0.8-1.3 parts by weight of a chelating agent, and 0.3-0.8 parts by weight of a thickener; The preparation method of the cyclodextrin-based sterilizing and deodorizing agent comprises: (1) adding β-cyclodextrin, 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine to N,N-dimethylformamide, stirring for reaction, and then distilling under reduced pressure, washing, and drying to obtain a cyclodextrin precursor; (2) adding a cyclodextrin precursor and an alkyl bromide compound to N,N-dimethylformamide, stirring for reaction, and then distilling under reduced pressure, washing, and drying to obtain a cyclodextrin quaternary ammonium salt; (3) Add cyclodextrin quaternary ammonium salt, thioglycolic acid, and benzoin dimethyl ether to N,N-dimethylformamide, irradiate under ultraviolet light for reaction, distill under reduced pressure, wash, and dry to obtain a cyclodextrin-based sterilizing and deodorizing agent.

2. The strong toilet cleaning liquid for sterilization and deodorization according to claim 1, characterized in that: The amount of β-cyclodextrin in (1) is 100 parts by weight, 4-[3-(dimethylamino)propoxy]-4-oxobut-2-enoic acid is 16-26 parts by weight, dicyclohexylcarbodiimide is 18-30 parts by weight, and 4-dimethylaminopyridine is 1.2-2 parts by weight; the reaction temperature is 25-40° C., and the reaction time is 18-24 hours.

3. The strong toilet cleaning liquid for sterilization and deodorization according to claim 1, characterized in that: The amount of the cyclodextrin precursor in (2) is 100 parts by weight, and the amount of the alkyl bromide compound is 20-42 parts by weight; the structural formula of the alkyl bromide compound is Br-C n H 2n+1 , n is any integer from 10 to 16; the reaction temperature is 100-120° C., and the reaction time is 24-48 h.

4. The strong toilet cleaning liquid for sterilization and deodorization according to claim 1, characterized in that: The amount of cyclodextrin quaternary ammonium salt in (3) is 100 parts by weight, thioglycolic acid is 7-12 parts by weight, and benzoin dimethyl ether is 0.4-0.7 parts by weight; the power of the ultraviolet lamp is 600-1000W, the central wavelength is 365nm, and the irradiation reaction time is 1-2h.

5. The strong toilet cleaning liquid for sterilization and deodorization according to claim 1, characterized in that: The surfactant includes any one or a combination of fatty alcohol polyoxyethylene ether AEO-7, fatty alcohol polyoxyethylene ether AEO-9, fatty alcohol polyoxyethylene ether sodium sulfate AES, nonylphenol polyoxyethylene ether TX-10, and alkyl polyglycoside APG0810.

6. The strong toilet cleaning liquid for sterilization and deodorization according to claim 1, characterized in that: The thickener includes carboxymethyl cellulose, xanthan gum or polyvinyl alcohol.

7. The strong toilet cleaning liquid for sterilization and deodorization according to claim 1, characterized in that: The organic acid includes any one or a combination of maleic acid, citric acid, oxalic acid, and aminosulfonic acid.

8. The strong toilet cleaning liquid for sterilization and deodorization according to claim 1, characterized in that: The chelating agent is disodium ethylenediaminetetraacetic acid or trisodium nitrilotriacetic acid.

9. A method for preparing a strong toilet cleaning liquid for sterilization and deodorization according to any one of claims 1 to 8, characterized in that: The preparation method comprises: adding a surfactant, a cyclodextrin-based sterilizing and deodorizing agent, an organic acid, a chelating agent, and a thickener into water, stirring and mixing the mixture to obtain a strong toilet cleaning liquid capable of sterilizing and deodorizing.

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