阅读说明：本技术 一种组分含量稳定的含碘消毒剂及其制备方法 (Iodine-containing disinfectant with stable component content and preparation method thereof ) 是由 王振兴 谭志坚 符德文 刘肖娟 赵一阳 黎剑坤 陈艺青 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种组分含量稳定的含碘消毒剂,其特征在于,所述含碘消毒剂是由原料在60～100℃反应5～18小时制备得到的,用于制备所述含碘消毒剂的原料包括单质碘、碘化物和下列六者中的任一者：(1)羧酸和醇(2)羧酸、醇和水(3)羧酸、醇、羧酸酯和水(4)醇、羧酸酯和水(5)羧酸、羧酸酯和水(6)羧酸酯和水,并且所述含碘消毒剂中水的质量含量不大于30％。本发明的含碘消毒剂的各个组分在碘作为催化剂的条件下通过可逆的酯化反应达到平衡。该含碘消毒剂的组分稳定性,经过长期储存(至少两年)其碘、碘化物、羧酸含量维持稳定,具有稳定的消毒杀菌效果。(The invention discloses an iodine-containing disinfectant with stable component content, which is characterized in that the iodine-containing disinfectant is prepared by reacting raw materials at 60-100 ℃ for 5-18 hours, and the raw materials for preparing the iodine-containing disinfectant comprise elementary iodine, iodide and any one of the following six materials: (1) carboxylic and alcohol (2) carboxylic acid, alcohol and water (3) carboxylic acid, alcohol, carboxylic ester and water (4) alcohol, carboxylic ester and water (5) carboxylic acid, carboxylic ester and water (6) carboxylic ester and water, and the iodine-containing disinfectant has a water content of no more than 30% by mass. The components of the iodine-containing disinfectant of the invention reach equilibrium through reversible esterification reaction under the condition that iodine is used as a catalyst. The iodine-containing disinfectant has stable components, and stable contents of iodine, iodide and carboxylic acid after long-term storage (at least two years), and has stable disinfecting and sterilizing effects.)

1. The iodine-containing disinfectant with stable component content is characterized in that the iodine-containing disinfectant is prepared by reacting raw materials at 60-100 ℃ for 5-18 hours, and the raw materials for preparing the iodine-containing disinfectant comprise the following components:

elemental iodine, iodide, and any one of the following six:

(1) carboxylic acids and alcohols

(2) Carboxylic acid, alcohol and water

(3) Carboxylic acid, alcohol, carboxylic ester and water

(4) Alcohol, carboxylic ester and water

(5) Carboxylic acid, carboxylic ester and water

(6) A carboxylic acid ester and water, wherein,

and the mass content of water in the iodine-containing disinfectant is not more than 30%.

2. An iodine-containing disinfectant with stable component content, which is prepared by mixing components and their contents measured in claim 1 at normal temperature.

3. The iodine-containing disinfectant according to claim 1 or 2, wherein the raw materials for preparing the iodine-containing disinfectant comprise the following components in mass content:

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of carboxylic acid and 60-90% of alcohol, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-25% of water, 5-30% of carboxylic acid and 35-80% of alcohol, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of water, 5-25% of carboxylic acid, 32-72% of alcohol, 5-25% of carboxylic ester, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 10-30% of water, 25-65% of alcohol and 15-45% of carboxylic ester, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of water, 5-35% of carboxylic acid and 30-75% of carboxylic ester, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of water and 50-90% of carboxylic ester.

4. Iodine-containing disinfectant according to claim 1 or 2 wherein the iodide is selected from the group consisting of hydrogen iodide, potassium iodide, sodium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide, monoquaternary ammonium iodide, diquaternary ammonium iodide, triquaternary ammonium iodide, polyquaternary ammonium iodide and hyperbranched quaternary ammonium iodide.

5. Iodine-containing disinfectant according to claim 1 or 2, wherein said carboxylic acid is selected from the group consisting of mixtures of one or more of citric acid, 1,3, 5-pentaric acid, 1,3, 5-cyclohexanetrioic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, gallic acid and salicylic acid.

6. Iodine-containing disinfectant according to claim 1 or 2, wherein said alcohol is an alcohol having less than 10 carbons in the molecule.

7. The iodine-containing disinfectant according to claim 6, wherein said alcohol having less than 10 carbon atoms in the molecule is selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol and pentaerythritol.

8. Iodine-containing disinfectant according to claim 1 or 2, wherein said carboxylic ester is formed by said carboxylic acid with said alcohol.

9. The iodine-containing disinfectant according to claim 8, wherein said carboxylic acid ester is selected from the group consisting of mixtures of one or more of citric 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, butyric acid, lactic acid, gallic acid or salicylic acid with carboxylic acid esters of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol or pentaerythritol.

10. The iodine-containing disinfectant according to claim 1 or 2, wherein the raw materials for preparing the iodine-containing disinfectant comprise the components: elemental iodine, iodide, water and carboxylic ester,

wherein the iodide is selected from one or more of a mixture of mono-quaternary ammonium iodide, bis-quaternary ammonium iodide, tri-quaternary ammonium iodide, polyquaternary ammonium iodide and hyperbranched quaternary ammonium iodide.

11. A method of preparing an iodine-containing disinfectant as claimed in any one of claims 1 to 10, comprising the steps of:

(1) adding elementary iodine and iodide into partial alcohol to dissolve or partially dissolve the elementary iodine and iodide,

(2) mixing the residual alcohol and carboxylic acid, adding the mixture into the mixed solution in the step (1),

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid and alcohol, mixing with the solution of step (1), adding residual water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid and alcohol, mixing with the solution of the step (1),

(3) reacting for 5-15 hours at 60-100 ℃, adding the rest water, and reacting for 0.5-2 hours to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid, alcohol and carboxylic ester, mixing with the solution of step (1), adding the rest water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing alcohol and carboxylic ester, mixing with the solution of step (1), adding the rest water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid and carboxylic ester, mixing with the solution of step (1), adding the rest water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing the carboxylic ester with the solution of step (1), then adding the remaining water,

(3) and reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant.

Technical Field

The invention belongs to the field of disinfectants, and particularly relates to an iodine-containing disinfectant with stable component content.

Background

Iodine-containing disinfectants have been used for over a hundred years, and a large number of iodine-containing disinfectants have been developed. Is used for disinfecting human skin, wound surface, mucosa surface, surgical instruments, pool water and drinking water, and for sanitary treatment and environmental disinfection of tableware.

Particularly, the iodine can show more excellent disinfection and sterilization effects under the coordination of some substances with disinfection and sterilization effects and acidity. Alcohol substances are also common components for disinfection and sterilization, and can play a role in coupling enhancement when matched with iodine and acid. Therefore, the iodine-containing disinfectant contains carboxylic acid and alcohol substances at the same time. In order to improve the solubility of elemental iodine, it is also a common method in the process of preparing iodine-containing disinfectants to first dissolve a certain iodide such as potassium iodide, sodium iodide and the like with water and then dissolve the elemental iodine. The mechanism by which iodide can promote the rate and amount of iodine dissolution is I₂+I-＝I₃ ^-In which I₃ ^-The solubility in water is far higher than that of the elementary iodine, and the generated I₃ ^-Does not affect the disinfection and sterilization effects.

However, the stability of the components of the above formulations containing elemental iodine, iodide, water, alcohol, and carboxylic acid has been a very challenging problem. Is mainly reflected in the reduction of the iodine content and/or the reduction of the carboxylic acid content in different iodine-containing disinfectant formulas. The unstable component content influences the shelf life of the product on one hand, and can generate certain influence on the actual disinfection and sterilization effect after long-term storage, thereby causing certain trouble to the use of the product.

