CN113383775B - Compound quaternary ammonium salt low-temperature disinfectant and preparation method thereof - Google Patents
Compound quaternary ammonium salt low-temperature disinfectant and preparation method thereof Download PDFInfo
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
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- A01N33/12—Quaternary ammonium compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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Abstract
The invention discloses a compound quaternary ammonium salt low-temperature disinfectant, which comprises a quaternary ammonium salt mixture, an antifreezing agent and water, wherein the quaternary ammonium salt mixture is a mixture of single-chain quaternary ammonium salt, double-chain quaternary ammonium salt and heterocyclic quaternary ammonium salt. The sterilization effect can be greatly improved through the coordination of the heterocyclic quaternary ammonium salt and the single-chain and double-chain quaternary ammonium salt. The bactericide is a quaternary ammonium salt compound, has no corrosiveness and no pungent smell, does not cause negative influence on operators and environment, and can be used for disinfection at-40 ℃ and above. The application also provides a preparation method of the compound quaternary ammonium salt low-temperature disinfectant.
Description
Technical Field
The invention relates to the technical field of chemical disinfectants, in particular to a compound quaternary ammonium salt low-temperature disinfectant and a preparation method thereof.
Background
In the field of disinfection, most researches mainly focus on the disinfection effect of disinfectants under normal temperature or high temperature, and concern is given to disinfection in low-temperature environment, and corresponding low-temperature disinfection products are few.
Patent CN112450220a discloses a disinfection material for low temperature environment and a preparation method thereof, wherein the disinfection material is chlorine-containing chemical substances, and the solvent is diethyl ether, acetone, DMF, carbon tetrachloride and the like. The known Zhou Hanlv disinfectant is relatively high in corrosiveness and smell in the use process, so that certain trouble is brought to operators; the solvents used in the patent have larger toxicity, can bring certain influence to the health of operators in the use process, and can cause certain hidden trouble to the food safety when being used for disinfecting the food cold chain ring.
Therefore, it is necessary to provide a low-temperature disinfectant of compound quaternary ammonium salt and a preparation method thereof to solve the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to provide a compound quaternary ammonium salt low-temperature disinfectant, wherein the disinfectant is a quaternary ammonium salt compound, the product has no corrosiveness and pungent smell, does not cause negative influence on operators and the environment, and can be used for disinfection at-40 ℃ and above.
The invention provides a compound quaternary ammonium salt low-temperature disinfectant, which comprises a quaternary ammonium salt mixture, an antifreezing agent and water, wherein the quaternary ammonium salt mixture is a mixture of single-chain quaternary ammonium salt, double-chain quaternary ammonium salt and heterocyclic quaternary ammonium salt.
Compared with the prior art, the compound quaternary ammonium salt low-temperature disinfectant comprises a quaternary ammonium salt mixture, an antifreezing agent and water, and the antifreezing agent is introduced to endow the disinfectant with the function of disinfecting at the low temperature of minus 40 ℃; the cell surface of bacteria often carries negative charges, the traditional disinfection mode only adopts single-chain and double-chain compound quaternary ammonium salt for disinfection, surfactant ions generated when the quaternary ammonium salt ionizes in aqueous solution carry positive charges and can interact with the surface of bacterial cell membranes carrying negative charges so as to achieve the aim of sterilization, and the technical scheme of the invention adopts the single-chain, double-chain and heterocyclic quaternary ammonium salt compound to play a synergistic effect on the sterilization effect of the single-chain, double-chain and heterocyclic quaternary ammonium salt, thereby greatly improving the sterilization effect. The double-chain quaternary ammonium salt contains two long-chain hydrophobic groups and two positively charged N in the structure + Through induction, the positive charge density of quaternary nitrogen is increased, and the adsorption capacity of disinfectant on the surface of bacteria is increased, so that the permeability of the membrane is changed, and the thalli are broken. In addition, the disinfectant contains two hydrophobic groups, so that the disinfectant is more beneficial to entering a lipoid layer and a protein layer of a bacterial cell, and related enzymes in bacteria are inactivated, so that the protein is denatured. The heterocyclic quaternary ammonium salt contains N atom in molecular structure, which makes it easy to form hydrogen bond with anion, enzyme, DNA and RNA in organismHas bactericidal effect. Therefore, the sterilization effect can be greatly improved through the coordination of the heterocyclic quaternary ammonium salt and the single-chain and double-chain quaternary ammonium salt.
