CN114208819A

CN114208819A - Iodine-containing disinfectant containing acetonitrile and having stable component content and preparation method thereof

Info

Publication number: CN114208819A
Application number: CN202111356809.4A
Authority: CN
Inventors: 赵一阳; 王振兴; 刘肖娟; 黎剑坤; 谭志坚; 符德文; 袁增辉
Original assignee: Foshan Standard Bio Tech Co Ltd
Current assignee: Foshan Standard Bio Tech Co Ltd
Priority date: 2021-11-16
Filing date: 2021-11-16
Publication date: 2022-03-22
Anticipated expiration: 2041-11-16
Also published as: CN114208819B

Abstract

The invention discloses an iodine-containing disinfectant containing acetonitrile and having stable components and a preparation method thereof. The iodine-containing disinfectant comprises the following components in percentage by weight: 20-99.5% of acetonitrile, 0.1-20% of elementary iodine, 0.1-15% of iodide, 0.1-60% of carboxylic acid and 0-70% of water. The disinfectant uses acetonitrile or acetonitrile and water as solvents, each component has good stability, and can be disinfected by various forms of environments. The disinfectant is prepared by mixing iodine simple substance, iodide, carboxylic acid, acetonitrile or acetonitrile and water. The preparation method is simple.

Description

Iodine-containing disinfectant containing acetonitrile and having stable component content and preparation method thereof

Technical Field

The invention belongs to the field of disinfectants, and particularly relates to an iodine-containing disinfectant containing acetonitrile and having stable content, and a preparation method and application thereof.

Background

Iodine disinfectants are widely used in various aspects of industrial production and daily life. In order to further improve the disinfecting performance of iodine-containing disinfectants, acids are usually added thereto. For example, inorganic acids: sulfuric acid, iodic acid mixed solution of phosphoric acid (containing complex iodine, phosphoric acid, sulfuric acid, etc.). For example: organic acid: citric acid, salicylic acid, and the like. The acidic condition has a promoting effect on the disinfection effect. The use of alcohol as solvent is also a common means, such as ethanol, glycerol, etc., because the alcohol solvent can greatly improve the stability of iodine (for example, iodine tincture is an iodine preparation using ethanol as main solvent, the water content is small, water is generally used only for dissolving potassium iodide, the stability of iodine tincture is generally good, the iodine content is not changed greatly when the iodine tincture is placed at normal temperature, and the reference can be specifically made to the literature, Zhaojianxin, 2% iodine tincture content stability observation [ J]Chinese medicine, 2004,11(3): 380-381). However, the iodine-containing disinfectant system containing carboxylic acid and alcohol has the problem of unstable carboxylic acid content. The instability of iodine-containing disinfectants is related to the property of iodine simple substance to react easily. To stabilize elemental iodine, an iodide such as potassium iodide, sodium iodide, etc. is generally added because of the formation of I₃ ^-The stability of iodine can be obviously improved; the instability of the iodine in the system is also related to the reaction property of carboxylic acid in a water-containing system, and generally, the iodine in the system with less water content has better stability; the increase of the water content can increase the instability of the iodine simple substance, and the condition is more obvious particularly in the presence of carboxylic acid such as citric acid and the like. The instability of iodine-containing disinfectant components increases the pressure on production, stocking, storage and transportation.

According to previous researches of the inventor of the application, the existence of carboxylic acid such as citric acid and acetic acid in an iodine-containing disinfectant system can cause the fluctuation of the quality of iodine, and the reduction of water content is an effective means for improving the fluctuation of the quality of iodine, so that in order to obtain higher stability of the iodine, the water content is reduced while alcohol solvents commonly used for disinfectants such as ethanol (such as ethanol which is a common solvent for iodine tincture), glycerol (glycerol which is a common solvent for iodine glycerol) and the like are increased. Although the increase of alcohol solvents such as ethanol and glycerol brings the beneficial result of stabilizing the content of iodine, the decrease of the content of carboxylic acid is caused because the carboxylic acid and the alcohol solvent are esterified in the presence of iodine according to the previous research results (see, for example, chinese patent publication No. CN112704080A (application No. 202011611608.X), chinese patent publication No. CN112640913A (application No. 202011613375.7), chinese patent publication No. CN112806387A (application No. 202011634817.6), etc.). In the presence of iodine, carboxylic acid reacts with alcohol to generate ester substances, thereby affecting the stability of the content of carboxylic acid, for example, the document K.Ramalinga, P.Vijayalakshmi, T.N.B.Kaimo.A. mil and effective method for esterification and transestification catalyzed by iodine [ J ] Tetrahedron Letters,2002,43: 879-. The inventor of the application detects that the components such as the citric acid glyceride and the like can appear in the product after the iodine-containing disinfectant containing citric acid, glycerin, iodine, potassium iodide and water is placed for a long time (even at room temperature). The nuclear magnetic and mass spectral data are shown in fig. 1 and fig. 2, respectively. The iodine-containing disinfectant with the initial composition of acetic acid, ethanol, iodine simple substance, potassium iodide and water can generate ethyl acetate, and the generation of the ethyl acetate can be confirmed even through simple olfaction.