Therefore, there is a need for iodine-containing disinfectants with a stable composition.

Disclosure of Invention

Aiming at the problem of unstable component content of the iodine-containing disinfectant in the prior art, the invention aims to provide the iodine-containing disinfectant with stable component content, which has stable contents of iodine, iodide and carboxylic acid after long-term storage (at least two years) and stable disinfection and sterilization effects.

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

the iodine-containing disinfectant with stable component content is prepared by reacting raw materials at 60-100 ℃ for 5-18 hours, and the raw materials for preparing the iodine-containing disinfectant comprise the following components:

elemental iodine, iodide, and any one of the following six

(1) Carboxylic acids and alcohols

(2) Carboxylic acid, alcohol and water

(3) Carboxylic acid, alcohol, carboxylic ester and water

(4) Alcohol, carboxylic ester and water

(5) Carboxylic acid, carboxylic ester and water

(6) A carboxylic acid ester and water, wherein,

and the mass content of water in the iodine-containing disinfectant is not more than 30%.

Preferably, the iodine-containing disinfectant with stable component content is prepared by measuring the components and the content of the iodine-containing disinfectant and mixing the components and the content at normal temperature.

Preferably, the raw materials for preparing the iodine-containing disinfectant comprise the following components in percentage by mass:

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of carboxylic acid and 60-90% of alcohol, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-25% of water, 5-30% of carboxylic acid and 35-80% of alcohol, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of water, 5-25% of carboxylic acid, 32-72% of alcohol, 5-25% of carboxylic ester, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 10-30% of water, 25-65% of alcohol and 15-45% of carboxylic ester, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of water, 5-35% of carboxylic acid and 30-75% of carboxylic ester, or

0.5-10% of elemental iodine, 0.5-8% of iodide, 5-30% of water and 50-90% of carboxylic ester.

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

Preferably, the carboxylic acid is selected from one or more of citric 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, butyric acid, lactic acid, gallic acid and salicylic acid.

Preferably, the alcohol is an alcohol having less than 10 carbons in the molecule.

Preferably, the alcohol is selected from one or more of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol and pentaerythritol.

Preferably, the carboxylic acid ester is formed by the carboxylic acid and the alcohol.

Preferably, the carboxylic ester is selected from one or more of citric 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, butyric acid, lactic acid, or gallic acid, and one or more of carboxylic esters formed from ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, or pentaerythritol.

More preferably, the carboxylic acid ester is selected from the group consisting of acetic acid, citric acid, 1,3, 5-pentanedioic acid or 1,3, 5-cyclohexanetricarboxylic acid, and one or more of the carboxylic acid esters of ethanol, n-propanol, diethylene glycol, triethylene glycol, glycerol or pentaerythritol.

More preferably, the raw materials for preparing the iodine-containing disinfectant comprise the components of elemental iodine, iodide, water and carboxylic acid ester, wherein the iodide is selected from a mixture of one or more of mono-quaternary ammonium iodide salt, bis-quaternary ammonium iodide salt, tri-quaternary ammonium iodide salt, polyquaternary ammonium iodide salt and hyperbranched quaternary ammonium iodide salt.

The invention also provides a preparation method of the iodine-containing disinfectant with stable content of the components, which comprises the following steps:

(1) adding elementary iodine and iodide into partial alcohol to dissolve or partially dissolve the elementary iodine and iodide,

(2) mixing the residual alcohol and carboxylic acid, adding the mixture into the mixed solution in the step (1),

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid and alcohol, mixing with the solution of step (1), adding residual water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid and alcohol, mixing with the solution of the step (1),

(3) reacting for 5-15 hours at 60-100 ℃, adding the rest water, and reacting for 0.5-2 hours to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid, alcohol and carboxylic ester, mixing with the solution of step (1), adding the rest water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing alcohol and carboxylic ester, mixing with the solution of step (1), adding the rest water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing carboxylic acid and carboxylic ester, mixing with the solution of step (1), adding the rest water,

(3) reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant;

or

(1) Dissolving iodide in a small amount of water, adding elementary iodine to completely dissolve the elementary iodine to obtain a solution containing iodide and elementary iodine,

(2) mixing the carboxylic ester with the solution of step (1), then adding the remaining water,

(3) and reacting for 5-18 hours at 60-100 ℃ to obtain the iodine-containing disinfectant.

The iodine-containing disinfectant with stable component content can be directly used for disinfection, and can also be used after being diluted by water. When the disinfectant is diluted by water for use, the disinfectant can be directly added into water to be diluted for dilution, preferably 50-1000 times, and can be disinfected by soaking, spraying and the like.

The main reason for obtaining the stability of the disinfectant is that the components such as acid, alcohol, water, ester and the like in the iodine-containing disinfectant can reach balance through reversible esterification reaction under the reaction condition under the condition that elemental iodine and/or iodide is used as a catalyst; meanwhile, the disproportionation reaction of the iodine simple substance in the presence of water and acid also has a certain influence on the stability of the disinfectant, but because the water content in the system of the invention is lower, generally lower than 30%, and the iodine simple substance, iodide, carboxylic acid, alcohol, ester and other substances have been added as raw materials, the disproportionation reaction of the simple substance iodine under the reaction condition can cause the reduction of the simple substance iodine content and the increase of iodine ions to a certain extent, but the degree of change is smaller, so the influence of the disproportionation reaction of the iodine simple substance on the system stability is smaller. Under the reaction conditions, the balance of esterification reaction (which plays a main role in the system) and the balance of disproportionation reaction of iodine simple substance (which plays a secondary role in the system) are combined to obtain a stable system with balanced components of the whole system. Therefore, the obtained iodine-containing disinfectant has stable components, and the contents of iodine, iodide and carboxylic acid are kept stable after long-term storage (at least two years), so that the iodine-containing disinfectant has stable disinfection and sterilization effects.

Detailed Description

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

In the description of the present invention, "iodide" is a compound composed of iodine anion (I)^-) With hydrogen ions, metal cations or ammonium ions or quaternary ammonium ions.

In the description of the present invention, "monoquaternary ammonium iodide" refers to an iodide composed of monoquaternary ammonium ions and iodide ions, and "bis-quaternary ammonium iodide", "tris-quaternary ammonium iodide", "poly-quaternary ammonium iodide" and "hyperbranched quaternary ammonium iodide" have similar definitions.

The iodine-containing disinfectant with stable component content is prepared by reacting raw materials at 60-100 ℃ for 5-18 hours, and the raw materials for preparing the iodine-containing disinfectant comprise the following components:

elemental iodine, iodide, and any one of the following six: (1) carboxylic and alcohol (2) carboxylic acid, alcohol and water (3) carboxylic acid, alcohol, carboxylic ester and water (4) alcohol, carboxylic ester and water (5) carboxylic acid, carboxylic ester and water (6) carboxylic ester and water. The iodine-containing disinfectant prepared finally comprises the following components: the iodine-containing water-based catalyst comprises elementary iodine, iodide, carboxylic acid, alcohol, carboxylic ester and water, wherein the elementary iodine, iodide, carboxylic acid, alcohol, carboxylic ester and water are obtained by balancing components in raw materials through reversible esterification reaction, and the iodine-containing water-based catalyst has the characteristic of long-term stable content. The iodine-containing disinfectant in the final product may also include other substances obtained by reacting the above-mentioned raw materials under reaction conditions, the content of which is less than about 2%.

In the actual production, the iodine-containing disinfectant can be prepared by measuring the components and the content thereof after obtaining the iodine-containing disinfectant and then preparing the iodine-containing disinfectant at normal temperature according to the components and the content thereof.