Preferably, the single-chain quaternary ammonium salt is at least one selected from benzalkonium chloride and benzalkonium bromide.
Preferably, the double-chain quaternary ammonium salt is at least one selected from didecyl dimethyl ammonium bromide, didecyl dimethyl ammonium chloride and dioctyl/decyl dimethyl ammonium chloride. Preferably, bis-octyl/decyl dimethyl ammonium chloride is used.
Preferably, the heterocyclic quaternary ammonium salt is a quaternary ammonium salt containing pyridine, triazole or imidazole in a molecular structure.
Preferably, the heterocyclic quaternary ammonium salt is at least one of cetylpyridinium chloride, dodecylethylpyridine bromide, imidazolinium oleate and imidazolinium chloride 1-hydroxyethyl-2-cycloalkyl-3-benzyl-2-imidazolinium chloride.
Preferably, the compound quaternary ammonium salt low-temperature disinfectant comprises the following components in percentage by mass:
wherein the content of the quaternary ammonium salt mixture can be, but is not limited to, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%; the content of the synergist can be, but is not limited to, 0.6%, 1%, 1.4%, 1.8%, 2.2%, 2.6%, 3%; the content of the antifreeze may be, but is not limited to, 20%, 25%, 30%, 35%, 40%; the content of the thickener may be, but is not limited to, 0.2%, 0.4%, 0.6%, 0.8%, 1%; the balance being water, 100% in total.
Preferably, the synergist is hexamethylenetetramine, and the quaternary ammonium salt and the hexamethylenetetramine are compounded, so that the hexamethylenetetramine has a synergistic effect on the sterilization effect of the quaternary ammonium salt under a certain compounding proportion. Further, the compounding ratio of the quaternary ammonium salt mixture and the synergistic agent is 1:3-1:6.
Preferably, the antifreezing agent is a compound of an organic solvent and inorganic salt. The addition amount of the organic solvent and the inorganic salt is reduced through the combination of the organic solvent and the inorganic salt, so that the dangerous situation caused by the organic solvent in the production, transportation and use processes of the product is avoided; the addition of the organic solvent can effectively reduce the viscosity of the finished product, and simultaneously avoid the negative influence on the environment caused by the large amount of inorganic salt. Preferably, the organic solvent adopts an alcohol solvent, and the alcohol solvent can play a synergistic role in sterilizing the quaternary ammonium salt. Wherein, the alcohol solvent can be but is not limited to ethanol and propylene glycol. The inorganic salt may be, but is not limited to, sodium chloride, calcium chloride. More preferably, the antifreeze is a mixture of ethanol, propylene glycol, sodium chloride, and calcium chloride.
Preferably, the thickener is at least one of tallow alkyl bishydroxyethyl amine oxide, dodecyl bishydroxyethyl amine oxide and coco alkyl bishydroxyethyl amine oxide. It should be understood that the present technical solution adopts a thickener as a nonionic type, and the main disinfection function of the disinfectant is a quaternary ammonium salt mixture, the quaternary ammonium salt is a cation, and the nonionic and the cation are used for compounding, and the nonionic surfactant molecules are "inserted" between the polar head groups of the ionic surfactant by means of the hydrophobic function and the interaction between the polar head groups, so that the repulsive force between the original cationic surfactant ion head groups is weakened, the charge density is reduced, the mixed surfactant is easier to form a micelle in the solution, and the bactericidal effect of the cation is synergistic, so that the bactericidal effect of the quaternary ammonium salt mixture can be greatly promoted.