According to the previous research results of the inventor, the solution for solving the problem of the reduction of the carboxylic acid content is to add ester substances in equilibrium with acid, alcohol and water in the system or obtain an equilibrium composition of acid, alcohol, water and ester in equilibrium with each other through self esterification reaction, thereby obtaining a system with stable acid content (determined by acid-base titration) and iodine content. However, these methods generally require esterification reaction, which requires a long time to reach equilibrium (like long-term storage of iodine-containing disinfectant at room temperature for a long time to stabilize and generate a certain amount of esters), or at a higher temperature, which requires increasing reaction temperature and heating equipment, and in the heating process, iodine simple substance volatilizes at high temperature to generate corrosive and acid substances, which also increases production cost and brings higher requirements for safety control of production. Therefore, it is necessary to directly prepare iodine-containing disinfectants containing carboxylic acid, iodine simple substances, iodide and other substances with higher stability at normal temperature.

Disclosure of Invention

Aiming at the problem of unstable component content of iodine-containing disinfectants containing carboxylic acid and alcohol in the prior art, in particular to the problem of unstable carboxylic acid content in the system, the invention aims to provide the iodine-containing disinfectants containing acetonitrile and having stable component content, and the disinfectants have good component stability, do not need to be heated in the preparation process and can be mixed at normal temperature.

The invention adopts the following technical scheme to realize the purpose:

an iodine-containing disinfectant containing acetonitrile in a stable content, comprising the following components:

20-99.5% of acetonitrile, 0.1-20% of elementary iodine, 0.1-15% of iodide, 0.1-60% of carboxylic acid and 0-70% of water.

More preferably, the iodine-containing disinfectant comprises the following components in percentage by weight:

25-95% of acetonitrile, 0.1-20% of elementary iodine, 0.1-15% of iodide, 0.1-60% of carboxylic acid and 1-50% of water.

30-90% of acetonitrile, 0.2-15% of elementary iodine, 0.2-15% of iodide, 0.1-30% of carboxylic acid and 5-35% of water.

35-85% of acetonitrile, 0.5-10% of iodine elementary substance, 0.3-10% of iodide, 0.5-30% of carboxylic acid and 10-30% of water.

More preferably, the mass content of acetonitrile in the iodine-containing disinfectant is more than 40%.

More preferably, the mass content of acetonitrile in the iodine-containing disinfectant is more than 50%.

More preferably, the mass content of acetonitrile in the iodine-containing disinfectant is more than 70%.

Preferably, the carboxylic acid is selected from citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentanedioic acid, 1,3, 5-cyclohexanetricarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid, malic acid, gallic acid, tartaric acid, p-toluenesulfonic acid or mixtures thereof; further preferred is one or more of formic acid, acetic acid, propionic acid, citric acid, salicylic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid, and 1,3, 5-cyclohexanetricarboxylic acid.

More preferably, the carboxylic acid is selected from one or more of acetic acid, propionic acid, citric acid and salicylic acid.

Preferably, the iodide is selected from one or more of hydrogen iodide, lithium iodide, potassium iodide, sodium iodide, strontium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide or a quaternary ammonium iodide salt, a diquaternary ammonium iodide salt, a triquaternary ammonium iodide salt, a polyquaternary ammonium iodide salt and a hyperbranched quaternary ammonium iodide salt.

Preferably, the above-mentioned mono-quaternary ammonium iodide salt is selected from one or more of cetyltrimethylammonium iodide, tetradecyltrimethylammonium iodide, dodecyltrimethylammonium iodide, decyltrimethylammonium iodide, benzyltrimethylammonium iodide and tetrabutylammonium iodide.

Preferably, the iodide is selected from potassium iodide and/or sodium iodide and/or ammonium iodide.

The compositions of the present invention allow for small amounts of possible reaction products including the above-described compositions.

In another aspect, the invention provides a method for preparing the iodine-containing disinfectant with stable acetonitrile-containing component content, and the method is implemented by mixing the components together according to the principle of easy dissolution.

Preferably, the above preparation method comprises the steps of:

(1) dissolving iodide with water and/or acetonitrile, adding iodine elementary substance into the solution to dissolve,

(2) dissolving carboxylic acid with water and/or acetonitrile, mixing with the iodide and iodine-containing solution,

(3) adding the rest water and/or acetonitrile, and uniformly mixing;

preferably, the above preparation method comprises the steps of:

the preparation method comprises the following steps:

(1) dissolving iodide in water, adding iodine into the solution to dissolve,

(3) adding the rest water and/or acetonitrile, and uniformly mixing;

in still another aspect, the present invention provides a method for using the iodine-containing disinfectant, which comprises applying or spraying the iodine-containing disinfectant directly on or soaking the object to be disinfected for disinfection, or performing a disinfection operation by diluting with water or a solvent in a certain ratio (for example, 50 to 1000 times).