The simple substance iodine in the iodine-containing disinfectant is a main disinfecting and sterilizing component. In the raw materials for preparing the iodine-containing disinfectant, the mass percentage of the elementary iodine is 0.1-10%, more preferably 0.5-4%, and still more preferably 1-3%.

Because of the solubility of elemental iodine, the use of small amounts of iodide to increase the solubility of elemental iodine is a very effective and commonly used method. Because of I^-Is present in₂+I^-＝I₃ ^-The reaction of (A) takes place, and I₃ ^-It is more water soluble. To form the above-mentioned I₃ ^-Moles of ion, preferably elemental iodine, with I in iodide^-The ratio of the mole numbers of (1: 0.8) to (1: 1.2).

In the present invention, the iodide is selected from iodides that are readily soluble in water and/or alcohol. Such iodides include, but are not limited to, hydrogen iodide, metal iodides (e.g., potassium iodide, sodium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide), ammonium iodide, or quaternary ammonium iodide salts.

The quaternary ammonium iodide salt can be used XI_yWherein X represents a quaternary ammonium ion, y represents the number of charges carried in the quaternary ammonium ion X, and also represents the number of quaternary ammonium structures contained in the quaternary ammonium ion X, and if y is equal to 1, it represents a quaternary ammonium iodide salt; y is equal to 2, then bis-quaternary ammonium iodide salt is represented; y is equal to 3, indicating a trisquaternary ammonium iodide salt; and so on. In the present invention, y is preferably 5 or less. The monoquaternary ammonium iodide salt (iodide of monoquaternary ammonium radical ion with iodide ion) can be represented as XI; the bis-quaternary ammonium iodide salt (iodide of bis-quaternary ammonium ion and iodide) can be represented by XI₂(ii) a Tri-quaternary iodonium salts can be represented by XI₃(ii) a The polyquaternary or hyperbranched quaternary iodonium salts may be represented by XI_y(y is an integer greater than 3). The quaternary ammonium iodide salt of the invention can be the single type of quaternary ammonium iodide salt or the combination of the single type of quaternary ammonium iodide salt or the different types of quaternary ammonium iodide saltsAnd (4) combining.

In the description of the invention, the monoquaternary ammonium iodide salt may be used as R₁R₂R₃R₄N⁺I^-Is represented by the formula (I) in which R₁R₂R₃R₄N⁺Represents a monoquaternary ammonium ion, I^-Represents an iodide anion, wherein R₁、R₂、R₃、R₄Each independently selected from hydrocarbyl groups having 1 to 20 carbon atoms; preferably R₁To R₄Three of them are selected from the same hydrocarbon group, and the remaining one is selected from an alkyl group having 2 to 20 carbon atoms; the hydrocarbon group is preferably an alkyl group, and the alkyl group is preferably a methyl group, an ethyl group, or a propyl group.

In the description of the present invention, the quaternary ammonium salts include, but are not limited to, octadecyl trimethyl ammonium iodide, hexadecyl trimethyl ammonium iodide, tetradecyl trimethyl ammonium iodide, dodecyl trimethyl ammonium iodide, decyl trimethyl ammonium iodide, octyl trimethyl ammonium iodide, hexyl trimethyl ammonium iodide, benzyl trimethyl ammonium iodide, octadecyl triethyl ammonium iodide, hexadecyl triethyl ammonium iodide, tetradecyl triethyl ammonium iodide, dodecyl triethyl ammonium iodide, decyl triethyl ammonium iodide, octyl triethyl ammonium iodide, hexyl triethyl ammonium iodide, benzyl triethyl ammonium iodide, and tetrabutyl ammonium iodide.

In the description of the present invention, bis-quaternary ammonium iodide salts include, but are not limited to, Gemini type bis-quaternary ammonium iodide salts.

Because the quaternary ammonium iodized salt has a surfactant effect, the addition of the quaternary ammonium iodized salt can promote the disinfection and sterilization effects of the iodine-containing disinfectant. It also promotes the hydrolysis reaction of carboxylic ester.

As for the acid in the raw material for preparing the iodine-containing disinfectant of the present invention, although inorganic acids such as sulfuric acid, phosphoric acid and the like may also play a role in maintaining the acidic environment of the system, organic acids are selected, and further carboxylic acids are selected in consideration of biocompatibility, safety in use and the like; compared with inorganic acid, the carboxylic acid has milder property and better biocompatibility, and iodine can exert more excellent disinfection and sterilization effects in an acidic medium environment.

In the present description, the carboxylic acid is preferably water-soluble and/or alcohol-and/or ester-soluble, and more preferably a carboxylic acid that can undergo esterification reaction under catalysis of elemental iodine. Such carboxylic acids include, but are not limited to, citric acid (citric acid), oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid and gallic acid, salicylic acid. Acetic acid and citric acid are preferable from the viewpoint of water solubility, alcohol solubility, and acidity and the sterilizing effect thereof.

The alcohol in the raw materials for preparing the iodine-containing disinfectant can be used as a solvent for dissolving acid and ester, iodine and iodide, and in the formula research, the inventor has very surprising found that the alcohol also has the obvious effect of stabilizing the elemental iodine and preventing the content of the elemental iodine from being reduced in the formula of the iodine-containing disinfectant. In the formulation of the iodine-containing disinfectant without alcohol, the reduction of the content of elemental iodine and the increase of the content of iodide ions occur simultaneously, which seriously affects the stability of the disinfectant product and the subsequent disinfection and sterilization effect. The mechanism by which alcohol can inhibit the reduction of elemental iodine and the increase of iodide ions in the iodine disinfectant formulation of the present invention is not well understood, and may be the result of interaction with other components in the system, such as acids, esters, etc., in the presence of alcohol, or may be related to the reduction of water content in the system caused by the addition of alcohol. However, alcohols are critical in the iodine disinfectant formulations of the present invention, are also indispensable to obtain the balanced composition of the final formulation, and need to have a large compositional ratio, more than the water content of the system.

In the present invention, alcohol with larger water solubility and better acid and ester solubility is generally selected, and alcohol with carbon number less than 10 in the molecule or polyethylene glycol 200 and polyethylene glycol 300 are preferred. Alcohols having less than 10 carbon atoms in the molecule include, but are not limited to, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, and pentaerythritol. Ethanol, n-propanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol and pentaerythritol are preferred. Although methanol also has good material solubility and can obtain iodine-containing disinfection liquid with long-term stability, methanol is not selected as the composition of the raw materials in the application in consideration of the toxicity of methanol.

The presence of carboxylic acid esters in the raw materials used to prepare the iodine-containing disinfectants of the present invention is of great importance in stabilizing the content of the components in the formulation. The prepared raw materials do not contain ester, and the method is one of the important reasons for the instability of the existing iodine disinfectant formula containing acid and alcohol. The carboxylic ester in the iodine disinfectant formula finally prepared by the invention can be generated by esterification reaction of carboxylic acid and alcohol in raw materials, and iodine is used as a catalyst of the esterification reaction in the process. The esterification reaction under the catalysis of iodine is the basis of the preparation method of the iodine-containing disinfectant, namely, the equilibrium state of the esterification reaction is the basis of the stability of the iodine-containing disinfectant prepared by the invention.