Correspondingly, the application also provides a preparation method of the compound quaternary ammonium salt low-temperature disinfectant, which comprises the following steps:
and uniformly stirring the quaternary ammonium salt mixture, the antifreezing agent and water to obtain the compound quaternary ammonium salt low-temperature disinfectant.
Preferably, when the disinfectant contains a synergist and a thickener, the preparation method comprises the following steps:
and uniformly stirring the quaternary ammonium salt mixture, the antifreezing agent, the synergist, the thickener and the water to obtain the compound quaternary ammonium salt low-temperature disinfectant.
Preferably, when the antifreeze is a complex of an organic solvent and an inorganic salt, the preparation method thereof comprises:
dissolving inorganic salt in water, adding an organic solvent, stirring uniformly, sequentially adding a quaternary ammonium salt mixture, a synergistic agent and a thickening agent, stirring uniformly, and finally supplementing the rest water.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a compound quaternary ammonium salt low-temperature disinfectant comprises the following steps:
dissolving 15g of calcium chloride in water, filtering, adding 10g of ethanol into the solution, and uniformly stirring the solution; then 0.2g of benzalkonium chloride, 0.3g of didecyl dimethyl ammonium bromide, 0.2g of oleic acid imidazoline quaternary ammonium salt, 0.8g of hexamethylenetetramine and 0.2g of tallow alkyl bishydroxyethyl amine oxide are added into the mixture in turn, and the mixture is stirred and dissolved uniformly, and the balance of water is added.
Example 2
A preparation method of a compound quaternary ammonium salt low-temperature disinfectant comprises the following steps:
dissolving 20g of calcium chloride in water, filtering, adding 10g of ethanol and 5g of propylene glycol into the solution, and uniformly stirring the solution; then 0.35g of benzalkonium chloride, 0.1g of didecyl dimethyl ammonium bromide, 0.05g of bromodecaalkyl ethyl pyridine, 1.8g of hexamethylenetetramine and 0.3g of dodecyl dihydroxyethyl amine oxide are added into the mixture in turn, and the mixture is stirred and dissolved uniformly, and the balance of water is added.
Example 3
A preparation method of a compound quaternary ammonium salt low-temperature disinfectant comprises the following steps:
15g of calcium chloride is dissolved in water, filtered, and then 0.2g of benzalkonium chloride, 0.3g of didecyl dimethyl ammonium bromide, 0.2g of imidazoline quaternary ammonium oleate, 0.8g of hexamethylenetetramine and 0.2g of tallow alkyl bishydroxyethyl amine oxide are sequentially added into the mixture, and the mixture is stirred and dissolved uniformly, so that the balance of water is supplemented.
Comparative example 1
A preparation method of a compound quaternary ammonium salt low-temperature disinfectant comprises the following steps:
dissolving 15g of calcium chloride in water, filtering, adding 10g of ethanol into the solution, and uniformly stirring the solution; then 0.7g of benzalkonium chloride, 0.8g of hexamethylenetetramine and 0.2g of tallow alkyl bis-hydroxyethyl amine oxide are added into the mixture in turn, and the mixture is stirred and dissolved uniformly, and the balance of water is added.
Comparative example 2
A preparation method of a compound quaternary ammonium salt low-temperature disinfectant comprises the following steps:
dissolving 15g of calcium chloride in water, filtering, adding 10g of ethanol into the solution, and uniformly stirring the solution; then 0.2g of benzalkonium chloride, 0.5g of didecyl dimethyl ammonium bromide, 0.8g of hexamethylenetetramine and 0.2g of tallow alkyl bishydroxyethyl amine oxide are added into the mixture in turn, and the mixture is stirred and dissolved uniformly, and the balance of water is added.