In the invention, acetonitrile is used as a solvent, does not react with carboxylic acid in the iodine-containing disinfectant, does not influence the contents of iodine simple substance and potassium iodide in the disinfectant, and has stable component content.

The iodine-containing disinfectant with stable acetonitrile component content is stored for two years conventionally, the iodine simple substance content is changed to 0.02-0.1, and the carboxylic acid content is basically unchanged.

Drawings

Fig. 1 is a nuclear magnetic spectrum of an iodine-containing disinfectant containing citric acid, glycerin, elemental iodine, potassium iodide and water after being left at room temperature for a long period of time (about 1 year and half). From this spectrum it can be seen that glycerol and monoglycerides of citric acid are present in the product. Glycerol: 3.46ppm, 3.52ppm, 3.66 ppm. Citric acid monoglyceride: 2.72ppm, 2.81ppm, 2.98ppm, 3.85ppm, 4.04ppm, 4.11 ppm.

Fig. 2 is a mass spectrum of an iodine-containing disinfectant containing citric acid, glycerin, iodine, potassium iodide and water after being left at room temperature for a long period of time (about 1 year and half). From the spectrum, it can be seen that glycerin (91 is its characteristic peak), iodine (127 is its characteristic peak), citric acid monoglyceride (265 is its characteristic peak), citric acid (191 is its characteristic peak), citric acid diglyceride (339 is its characteristic peak), and citric acid triglyceride (413 is its characteristic peak) are present in the product.

Detailed Description

For the inventor of the present application, previous research inventions thereof are as follows: after the disinfectant formula containing carboxylic acid, alcohol, iodine, iodide and water is placed at room temperature, the content of the carboxylic acid is reduced, and detection finds that an esterification product of the carboxylic acid and the alcohol is generated, and the formation of the esterification product is accelerated along with the increase of the temperature, so that the carboxylic acid and alcohol component containing disinfectant formula is an important reason for destroying the stability of the iodine containing disinfectant. The inventor continuously researches the iodine-containing disinfectant, and finds that the iodine-containing disinfectant with better stability can be obtained by replacing alcohol with a solvent which does not react with carboxylic acid and does not influence the contents of iodine simple substance and potassium iodide in the disinfectant. Through a large number of experiments, the inventor finds that acetonitrile has the required ideal properties and excellent property of infinite mutual solubility with water, and can be used for iodine-containing disinfectants to prepare stable formula compositions. The iodine disinfectant formulation of the present invention is such that there is a reaction of iodine and water to form iodide, iodate and hydrogen ions and the inventors have found that this reaction is reversible and that this equilibrium reaction can be expressed as

(or

). When the balance is finally achieved, the elementary iodine (possibly the elementary iodine and the iodide ion form combined combination), the iodide ion, the iodic acid and/or iodate ion, water and hydrogen ion (acid) in the system reach a certain balance, so that the whole system can be stable. This content is also described in chinese patent publication No. CN112806387A (application No. 2020116348176), which is incorporated herein by reference. Alternatively, there may be a reaction in which iodide ions are oxidized to form elemental iodine, but the above reaction degree is generally low as a whole.

Acetonitrile is relatively less toxic than other nitrile solvents and its oral LD to rats₅₀2460mg/kg is, which is far less toxic than 40mg/kg for propionitrile and 50mg/kg for butyronitrile; LD of acetonitrile oral dosage form toxicity than n-propanol₅₀: 1870mg/kg (per rat) is also low and far less toxic than phenol (LD)₅₀: 317mg/kg per rat), but much less than the toxicity of glutaraldehyde, a commonly used environmental disinfectant (rat oral: LD₅₀: 252mg/kg), and is also much less toxic than some common disinfectants, preservatives, etc. (benzalkonium chloride (i.e. alkylbenzyldimethylammonium chloride) administered orally to rats: LD₅₀: 1420 mg/kg; oral administration of benzoic acid to rats: LD₅₀: 1700 mg/kg; benzyl alcohol oral administration to rats: LD₅₀: 1230 mg/kg; ). The disinfectant containing acetonitrile can be used for instrument disinfection and environment disinfection, and particularly for disinfection of livestock and poultry houses. It is generally considered that acetonitrile in water is unstable and can be hydrolyzed into acetic acid and ammonia or to form amide or carboxylic acid, but according to the research of the inventor, if the system uses amide such as N, N-dimethylformamide or urea, etc., the stability of the system is obviously affected, but the stability of the system components using acetonitrile is strong, so that it is inferred that the above reaction does not occur in the disinfectant system and the disinfectant system is stable in the system. The present invention has been completed on the basis of the above-mentioned studies.