In general, in the esterification reaction, a water-carrying agent is generally used to cause the esterification reaction to proceed in the direction of ester formation in order to obtain an esterified product. The equation for the esterification reaction can be simply expressed as:

however, the reaction of acid and alcohol to form ester or the hydrolysis reaction or ester exchange reaction of ester generally has higher activation energy, and is difficult to occur in the absence of a catalyst. But in the presence of elemental iodine as a catalyst, the activation energy of the reaction is greatly reduced, which is why conventional iodine-containing disinfectant compositions containing carboxylic acids, alcohols are unstable. Particularly because the components of carboxylic acid and alcohol are subjected to esterification reaction under the catalysis of iodine, so that the acid content is reduced and the water content is increased, which in turn leads to the reduction of the iodine simple substance, because when the water is increased and the acid is reduced in the system, the phenomena of the increase of the water and the reduction of the acid occurOrIs balanced toRight shift, resulting in a decrease in elemental iodine content. And the reduction of the content of the elemental iodine directly influences the disinfection and sterilization effect of the whole disinfectant.

Elemental iodine has been reported as a catalyst for the reaction of carboxylic acids and alcohols to esters. Elemental iodine is reported as a mild Lewis acid to catalyze esterification and transesterification of carboxylic acids with alcohols, as well as esterification reaction, as described in K.Ramalinga, P.Vijayalakshmi, T.N.B.Kaima.A. mil and effective method for esterification and transesterification of byy iodine [ J ]. Tetrahedron Letters,2002, 43: 879-.

According to the stability research of the formula containing carboxylic acid, alcohol, iodine, iodide and water by the inventor, the content of the carboxylic acid is reduced even if the formula is placed at room temperature, and the detection finds that an esterification product of the carboxylic acid and the alcohol is generated, such as that after the iodine-containing disinfectant containing citric acid and ethanol is placed for a long time, more components of the monoethyl citrate ester and the diethanol citrate ester are detected, and a small amount of components of the triester citrate are detected; esterified products of citric acid and glycerol were detected in iodine-containing disinfectants containing citric acid and glycerol; moreover, the formation of this esterification product increases with increasing temperature and is a significant cause of the deterioration of the stability of the disinfectant components. However, unlike the above-mentioned documents for the purpose of obtaining an esterified product, the inventors have unexpectedly found that a composition comprising elemental iodine, an iodide, a carboxylic acid, an alcohol, an ester, water, and the like, all in equilibrium, can be obtained by using the composition of the raw material of the disinfectant to perform an esterification reaction and/or a hydrolysis reaction of the ester and/or a transesterification reaction under a high temperature condition to reach a final composition equilibrium, based on the characteristics of the iodine-containing disinfectant. In the process, the iodine-containing disinfectant with stable composition can be obtained by heating reaction only by controlling the initial proportion of the raw materials.

The iodine-containing disinfectant obtained through the balancing process can control the balance moving range within a very small range by the balance relation of each component in the composition even if the temperature of the system changes again, and the range requirement of the composition stability is met. And when the temperature is restored to the normal storage temperature, the components of the iodine-containing disinfectant return to the original balance state, so that the components are restored to the balance components, and the iodine-containing disinfectant with stable component content is obtained.

The esterification reaction reported in the above-mentioned document is determined by the esterification reaction concerned in the document, and only the esterification reaction using iodine as a catalyst is discussed, and no discussion is made about the change of the content of iodine itself. The reaction system of the above document is designed to improve the yield of the ester and to improve the conversion of the acid, and no additional water is added to the reaction system (in general, a water-carrying agent is often added to the esterification reaction, and the amount of water in the system is reduced to improve the degree of the esterification reaction). In the raw materials in the preparation method of the iodine-containing disinfectant, under the condition that acid and alcohol exist, moisture is certainly still present, and a certain amount of moisture also has a special effect, for example, water can be used as a medium for dissolving iodide on one hand, so that the dissolution of elemental iodine is accelerated, and the dissolution amount of the elemental iodine is increased; on the other hand, the esterification reaction can be balanced, because the balance of the reversible esterification reaction involving acid, alcohol, water and ester can be shifted, and the water can shift the balance of the reaction. In order to maintain a certain acid content, a large amount of acid needs to be added, which has a negative influence on the cost of the formulation of the whole composition, and a certain amount of water exists in the system, so that the degree of the esterification reaction balance can be controlled, the ratio of the amount of carboxylic acid to the amount of carboxylic ester in the system is maintained in a high range, and the iodine-containing disinfectant has obvious advantages on maintaining reasonable cost of iodine-containing disinfectant products, and the system does not need to contain a large amount of ester substances.

However, the water content is controlled at a certain level, and it is found that the change of the iodine content in the finally prepared iodine-containing disinfectant is obvious when the water content is higher, and the specific reason is not clear, but the change may be related to the weakening of the stabilizing effect of the alcohol and/or acid and/or ester substances on the iodine when the water content is higher, and the iodine and the water have certain reactions in the presence of the substances. According to the results of previous studies by the inventors, it is possible that the reason is that disproportionation of iodine in the presence of water occurs with simple iodine:

(or)

In the presence of a large amount of water in the system, the disproportionation reaction of iodine proceeds rightward, and although iodide ions (supplied by iodide) and hydrogen ions (mainly supplied by carboxylic acid) are present in the system, a certain amount of iodate (or iodic acid) must be present to maintain the equilibrium of the reaction because of the absence of iodate (or iodic acid) in the system. This results in a decrease in the amount of elemental iodine with a concomitant increase in iodide ion. This was also found to occur during the actual experiment. This is why the amount of raw material water and/or the amount of water after the balance of the iodine-containing disinfectant to be prepared in the preparation method of the present invention needs to be controlled to be not more than 30%, and further optimized to be within 25%. Only when the water quantity is less, the equilibrium shift of the reversible reaction is less, the influence on the stability of the iodine is less, and the requirement of keeping the stability of the iodine content after being placed at room temperature for two years can be basically met. The balance is also related to the change of the carboxylic acid content, and finally a complex balance system with carboxylic acid esterification balance as the main part and iodine simple substance disproportionation reaction balance as the auxiliary part is achieved, and finally the result of stable system components is achieved. According to the principle of chemical equilibrium, the addition of iodide (iodide ion) to the disinfectant plays a significant role in stabilizing the iodine content, because according to the above reaction formula, the molar ratio of iodide ion to iodate (and/or iodic acid) is 5:1, so that the influence of the change of the iodide ion content on the system is the relationship of the fifth power of the change of the iodate (and/or iodic acid) content, therefore, in the system in which the iodide exists, the change of the iodine content and the change of the iodide ion under the conditions of the system can be ensured to be small, which is also the main reason for using the iodide as a stable iodine simple substance in the application.

In order to obtain the iodine-containing disinfectant with stable content of the components, the preparation method is to mix the elementary iodine and the iodide with 2 to 4 of carboxylic acid, alcohol, water and carboxylic ester, and then to make the system reach an equilibrium state mainly by the esterification reaction and/or the hydrolysis reaction of the carboxylic ester and/or the alcohol exchange reaction of the carboxylic ester and/or the acid exchange reaction of the carboxylic ester under the catalysis of iodine. Specifically, the raw materials for preparing the iodine-containing disinfectants of the present invention include any one of the following six in addition to elemental iodine and iodide: (1) carboxylic and alcohol (2) carboxylic acid, alcohol and water (3) carboxylic acid, alcohol, carboxylic ester and water (4) alcohol, carboxylic ester and water (5) carboxylic acid, carboxylic ester and water (6) carboxylic ester and water.