Comparative example 3
A preparation method of a compound quaternary ammonium salt low-temperature disinfectant comprises the following steps:
dissolving 15g of calcium chloride in water, filtering, adding 10g of ethanol into the solution, and uniformly stirring the solution; then 0.2g of benzalkonium chloride, 0.3g of didecyl dimethyl ammonium bromide, 0.2g of oleic acid imidazoline quaternary ammonium salt and 0.2g of tallow alkyl bishydroxyethyl amine oxide are added into the mixture in turn, and the mixture is stirred and dissolved uniformly, and the balance of water is added.
The compound quaternary ammonium salt low-temperature disinfectants of examples 1-3 and comparative examples 1-3 were subjected to performance tests, the items and methods of which are as follows:
(1) Low temperature test
According to the requirements of the national health Committee office on the notice of the technical requirement of the evaluation of the health safety of the printed low-temperature disinfectant, 5ml of the low-temperature disinfectant is taken and placed at the corresponding low temperature overnight (> 8 h) at the temperature of-20 ℃ or-40 ℃, and the properties are observed and recorded, referring to Table 1.
(2) Sterilization experiment
According to the method of the 'Notification of the national health Committee office on the requirements of the evaluation technology of the health safety of the printed low-temperature disinfectant' of the 'disinfection technical Specification' (2002 edition). The concentration of the active ingredients is the stock solution, the active time is 15min, and refer to Table 2.
TABLE 1 Low temperature test results
| Test group | Status of |
| Example 1 | The sample is liquid, has no precipitation and no crystallization |
| Example 2 | The sample is liquid, has no precipitation and no crystallization |
| Example 3 | The sample is liquid, has no precipitation and no crystallization |
| Comparative example 1 | The sample is liquid, has no precipitation and no crystallization |
| Comparative example 2 | The sample is liquid, has no precipitation and no crystallization |
| Comparative example 3 | The sample is liquid, has no precipitation and no crystallization |
TABLE 2 Sterilization test results
Note that: positive control colony count/(cfu/sheet): staphylococcus aureus 3.48 x 106; coli 3.38X106.
The experimental results in tables 1-2 show that the compound quaternary ammonium salt low-temperature disinfectant is quite stable in low-temperature conditions, free of precipitation and crystallization, particularly capable of achieving excellent sterilization effect at low temperature of-40 ℃, strong in low-temperature adaptability and good in sterilization effect.
As is clear from comparison between example 1 and example 3, when the alcohol solvent is contained in the antifreeze, the bactericidal effect of the quaternary ammonium salt can be enhanced.
As is clear from comparison of example 1 and comparative examples 1-2, the sterilizing effect is reduced when the quaternary ammonium salt mixture lacks the heterocyclic quaternary ammonium salt, which means that the heterocyclic quaternary ammonium salt and the single-chain and double-chain quaternary ammonium salt are compounded to have a synergistic effect, and the sterilizing effect can be greatly improved by adding the heterocyclic quaternary ammonium salt
As is clear from comparison between example 1 and comparative example 3, when hexamethylenetetramine is not contained in the disinfectant, the sterilization effect is significantly reduced.
The foregoing description of the preferred embodiments of the present invention is not intended to limit the scope of the claims, which follow, as defined in the claims.
Claims (2)
1. The compound quaternary ammonium salt low-temperature disinfectant is characterized by comprising the following components in percentage by mass:
2. a method for preparing the compound quaternary ammonium salt low-temperature disinfectant as set forth in claim 1, comprising the steps of:
dissolving calcium chloride in water, filtering, adding ethanol, and stirring; and then sequentially adding benzalkonium chloride, didecyl dimethyl ammonium bromide, imidazoline quaternary ammonium oleate, hexamethylenetetramine and butter alkyl bishydroxyethyl amine oxide into the mixture, stirring the mixture to dissolve the mixture uniformly, and supplementing the balance of water.
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| CN115606592A (en) * | 2022-10-31 | 2023-01-17 | 大连理工大学 | Low-temperature quaternary ammonium salt disinfectant and application thereof |
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| CN115943954A (en) * | 2023-03-10 | 2023-04-11 | 广州市拓瑞科技有限公司 | Halogen-free composite cationic low-temperature disinfectant and preparation method thereof |
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