In order to exert the effect of acetonitrile in stabilizing the content of each component of the iodine-containing disinfectant, it is advantageous that the content of acetonitrile in the system is slightly larger, because according to earlier studies, the stability of the iodine content gradually deteriorates as the water content increases, and therefore, the reduction of the water content is advantageous for the stabilization of iodine, and because acetonitrile has the characteristic of not significantly reacting with acids such as citric acid, the amount of water required in the formulation for maintaining the system stable is smaller, and accordingly, the amount of acetonitrile can be correspondingly larger. In the disinfectant, the proportion of acetonitrile in the solvent is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. The solvent herein refers to a medium for dissolving iodine, iodide, acid, etc., which are effective ingredients of the iodine-containing disinfectant, and generally refers to acetonitrile and/or water herein. An increase in the acetonitrile content means a decrease in the content of other solvents, including other solvents other than water and acetonitrile, and if the other solvents have an adverse effect on the system stability, an increase in the acetonitrile content can reduce the adverse effect of the other solvents on the system stability.

In order to make the iodine-containing disinfectant simpler to formulate and more stable, it is preferred that the proportion of acetonitrile in the solvent is greater than 70%, more preferably greater than 80%, most preferably the solvent is acetonitrile alone (i.e. free of water).

To further enhance the disinfecting effect of iodine-containing disinfectants, an acid is generally added thereto. Although sulfuric acid and phosphoric acid are also commonly used in iodine-containing disinfectants to further enhance the disinfection effect of iodine-containing disinfectants, such as iodic acid mixed solution (Shuiteng)^TM30) and the product has stable content of iodine elementary substance and the like under the strong acid environment, and the disinfectant has strong disinfection effect because the system contains complex iodine and is stable per se, but has the problem of strong irritation. In the present invention, an organic acid is preferably added, and a carboxylic acid is more preferably used as the organic acid. Carboxylic acids include, but are not limited to, citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentanedioic acid, 1,3, 5-cyclohexanetrioic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid, malic acid, gallic acid, tartaric acid, p-toluenesulfonic acid. The acidic environment provided by the carboxylic acid in the invention can effectively improve the disinfection effect, and the relatively mild property of the carboxylic acid is less irritant than inorganic acids such as sulfuric acid, phosphoric acid and the like. Experiments show that under the condition of the invention, the contents of iodine, acid and the like are stable, and the components of the composition using acetonitrile as a solvent are stable.

The iodine is added into the iodine-containing disinfectant, so that on one hand, the iodine-containing disinfectant is used as a cosolvent of iodine simple substances, the dissolution of the iodine simple substances is promoted, and the preparation process is convenient; on the other hand, the iodine stabilizer has the function of stabilizing iodine simple substance. The reason why the iodide can stabilize the elementary iodine may be related to the complex reaction of iodine, and may be related to the generation I between the elementary iodine and iodide ions₃ ^-Plasma series of ions, it is also possibleAssociated with the disproportionation of iodine to produce iodide and iodate ions; or it is also possible that the iodide ion is involved in the redox reaction with an oxidizing agent (e.g., air, oxygen) or the like, or in a complicated combined action involving the above-mentioned processes, but in any case, the addition of a certain amount of iodide is effective for the stabilization of the reaction system.

The iodide used in the present invention includes, but is not limited to, lithium iodide, potassium iodide, sodium iodide, strontium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide or a quaternary ammonium iodide salt, a diquaternary ammonium iodide salt, a triquaternary ammonium iodide salt, a polyquaternary ammonium iodide salt or a hyperbranched quaternary ammonium iodide salt or a mixture thereof. The above monoquaternary ammonium iodide salts include, but are not limited to, hexadecyltrimethylammonium iodide, tetradecyltrimethylammonium iodide, dodecyltrimethylammonium iodide, decyltrimethylammonium iodide, benzyltrimethylammonium iodide, tetrabutylammonium iodide. The monoquaternary ammonium iodide salt herein refers to an iodide consisting of a monoquaternary ammonium radical ion and an iodide ion, and a diquaternary ammonium iodide salt, a triquaternary ammonium iodide salt, a polyquaternary ammonium iodide salt or a hyperbranched quaternary ammonium iodide salt has a similar definition.