When elementary iodine, iodide, carboxylic acid and alcohol are selected as starting raw materials, the preparation method of the iodine-containing disinfectant comprises the steps of adding the elementary iodine, the iodide, the carboxylic acid and the alcohol into a system, heating to react to enable part of the carboxylic acid to react with the alcohol to generate reaction of carboxylate and water, and the like, slowly cooling to room temperature after the balance of system composition is achieved, and obtaining iodine-containing disinfectant with balanced and stable components; more specifically, the preparation method comprises the steps of: adding simple substance iodine and iodide into alcohol to dissolve or partially dissolve the simple substance iodine and iodide, then mixing the residual alcohol and carboxylic acid, adding the mixture into the mixed solution of iodine, iodide and alcohol, then reacting the system under the heating condition to reach the balance of alcohol, acid, ester, water and the like, and then cooling to room temperature to obtain the iodine-containing disinfectant with stable components;

the iodine-containing disinfectant with stable long-term components obtained by the method is accurately measured for the content of each component, and then the iodine-containing disinfectant with stable long-term components, which is obtained without a high-temperature reaction process, can be obtained by preparing according to the content of each component, and the process is a cold splicing process.

For the preparation method using elemental iodine, iodide, carboxylic acid and alcohol as starting materials, some iodides may not have a high solubility or a slow dissolution rate therein, and do not significantly affect the whole preparation process. Iodide or elemental iodine may not be rapidly dissolved in the system at the beginning, but in the subsequent heating reaction process, the iodide and the elemental iodine are dissolved along with the increase of the temperature and part of water generated in the esterification reaction; meanwhile, the temperature rise and the dissolution of iodide and/or elementary iodine further accelerate the esterification reaction speed, so that the whole reaction system is finally balanced. Generally, the raw material solution reacts for 5 to 18 hours at the temperature of 60 to 100 ℃, the balance can be achieved, then the raw material solution is cooled to the room temperature, and the subsequent canning operation can be carried out, so that a product with stable components can be obtained;

when elementary iodine, iodide, carboxylic acid, alcohol and water are selected as starting raw materials, the preparation method of the iodine-containing disinfectant comprises the steps of mixing the elementary iodine, the iodide, the carboxylic acid, the alcohol and the water, heating and reacting a raw material liquid for a period of time, reacting the carboxylic acid and the alcohol to generate a certain amount of ester, balancing the carboxylic acid, the alcohol, the carboxylic ester, the water and the like, and then cooling a feed liquid to obtain the iodine-containing disinfectant with balanced and stable components. More specifically, although the preparation method can add all the materials in a certain order, and then carry out esterification reaction under the condition of controlling a certain temperature to obtain feed liquid with balanced components, the preferable process is carried out by utilizing water to dissolve iodide faster and iodide aqueous solution to dissolve elementary iodine faster. Dissolving iodide in a small amount of water, adding elemental iodine to obtain a uniform solution, mixing acid, alcohol and the rest water, adding the mixture into the iodine-containing solution, heating to balance the materials, and cooling the materials to obtain the iodine-containing disinfectant with stable component content. The preparation method can also be realized by only mixing carboxylic acid and alcohol, adding the mixture into aqueous solution containing elemental iodine and iodide, heating to stabilize the system composition, then adding the rest water 1-3h before the basic stabilization, and continuously preserving the heat for 0.5-2h to stabilize the system components, thereby reducing the time for stabilizing each composition. Since the esterification reaction is a reversible reaction, if the system contains more water at the beginning, the esterification reaction is obviously inhibited, and the composition of the system contains less esterification products at the equilibrium of the reaction, which is beneficial to the utilization rate of carboxylic acid, but the reaction speed is obviously reduced by more water, and the time for reaching the equilibrium is also obviously prolonged. Therefore, only a small amount of water is used for dissolving at the beginning to dissolve the elementary iodine, on one hand, the dissolution of the elementary iodine can accelerate the reaction of the system, on the other hand, the small amount of water can enable the reaction to be carried out in the direction of generating the ester in a balanced way, and then the water is added 1 to 3 hours before the reaction reaches the balance. This allows the esterification reaction to reach equilibrium quickly, thereby obtaining a stable component content. The reason is that the esterification reaction can be further carried out towards the direction of generating ester when water is not added in the esterification reaction 1-3 hours before the reaction is balanced, but the reaction does not reach complete balance at the moment, and the system can be closer to the balanced state after the water is added, so that the system can reach the balanced state more quickly; however, if the remaining water is added after the whole system is balanced, the addition of water is required to further move the ester formed in the system toward the alcohol and carboxylic acid because the system is balanced, and this eventually makes the system balanced, but the time required for the balance to be reached is prolonged, which is disadvantageous from the viewpoint of production.

The iodine-containing disinfectant with stable long-term components obtained by the method is accurately measured for the content of each component, and then the iodine-containing disinfectant with stable long-term components, which is obtained without a high-temperature reaction process, can be obtained by preparing according to the content of each component, and the process is a cold splicing process.

When elemental iodine, iodide, carboxylate, carboxylic acid, alcohol and water are selected as the starting raw materials, the iodine-containing disinfectant of the present invention is obtained by esterification reaction and/or hydrolysis of carboxylate, alcohol exchange, carboxylic acid, ester exchange reaction, etc. The preparation method comprises the steps of mixing elemental iodine, iodide, carboxylate, carboxylic acid, alcohol and water, heating to enable partial carboxylic acid and alcohol to generate esterification reaction and/or carboxylate hydrolysis to generate corresponding ester exchange reaction of carboxylic acid and alcohol and/or carboxylate and/or carboxylic acid exchange reaction of carboxylate and/or alcohol exchange reaction of carboxylate and the like, so that the system is balanced, and then slowly cooling to room temperature to obtain the iodine-containing disinfectant with balanced and stable components. More specifically, the preparation method of the iodine-containing disinfectant comprises the following steps: adding iodide into a small amount of water to completely dissolve the iodide, adding elementary iodine into the water to dissolve the iodine, adding alcohol, carboxylic acid, carboxylic ester and the rest water into the mixed solution after mixing, quickly carrying out esterification reaction and/or carboxylic ester hydrolysis and/or carboxylic ester transesterification and/or carboxylic ester acid exchange reaction and/or carboxylic ester alcohol exchange reaction under the heating condition on the mixture to reach the balance among alcohol, acid, ester, water and the like, and then cooling to room temperature to obtain the iodine-containing disinfectant with stable components; the carboxylic acid esters for the purposes of the present invention may be mono-, di-or polyesters of the corresponding carboxylic acid starting materials, also mono-, di-or polycarboxylic acid esters of the corresponding alcohols, and also crosslinked esterification products of polycarboxylic acids with polyhydric alcohols.

The iodine-containing disinfectant with stable long-term components obtained by the method is accurately measured for the content of each component, and then the iodine-containing disinfectant with stable long-term components, which is obtained without a high-temperature reaction process, can be obtained by preparing according to the content of each component, and the process is a cold splicing process.

When elementary iodine, iodide, carboxylate, alcohol and water are selected as initial raw materials, the iodine-containing disinfectant is obtained by mixing the elementary iodine, the iodide, the carboxylate, the alcohol and the water and then heating. Heating to hydrolyze partial carboxylic ester into corresponding carboxylic acid and alcohol and/or alcohol ester exchange reaction of carboxylic ester and/or ester exchange reaction of carboxylic ester, etc., to make the system reach equilibrium, then slowly cooling to room temperature, and obtaining iodine-containing disinfection solution with equilibrium components and stable existence. More specifically, the method for preparing iodine-containing disinfectants of the present invention comprises the following steps: adding iodide into a small amount of water to completely dissolve the iodide, adding simple substance iodine into the water to dissolve the iodine, adding alcohol, carboxylic ester and the rest water into a system, quickly performing carboxylic ester hydrolysis and/or carboxylic ester alcohol exchange reaction and/or carboxylic ester exchange reaction and the like on the mixture under the heating condition to reach the balance of alcohol, carboxylic acid, carboxylic ester, water and the like, and cooling to room temperature to obtain the iodine-containing disinfectant with stable components; the carboxylic ester can be monoester, diester or triester of corresponding carboxylic acid raw material, and can also be monocarboxylic ester, dicarboxylic ester or polycarboxylic ester of corresponding alcohol, and can also be cross-linked esterification product of polycarboxylic acid and polyalcohol.

The iodine-containing disinfectant with stable long-term components obtained by the method is accurately measured for the content of each component, and then the iodine-containing disinfectant with stable long-term components, which is obtained without a high-temperature reaction process, can be obtained by preparing according to the content of each component, and the process is a cold splicing process.

When elemental iodine, iodide, carboxylic acid ester, carboxylic acid and water are selected as the starting raw materials, the iodine-containing disinfectant of the present invention is obtained by mixing elemental iodine, iodide, carboxylic acid ester, carboxylic acid and water, followed by heating. Heating to hydrolyze partial carboxylic ester into corresponding carboxylic acid and alcohol and/or carboxylic ester, and/or ester exchange reaction of carboxylic ester, etc., to balance the system, and slowly cooling to room temperature to obtain iodine-containing disinfection solution with balanced and stable components. More specifically, the preparation method of the iodine-containing disinfectant comprises the following steps: adding iodide into a small amount of water to dissolve the iodide, then adding elementary iodine into the water to dissolve the iodine, then adding carboxylic acid, carboxylic ester and the rest water into the system, then rapidly carrying out hydrolysis reaction of the carboxylic ester on the mixture under the heating condition to reach the balance of alcohol, acid, ester, water and the like, and then cooling to room temperature to obtain the iodine-containing disinfection solution with stable component content. The carboxylic ester can be monoester, diester or triester of corresponding carboxylic acid raw material, and can also be monocarboxylic ester, dicarboxylic ester or polycarboxylic ester of corresponding alcohol, and can also be cross-linked esterification product of polycarboxylic acid and polyalcohol.

The iodine-containing disinfectant with stable long-term components obtained by the method is accurately measured for the content of each component, and then the iodine-containing disinfectant with stable long-term components, which is obtained without a high-temperature reaction process, can be obtained by preparing according to the content of each component, and the process is a cold splicing process.

When elemental iodine, iodide, carboxylate and water are selected as starting materials, the iodine-containing disinfectant of the present invention is obtained by mixing elemental iodine, iodide, carboxylate and water, followed by heating. Heating to hydrolyze partial carboxylic ester into corresponding carboxylic acid, and performing ester exchange reaction between the carboxylic acid and alcohol and/or carboxylic ester to balance the system, and slowly cooling to room temperature to obtain iodine-containing disinfectant with balanced and stable components; the carboxylic ester can be monoester, diester or triester of corresponding carboxylic acid raw material, and can also be monocarboxylic ester, dicarboxylic ester or polycarboxylic ester of corresponding alcohol, and can also be cross-linked esterification product of polycarboxylic acid and polyalcohol. More specifically, the preparation method of the iodine-containing disinfectant comprises the following steps: adding iodide into a small amount of water to completely dissolve the iodide, adding elementary iodine into the water to dissolve the iodine, adding carboxylic ester and the rest water into a system, rapidly carrying out ester hydrolysis and/or ester exchange reaction of the ester and other reactions of the mixture under the heating condition to reach the balance of alcohol, acid, ester, water and the like, and then cooling to room temperature to obtain the iodine-containing disinfectant with stable component content. However, for a carboxylic ester having a small water solubility, the above-mentioned production method may include the steps of, in view of elemental iodine being soluble in the carboxylic ester: adding iodide into a small amount of water to completely dissolve the iodide, dissolving elemental iodine into carboxylic ester, mixing the iodine with an iodide water solution, adding the rest water into a system, and finally quickly carrying out ester hydrolysis reaction and/or ester exchange reaction of ester under the heating condition of the mixture to reach the balance of alcohol, acid, ester, water and the like, and then cooling to room temperature to obtain the iodine-containing disinfectant with stable components. For such iodine-containing disinfectant formulations, the presence of water is advantageous for the rapid hydrolysis reaction of the ester, and so it is generally chosen that the entire formulated amount of water is added at the beginning.

In the preparation process, the iodide further preferably comprises quaternary ammonium iodide salt as a formula component, and the quaternary ammonium iodide salt can play a role of a phase transfer catalyst and can further accelerate the equilibrium reaction of esterification.

The iodine-containing disinfectant with stable long-term components obtained by the method is accurately measured for the content of each component, and then the iodine-containing disinfectant with stable long-term components, which is obtained without a high-temperature reaction process, can be obtained by preparing according to the content of each component, and the process is a cold splicing process.

The preparation method of the iodine-containing disinfectant with stable component content obtains an indispensable formula system with mutual balance, interaction and mutual coupling of various substances in the components through esterification reaction and/or carboxylic ester hydrolysis reaction and/or carboxylic ester alcohol exchange reaction and/or carboxylic ester acid exchange reaction and/or carboxylic ester exchange reaction under the catalysis of elemental iodine, so that the final formula of the iodine-containing disinfectant has the characteristic of stable component content, the composition of the system can not be obviously changed even after long-term placement, the high shelf life can be maintained, and the requirement of quality standard can be met, and the preparation method is simple and feasible. Particularly for an iodine-containing disinfectant system with complex components, the iodine-containing disinfectant with stable final components can be obtained more conveniently by using esterification reaction and/or carboxylic ester hydrolysis reaction and/or carboxylic ester alcohol exchange reaction and/or carboxylic acid exchange reaction and/or carboxylic ester transesterification reaction under the catalysis of elemental iodine. The iodine-containing disinfectant obtained by the cold-splicing process is prepared on the basis of the formula composition obtained by high-temperature balance, and the iodine-containing disinfectant product with long-term component stability can be obtained by the process, so that the iodine-containing disinfectant has more advantages on the formula with simple and easily obtained components.

Preferably, in the above preparation method, the order of addition of the raw materials may be appropriately adjusted according to the solubility between the materials.

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, iodide, and acid in the following examples are as follows:

elemental iodine: precisely measuring 10ml of the product, and weighingThe solution was placed in an iodine flask and titrated with sodium thiosulfate titrant (0.1mol/L) until the solution was 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 (calculated by a certain carboxylic acid if the system contains multiple acids) determined by acid-base titration is specifically as follows: 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, placing the product 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 color of a trichloromethane layer disappears. And removing the content of the elementary iodine to obtain the content of iodide. If precipitation occurs due to the problem of acid solubility during titration, an appropriate amount of ethanol may be added before titration. Unless otherwise specified, the iodide is typically calculated as potassium iodide.

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 (3) 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 timing when the temperature is raised to 80 ℃, preserving heat for 8 hours, stopping heating, naturally cooling to room temperature along with a furnace, taking a period of 24 hours from the start of timing, and then continuously repeating the process for 10 cycles. Sampling and measuring the contents of the elementary iodine, the iodide and the carboxylic acid within 3h (called as 0 day) after the disinfectant is prepared and after the 10 th day circulation (called as 10 days) respectively. It has been shown from earlier experimental results that one cycle (1 day) for the iodine-containing disinfectants of the present invention corresponds to approximately 2.5 months of storage at room temperature and 10 cycles corresponds to approximately 2 years.

Example 1:

1.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

2% of elementary iodine, 1.5% of potassium iodide, 20% of anhydrous citric acid and 76.5% of anhydrous ethanol.