In the present invention, the weight ratio of the iodide in the system is preferably 0 to 15%, more preferably 0.1 to 15%. If the iodide in the system is 0% (i.e., no iodide), then preferably the water content of the system is 0% (0% means no water). The mole number of the iodine is preferably selected according to the addition amount of the iodine: the molar ratio of the iodide is 1: 0.5-1: 5; further optimized to be 1:1-1: 4. The stability of iodine simple substance and iodide ion in the range is relatively higher, which is beneficial to the stability of components. The reason why the iodine compound stabilizes the iodine-containing disinfectant system may be counteracted by the reaction of iodine ions with oxygen, light and the like to generate iodine simple substance and the reduction of iodine simple substance caused by the action of iodine simple substance and water, thereby stabilizing the iodine content in the iodine-containing disinfectant.

In a preferred embodiment of the invention, the iodine containing disinfectant with a stable content of acetonitrile containing components comprises the components (in weight percent): 35-85% of acetonitrile, 0.5-10% of elementary iodine, 0.5-10% of iodide, 1-30% of carboxylic acid and 2-50% of water. In another preferred embodiment of the invention, the iodine containing disinfectant having a stable content of acetonitrile containing components comprises the components: 35-85% of acetonitrile, 0.5-10% of elementary iodine, 0.5-10% of iodide, 2-30% of carboxylic acid and 5-30% of water. In another preferred embodiment of the invention, the iodine containing disinfectant having a stable content of acetonitrile containing components comprises the components: 45-75% of acetonitrile, 0.5-10% of elementary iodine, 0.5-10% of iodide, 2-25% of carboxylic acid and 5-30% of water. In another preferred embodiment of the invention, the iodine containing disinfectant having a stable content of acetonitrile containing components comprises the components: 55-70% of acetonitrile, 0.5-7% of elementary iodine, 0.5-7% of iodide, 5-20% of carboxylic acid and 5-30% of water.

The preparation process of the iodine-containing disinfectant does not need specific heating operation and is carried out at normal temperature and normal pressure.

The iodine-containing disinfectant of the present invention can be prepared into a solution by generally using the principle that materials are easy to dissolve each other, and then mixing the solution. For the iodine disinfectant system containing iodide and water, the iodide can be dissolved in water, the iodine simple substance is dissolved in the iodide solution, the acid is dissolved in the water or acetonitrile, the feed liquid is mixed, and finally the residual solvent is supplemented to the specified amount. For the dissolution of iodide, a mixed solution of water and acetonitrile or acetonitrile alone may be used. For systems that do not contain water, it is possible to dissolve with acetonitrile only; for systems that do not contain iodide, acetonitrile may be used to dissolve the elemental iodine.

The invention has good stability, in an accelerated experiment, the content of carboxylic acid measured by an acid-base titration method is changed by less than 10 percent after the thermal storage is carried out for 8h 10 days at 80 ℃, and the quality requirement of two years can be met.

The iodine-containing disinfectant can be directly prepared at normal temperature, does not need heating operation or heating equipment, is more convenient to operate, does not need a complex and accurately set feeding sequence and process, has consistent component content of disinfectant products in different batches, and is suitable for industrial mass production. The iodine disinfectant has stable components, relatively stable contents of elemental iodine and carboxylic acid after long-term storage (at least two years), and relatively stable disinfection and sterilization effects.

In the description of the present invention, "plural" means two or more.

The invention will be further illustrated with reference to the following specific examples. The specific embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and an operation process are given. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions. Unless otherwise indicated, ratios and percentages are by weight.

The detection methods of elemental iodine, acid, iodide in the following examples are as follows:

elemental iodine: the product is precisely measured and weighed with 10ml, and is placed in an iodine bottle and titrated by sodium thiosulfate titration solution (0.1mol/L) until the solution is colorless. The elemental iodine content was calculated as follows: na (Na)₂S₂O₃+I₂＝Na₂S₄O₆+₂NaI. If the acid is poorly soluble in water, a suitable amount of ethanol may be added prior to titration.

Carboxylic acid: the acid amount of the system determined by acid-base titration (calculated for a particular carboxylic acid indicated, if a plurality of acids are present) is specifically: and (3) adding phenolphthalein indicator solution into the solution with the iodine content measured, titrating with sodium hydroxide titration solution (1mol/L) until the color of the system turns pink, and calculating the content of carboxylic acid.

Iodide: precisely measuring 10ml of the product, weighing, placing in an iodine bottle, adding 10ml of water, adding 20ml of hydrochloric acid, titrating to yellow by using potassium iodate titration solution (0.05mol/L), adding 5ml of trichloromethane, continuing to titrate, and simultaneously strongly shaking until the purple red of the trichloromethane layer disappears to indicate an end point. And removing the content of the elementary iodine to obtain the content of iodide. If precipitation occurs due to problems of acid solubility during titration, an appropriate amount of ethanol may be added prior to titration to increase the solubility. The calculation based on the potassium iodide content is not particularly specified.