1.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking about 300g of absolute ethyl alcohol, adding 20g of elemental iodine, stirring and dissolving, and adding 15g of potassium iodide to dissolve to obtain an A1 solution; dissolving 200g of citric acid in 400g of absolute ethyl alcohol to obtain a B1 solution; adding the B1 solution into the A1 solution under stirring, fully stirring, adding the rest 65g of absolute ethyl alcohol into the mixed solution under stirring to obtain a uniform solution, namely disinfectant raw material solution; the raw material solution is reacted for 18h at the temperature of 60 ℃ under the stirring state, and then is placed and cooled to obtain the iodine-containing disinfectant with long-term component stability.

1.3, the iodine simple substance, the iodide and the citric acid in the iodine-containing disinfectant prepared in the step 1.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is as follows: 1.98% of elementary iodine, 1.53% of iodide (calculated as potassium iodide) and 8.9% of carboxylic acid (calculated as citric acid).

And (3) performing full component analysis on the iodine-containing disinfectant prepared in the step (1.2), wherein the obtained iodine-containing disinfectant comprises the following components in percentage by weight: 1.97 percent of elementary iodine, 1.53 percent of iodide (calculated by potassium iodide), 0.15 percent of citric acid, 7.5 percent of citric acid monoethyl ester, 16.9 percent of diethyl citrate, 0.2 percent of triethyl citrate, 68.5 percent of ethanol and 3.1 percent of water. The above-mentioned substances add up to 99.86% and are not equal to 100%, and the possible reasons are measurement errors or small amounts of substances are not detected.

Since both monoethyl citrate and diethyl citrate contain carboxyl groups, both are normalized to citric acid for calculation when titrating with sodium hydroxide, resulting in inconsistency between the results of the titration of carboxylic acid and the results of the compositional analysis.

1.4, the disinfectant is subjected to 10 cycles of accelerated experiments at 80 ℃, the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiments are respectively 1.97%, 1.55% and 8.70, the change rates of the elemental iodine, the iodide and the carboxylic acid are respectively 0.51%, 1.31% and 2.25%, the change values are all less than 5%, and the product stability standard is met.

1.5 disinfectant is formulated according to the balanced disinfectant components determined above:

the preparation is carried out according to 1000 g:

dissolving 31g of water into 15.3g of potassium iodide, then adding 19.7g of elemental iodine, dissolving 1.5g of citric acid, 75g of citric acid monoethyl ester, 169% of diethyl citrate and 2% of triethyl citrate into 685g of ethanol, and then uniformly mixing the solution containing iodine and potassium iodide with the ethanol solution containing acid and ester to obtain the iodine-containing disinfectant with stable components. The initial elemental iodine, iodide, and carboxylic acid were tested as: 1.96%, 1.54% and 8.85%; the disinfection solution is subjected to accelerated test at 80 ℃ for 10 cycles, and after the accelerated stability test, the contents of elemental iodine, iodide and carboxylic acid in the disinfection solution tested at room temperature are respectively as follows: 1.93%, 1.61%, 8.89%; compared with the originally prepared disinfectant, the change rates of the simple substance iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively 1.53%, 4.55% and 0.45%, and are all less than 5%, so that the product stability standard is met. However, it was also found that the stability of the above formulated samples varied slightly (but still less than 5%) from the iodide content directly obtained by stabilization of the above starting materials by heating, probably due to the accuracy of the component content for the compositional analysis after equilibration, and in addition possibly a small amount of reaction products between the starting materials could not be detected (most probably iodic acid), which affected the stability between the components.

Example 2:

2.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

20% of citric acid, 2% of elementary iodine, 1.5% of potassium iodide, 61.5% of ethanol and 15% of water.

2.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking a small amount of water of about 25g, adding 15g of potassium iodide for dissolving, and then adding 20g of elementary iodine to completely dissolve the iodine to obtain an A2 solution; dissolving 200g of citric acid in 615g of ethanol to obtain a B2 solution; adding the B2 solution into the A2 solution under stirring, fully stirring, adding the rest 125g of water into the mixed solution under stirring to obtain a uniform solution, namely disinfectant raw material solution; the raw material solution is reacted for 12 hours at the temperature of 80 ℃ under the stirring state, and then the obtained product is placed and cooled to obtain the iodine-containing disinfectant with long-term component stability.

2.3 the iodine simple substance, the iodide and the citric acid in the iodine-containing disinfectant prepared by the 2.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is as follows: 1.96% of elementary iodine, 1.58% of iodide (calculated as potassium iodide) and 9.8% of carboxylic acid (calculated as citric acid).

And (3) performing full component analysis on the iodine-containing disinfectant prepared in the step (2.2) to obtain the iodine-containing disinfectant with the following component contents: 1.94 percent of elemental iodine, 1.59 percent of iodide (calculated by potassium iodide), 0.3 percent of citric acid, 10.0 percent of citric acid monoethyl ester, 14.1 percent of diethyl citrate, 0.1 percent of triethyl citrate, 54 percent of ethanol and 17.9 percent of water. The above results add up to 99.93%, which may be due to errors, or a small amount of material may not be detected. Since both monoethyl citrate and diethyl citrate contain carboxyl groups, both are normalized to citric acid for calculation when titrating with sodium hydroxide, resulting in inconsistency between the results of the titration of carboxylic acid and the results of the compositional analysis.

2.4 after the disinfection solution is subjected to 10 circulation accelerated stabilization experiments at 80 ℃, the contents of elemental iodine, carboxylic acid and iodide in the disinfection solution are respectively tested according to the detection methods of the elemental iodine, the iodide and the carboxylic acid at room temperature as follows: 1.95%, 1.56% and 9.55%. Compared with the originally prepared disinfectant, the change rates of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 0.51%, 1.27% and 2.55%, and the change rate is less than 5%, which meets the product stability standard.

2.5 disinfectant is prepared according to the balanced disinfectant components determined as follows:

the preparation is carried out according to 1000 g:

dissolving 15.9g of potassium iodide in 25g of water, adding 19.4g of elemental iodine, dissolving 3.0g of citric acid, 100g of monoethyl citrate, 141% of diethyl citrate and 1% of triethyl citrate in 540g of ethanol, uniformly mixing the solution containing the iodine and the potassium iodide with the ethanol solution containing the acid and the ester, and adding the residual water of 154g under stirring to obtain the iodine-containing disinfectant with stable components. The initial elemental iodine, iodide, and carboxylic acid were tested as: 1.93%, 1.60% and 9.81%; after 10 circulation accelerated stabilization experiments at 80 ℃, the contents of elemental iodine, iodide and carboxylic acid in the disinfectant tested at room temperature are respectively as follows: 1.90%, 1.64% and 9.49%; compared with the originally prepared disinfectant, the change values of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 1.55%, 2.50% and 3.26%, all less than 5%, and meets the product stability standard. However, it was also found that the stability of the above formulated sample was slightly inferior to that obtained directly by the above raw material stabilization by heating, which may be attributed to the accuracy of the component content for the component analysis after the equilibration, and further, a reaction product between the raw materials may not be detected in a small amount, which affects the stability between the components. The most probable reason is that a small amount of iodic acid compounds are generated by disproportionation reaction of water and iodine in the system and are not detected in measurement, and the cold splicing process lacks iodic acid compounds (iodic acid or iodate ions) which are balanced with elementary iodine, water, iodide, acid (hydrogen ions) and the like due to no addition of the substances, so that the balance of the system is shifted, and the content of the iodine elementary substances, the iodide, carboxylic acid and the like is slightly changed. But overall the stability of the formulation is less affected because of the lower amount of water.

Example 3:

3.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

10% of acetic acid, 2% of elemental iodine, 3% of potassium iodide, 15% of ethyl acetate, 52% of ethanol and 18% of water.