And (3) stability testing:

the stability tests in the following examples were carried out by means of accelerated tests. The method specifically comprises the following steps: and (2) sealing the disinfectant in a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature drying box, starting timing, heating to 80 ℃ within 2 hours, starting counting the heat preservation time after the temperature is raised to 80 ℃, preserving the heat for 8 hours, stopping heating, naturally cooling to room temperature, taking a period of 24 hours from the start of timing, and then continuously repeating the process for 10 cycles. The contents of elemental iodine and carboxylic acid were measured by sampling before accelerated test (referred to as 0 day) and after circulation (referred to as 3,5 and 10 days) on day 3,5 and 10, respectively. Based on previous findings one cycle (1 day) of iodine-containing disinfectant in this test corresponds approximately to 2.5 months of storage at room temperature and 10 cycles corresponds approximately to 2 years.

Example 1:

1.1 composition of disinfectant containing carboxylic acid and iodine using acetonitrile as solvent:

10g of iodine simple substance, 8.0g of potassium iodide, 75g of water, 50g of citric acid and acetonitrile to 500mL (about 330 g).

1.2 the preparation method of the iodine-containing disinfectant comprises the following steps:

dissolving 8.0g of potassium iodide in 8.0g of water, and then adding 10g of elemental iodine to dissolve the potassium iodide to obtain a1 liquid; weighing the residual 67g of water, adding 50g of citric acid to dissolve the residual 67g of water, then adding 100g of acetonitrile, and uniformly mixing to obtain a b1 solution; and then adding the solution a1 into the solution b1, uniformly stirring, then adding the rest acetonitrile, and uniformly stirring to obtain 500mL of feed liquid.

The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 1 below.

Comparative examples 1 to 1

The composition of the disinfectant containing carboxylic acid and iodine by using ethanol as a solvent comprises the following components:

10g of iodine simple substance, 8.0g of potassium iodide, 75g of water, 50g of citric acid and ethanol for constant volume, and 500mL of the total solution is prepared.

The preparation method of the iodine-containing disinfectant comprises the following steps:

dissolving 8.0g of potassium iodide in 8.0g of water, and then adding 10g of elemental iodine to dissolve to obtain a 11; weighing the residual 67g of water, adding 50g of citric acid to dissolve the water, and then adding 100g of ethanol to obtain b 11; then a11 is added into b11, the mixture is stirred evenly, and then the rest ethanol is added to 500mL and mixed evenly.

TABLE 1 stability test results of iodine-containing disinfectants prepared in example 1 and comparative examples 1-1

From the results, the content of carboxylic acid in example 1 is not changed basically, which is different from the acid content in comparative example 1, and shows that acetonitrile can obviously play a role in stabilizing the content of carboxylic acid, thereby providing a foundation for the stability of the whole disinfectant. In example 1, under the water content of 15%, the contents of elemental iodine and potassium iodide are relatively stable, and the changes are similar to those in comparative example 1, namely the contents of elemental iodine and iodide ions are slightly changed, which further illustrates that the reaction of ethanol and citric acid is the main reason for influencing the acid content; the ethanol and the acetonitrile have similar effects on iodine simple substance and potassium iodide, and the content change of the iodine simple substance and the potassium iodide is not considered to be influenced basically. The relationship between the content change of the iodine simple substance and the potassium iodide and the water content in the system is larger. For the iodine element, in a system with 15% of water, the detection result shows that the iodine content slightly rises, which appears in systems using different solvents, and the result is considered to be related to the conversion of iodine ions to the direction of the iodine element when the water is less. When the amount of water is large, the iodine tends to decrease.

Either example 1 or comparative example 1 can be mixed with water in any proportion.

Example 2:

2.1 composition of disinfectant containing carboxylic acid and iodine using acetonitrile as solvent:

10g of iodine simple substance, 8.0g of potassium iodide, 150g of water, 50g of citric acid and acetonitrile to a constant volume of 500 mL.

2.2 the preparation method of the iodine-containing disinfectant comprises the following steps:

dissolving 8.0g of potassium iodide in 8.0g of water, and then adding 10g of elemental iodine to dissolve the potassium iodide to obtain a2 liquid; weighing the residual 142g of water and 100g of acetonitrile, mixing, adding 50g of citric acid to dissolve, and uniformly mixing to obtain a b2 solution; and then adding the solution a2 into the solution b2, uniformly stirring, then adding the rest acetonitrile, and uniformly stirring to obtain 500mL of feed liquid.

The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 2 below.

TABLE 2 stability test results for iodine-containing disinfectants prepared in example 2

Similar to the stability test result of example 1, the stability of the content of carboxylic acid can be maintained by using acetonitrile as a solvent, and in a system with a large amount of water, the content of iodine is reduced and the content of potassium iodide is increased. This result is close to the trend of elemental iodine, decrease in iodine content and results when ethanol was used as a solvent with the same amount of water, indicating that the change in iodine content is mainly related to the amount of water, while the acid content is likely to maintain higher stability because acetonitrile cannot react with it.

Example 3:

3.1 composition of disinfectant containing carboxylic acid and iodine using acetonitrile as solvent:

10g of iodine simple substance, 8.0g of potassium iodide, 250g of water, 50g of citric acid and acetonitrile to a constant volume of 500 mL.

3.2 the preparation method of the iodine-containing disinfectant comprises the following steps:

dissolving 8.0g of potassium iodide in 8.0g of water, and then adding 10g of elemental iodine to dissolve the potassium iodide to obtain a3 liquid; weighing the residual 242g of water and 100g of acetonitrile, mixing, adding 50g of citric acid to dissolve, and uniformly mixing to obtain a b3 solution; and then adding the solution a3 into the solution b3, uniformly stirring, then adding the rest acetonitrile, and uniformly stirring to obtain 500mL of feed liquid.

The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 3 below.

TABLE 3 stability test results for iodine-containing disinfectants prepared in example 3

Disinfectant	Acceleration time/day	Iodine simple substance/%)	Potassium iodide/%)	Carboxylic acid/%)
					Example 3	0	1.96	1.60	9.97
	3	1.84	1.77	9.99
						5	1.74	1.90	10.23
	10	1.70	1.93	10.35

The stability test results are similar to those of examples 1 and 2, and acetonitrile as a solvent can maintain the content of carboxylic acid stable. With the increase of the water content, the iodine simple substance content is reduced, and the potassium iodide content is increased. But for acetonitrile as solvent, no reduction in acid content is caused.

Example 4:

4.1 composition of disinfectant containing carboxylic acid and iodine using acetonitrile as solvent:

10g of iodine simple substance, 15.0g of ammonium iodide, 100g of water, 100g of acetic acid and acetonitrile to a constant volume of 500 mL.

4.2 the preparation method of the iodine-containing disinfectant comprises the following steps:

dissolving 15g of ammonium iodide in 15g of water, and then adding 10g of elemental iodine to dissolve the ammonium iodide to obtain a4 liquid; weighing 85g of water, 50g of acetonitrile and 100g of acetic acid, and uniformly mixing to obtain a b4 liquid; and then adding the solution a4 into the solution b4, uniformly stirring, then adding the rest acetonitrile, and uniformly stirring to obtain 500mL of feed liquid.

The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 4 below.

TABLE 4 stability test results for iodine-containing disinfectants prepared in example 4

Disinfectant	Acceleration time/day	Iodine simple substance/%)	Ammonium iodide/%)	Carboxylic acid/%)
					Example 4	0	2.02	3.07	19.95
	3	2.01	3.07	19.97
						5	2.02	3.06	19.95
	10	2.03	3.07	19.93

The stability test results were similar to those of examples 1 and 2, but showed better stability. The reason for this is that although the water content of the system of comparative example 4 is intermediate between those of examples 1 and 2, the iodine content can be made to be in a more stable range; on the other hand, since the iodine content tends to be slightly increased with a large amount of ammonium iodide, the total iodine content and the ammonium iodide content are slightly changed. On the other hand, acetonitrile stabilizes the carboxylic acid content and thus exhibits very stable properties.

Example 5:

5.1 composition of disinfectant containing carboxylic acid and iodine using acetonitrile as solvent:

15g of iodine simple substance, 30g of sodium iodide, 100g of water, 150g of propionic acid and acetonitrile to a constant volume of 500 mL.

5.2 the preparation method of the iodine-containing disinfectant comprises the following steps:

dissolving 30g of sodium iodide in 40g of water, and then adding 15g of elemental iodine to dissolve the sodium iodide to obtain a5 solution; weighing 60g of water, 100g of acetonitrile and 150g of propionic acid, and uniformly mixing to obtain a b5 liquid; and then adding the solution a5 into the solution b5, uniformly stirring, then adding the rest acetonitrile, and uniformly stirring to obtain 500mL of feed liquid.

The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 5 below.

TABLE 5 stability test results for iodine-containing disinfectants prepared in example 5

Disinfectant	Acceleration time/day	Iodine simple substance/%)	Sodium iodide/%)	Carboxylic acid/%)
					Example 5	0	3.01	5.99	29.87
	3	3.02	5.98	29.89
						5	3.03	5.98	30.00
	10	3.03	5.97	29.96

The stability test result shows that the iodine simple substance, the iodide and the carboxylic acid of the system can be kept in a very stable state under the system.

The values of the carboxylic acid contents in examples 1 to 5 above are mostly shown to be slightly increased because the carboxylic acid contents measured in these examples were determined by acid-base titration, because the system contained water, and the presence of the above-mentioned elemental iodine reacted with water to form iodide ions, iodate ions, and hydrogen ions, wherein the hydrogen ions resulted in the actually measured H⁺An increase, manifested as an increase in carboxylic acid content. From the standpoint of the reaction principle, these examplesThe disinfectant system of (a) is free of substances that react with carboxylic acids, the content of carboxylic acids theoretically being unchanged. In the process of measuring the content of carboxylic acid by actual acid-base titration, the slightly increased amount of the content of carboxylic acid reacts with H generated by the reaction of iodine simple substance and water in the iodine-containing disinfectant⁺The amount is proportional. For example, in examples 1, 4 and 5 having a relatively low water content, the measured H was determined because the reaction of elemental iodine with water produced relatively few hydrogen ions⁺Less, as indicated by less variation in carboxylic acid content, in examples 2 and 3, which contained more water, H was measured due to more hydrogen ions generated by the reaction of iodine and water⁺More, as indicated by the higher carboxylic acid content. The carboxylic acid content of these systems is virtually unchanged. The method for measuring the disinfection and sterilization effects of the iodine-containing disinfectant formula specifically refers to the method described in the invention patent publication No. CN101803611A (application No. CN201010163683.4, the name of the invention is citric acid iodine disinfectant and a preparation method thereof).

The citric acid iodine disinfectant of the embodiment of the invention has the following sterilization effect:

the experimental results show that: diluting stock solution of disinfectant at 20 deg.C according to iodine content measured during preparation or before hot storage (0 day), wherein the effective iodine content after dilution is 100mg/L, the diluent acts on Escherichia coli and Staphylococcus aureus for 3min, and the sterilization logarithm value is not less than 5.0; diluting stock solution of the disinfectant according to iodine content measured in preparation (0 day) and effective iodine content of 500mg/L after dilution, wherein the diluted solution acts on black variant spores of bacillus subtilis for 5min, and the sterilization logarithm value is more than or equal to 5.0. And the samples after 10 cycles of heat storage are diluted according to the dilution times in 0 day, and the disinfection and sterilization effects of the samples are almost the same as those of newly prepared samples (0 day).

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.

Claims

1. An iodine-containing disinfectant containing acetonitrile and having stable component content, which is characterized by comprising the following components in percentage by weight:

2. The iodine disinfectant containing stable acetonitrile components of claim 1 wherein said iodine disinfectant contains the following components in weight percent:

35-85% of acetonitrile, 0.5-10% of iodine elementary substance, 0.3-10% of iodide, 0.5-30% of carboxylic acid and 1-50% of water.

3. The iodine disinfectant containing stable acetonitrile component of claims 1 or 2 wherein the water is present in an amount of 5-30% by weight.

4. The iodine-containing disinfectant containing stable amounts of acetonitrile containing components according to claim 1 or 2, wherein said carboxylic acid is selected from the group consisting of citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid, 1,3, 5-cyclohexanetricarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid, malic acid, gallic acid, tartaric acid, p-toluenesulfonic acid or mixtures thereof; further preferred is one or more of formic acid, acetic acid, propionic acid, citric acid, salicylic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid, and 1,3, 5-cyclohexanetricarboxylic acid.

5. Iodine-containing disinfectant with a stable content of acetonitrile components according to claim 1 or 2, wherein said iodide is selected from one or more of the group consisting of hydrogen iodide, lithium iodide, potassium iodide, sodium iodide, strontium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide or mono-quaternary ammonium iodide, bis-quaternary ammonium iodide, tris-quaternary ammonium iodide, poly-quaternary ammonium iodide and hyperbranched quaternary ammonium iodide.

6. Iodine-containing disinfectant with a stable content of acetonitrile components according to claim 5, wherein said mono-quaternary ammonium iodide salt is selected from one or more of the group consisting of cetyl trimethyl ammonium iodide, tetradecyl trimethyl ammonium iodide, dodecyl trimethyl ammonium iodide, decyl trimethyl ammonium iodide, benzyl trimethyl ammonium iodide and tetrabutyl ammonium iodide.

7. The method for preparing iodine disinfectant containing stable amount of acetonitrile containing component according to claims 1-6 wherein the method is characterized by mixing the components together according to the principle of easy dissolution.

8. The method of preparing iodine disinfectant containing stable amounts of acetonitrile containing components of claim 7 wherein said method comprises the steps of:

(3) adding the rest water and/or acetonitrile, and mixing uniformly.

9. The method of preparing iodine disinfectant containing stable amounts of acetonitrile containing components of claim 7 wherein said method comprises the steps of:

(1) dissolving iodide in water, adding iodine into the solution to dissolve,

(3) adding the rest water and/or acetonitrile, and mixing uniformly.

10. The iodine-containing disinfectant containing stable acetonitrile components of claims 1-6, which is stored for two years conventionally, the content of iodine simple substance is changed to 0.02-0.1, and the content of carboxylic acid is basically unchanged.