3.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking a small amount of water of about 25g, adding 30g of potassium iodide for dissolving, and then adding 20g of elementary iodine to completely dissolve the iodine to obtain an A3 solution; dissolving 100g of acetic acid and 150g of ethyl acetate in 520g of ethanol to obtain a B3 solution; adding the B3 solution into the A3 solution under stirring, and adding the residual water of about 155g under stirring to obtain a uniform solution, namely a disinfectant raw material solution; the raw material liquid is stirred and reacted for 8 hours at the temperature of 80 ℃, and then the material liquid is placed and cooled, so that the iodine-containing disinfectant with long-term component stability is obtained.

3.3 the iodine simple substance, the iodide and the acetic acid in the iodine-containing disinfectant prepared by the method 3.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is as follows: 1.95% of elementary iodine, 3.08% of iodide (calculated as potassium iodide) and 7.4% of carboxylic acid (calculated as acetic acid).

And 3.2, performing full component analysis on the iodine-containing disinfectant to obtain the iodine-containing disinfectant with the following component contents: 1.94 percent of elementary iodine, 3.10 percent of iodide (calculated as potassium iodide), 7.3 percent of acetic acid, 19.0 percent of ethyl acetate, 50.0 percent of ethanol and 18.8 percent of water. The sum of the above results is 100.14%, which may be due to errors, or a small amount of material may not be detected.

The above content measurement results are consistent with the results of titration measurement within the error range.

3.4 after the disinfection solution is subjected to 10 circulation accelerated stabilization experiments at 80 ℃, the contents of the elemental iodine, the iodide and the carboxylic acid in the disinfection solution are respectively tested according to the detection methods of the elemental iodine, the iodide and the carboxylic acid at room temperature as follows: 1.93%, 3.12%, 7.38%; compared with the originally prepared disinfectant, the change values of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 1.03%, 1.30% and 0.27%, all less than 5%, and meets the product stability standard.

3.5 preparing the disinfectant according to the balanced disinfectant components determined as follows:

the preparation is carried out according to 1000 g:

dissolving 310g of potassium iodide in 50g of water, then adding 19.4g of elemental iodine, dissolving 73.0g of acetic acid and 190g of ethyl acetate in 500g of ethanol, uniformly mixing the solution containing the iodine and the potassium iodide with the ethanol solution containing the acid and the ester, and then adding the residual 138g of water under the stirring state to obtain the iodine-containing disinfectant with stable components. The initial elemental iodine, iodide, and carboxylic acid were tested as: 1.94%, 3.10%, 7.42%; after 10 circulation accelerated stabilization experiments at 80 ℃, the contents of elemental iodine, iodide and carboxylic acid in the disinfectant tested at room temperature are respectively as follows: 1.90%, 3.15%, 7.23%; compared with the originally prepared disinfectant, the change rates of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 2.06 percent, 1.61 percent and 2.56 percent, which are all less than 5 percent, and meet the standard of product stability.

Example 4:

4.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

15% of citric acid, 3% of elementary iodine, 2% of sodium iodide, 60% of glycerol and 20% of water.

4.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking a small amount of water about 20g, adding 20g of sodium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A4 solution; dissolving 200g of citric acid in 130g of water, and slowly adding the citric acid into glycerol to obtain a B4 solution; adding the B4 solution into the A4 solution under stirring to obtain a uniform solution, namely disinfectant raw material solution; the raw material solution is reacted for 5 hours at 100 ℃ under the stirring state, and then is placed and cooled to obtain the iodine-containing disinfectant with long-term component stability.

4.3 the iodine simple substance, the iodide and the citric acid in the iodine-containing disinfectant prepared by the step 4.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is as follows: 2.90 percent of elementary iodine, 2.13 percent of iodide (calculated as sodium iodide) and 6.4 percent of carboxylic acid (calculated as citric acid).

And 3.2, performing full component analysis on the iodine-containing disinfectant to obtain the iodine-containing disinfectant with the following component contents: 2.92 percent of elemental iodine, 2.15 percent of iodide (calculated as sodium iodide), 0.1 percent of citric acid, 48 percent of glycerol, 22.4 percent of water and 24 to 26 percent of esterification product of citric acid and glycerol.

4.4, after the disinfectant is subjected to the accelerated test at 80 ℃ for 10 cycles, and the accelerated stability test, the contents of the elemental iodine, the iodide and the carboxylic acid in the disinfectant are respectively tested according to the detection methods of the elemental iodine, the iodide and the carboxylic acid at room temperature as follows: 2.88%, 2.17%, 6.23%; compared with the originally prepared disinfectant, the change values of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 0.69%, 1.88% and 2.66%, all less than 5%, and meet the product stability standard.

Example 5:

5.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

2% of elemental iodine, 1% of tetrabutylammonium iodide, 45% of ethanol, 30% of ethyl acetate and 22% of water.

5.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking a small amount of water of about 25g, adding 10g of tetrabutylammonium iodide for dissolving, and then adding 20g of elementary iodine to completely dissolve the elementary iodine to obtain an A5 solution; then 450g of ethanol is mixed with 300g of ethyl acetate to obtain B5 solution; adding the B5 solution into the A5 solution under stirring, and then adding the balance of about 195g of water under stirring to obtain a uniform solution, namely disinfectant raw material solution; and heating the raw material liquid to 80 ℃ for reaction for 14h, and cooling to ensure that the reaction reaches a balanced state, thereby obtaining the iodine-containing disinfectant with stable components.

5.3 the iodine simple substance, the iodide and the acetic acid in the iodine-containing disinfectant prepared by the step 5.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is that: 1.97 percent of elementary iodine, 1.05 percent of iodide (calculated as tetrabutylammonium iodide), 7.6 percent of carboxylic acid (calculated as acetic acid),

5.4, the disinfectant is subjected to 10 cycles of accelerated experiments at 80 ℃, and after the accelerated stabilization experiments, the contents of the elemental iodine, the iodide and the carboxylic acid in the disinfectant are respectively tested according to the detection methods of the elemental iodine, the iodide and the carboxylic acid at room temperature: 1.95%, 1.03%, 7.50%; compared with the originally prepared disinfectant, the change rates of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 1.02%, 1.90% and 1.32%, all less than 5%, and meets the product stability standard.

Example 6:

6.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

2.5 percent of elementary iodine, 2.0 percent of hexadecyl trimethyl ammonium iodide, 20 percent of acetic acid, 54 percent of ethyl acetate and about 21.5 percent of water.

6.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking a small amount of water of about 25g, adding 10g of hexadecyl trimethyl ammonium iodide for dissolving, and then adding 25g of elementary iodine to completely dissolve the iodine to obtain an A6 solution; mixing acetic acid and ethyl acetate to obtain a B6 solution; adding the B6 solution into the A6 solution under stirring, and then adding the balance of water into the mixture under stirring to obtain a disinfectant raw material solution; and heating the raw material liquid to 80 ℃ under a stirring state, reacting for 8h, and cooling to make the reaction reach a balanced state, thereby obtaining the iodine-containing disinfectant with stable components.

6.3 the iodine simple substance, the iodide and the acetic acid in the iodine-containing disinfectant prepared by the 6.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is that: 2.45 percent of elementary iodine, 2.09 percent of iodide (calculated as hexadecyl trimethyl ammonium iodide), 36.9 percent of carboxylic acid (calculated as acetic acid),

the iodine-containing disinfectant prepared by 6.2 is subjected to full component analysis, and the obtained iodine-containing disinfectant comprises the following components in percentage by weight: 2.46 percent of elementary iodine, 2.09 percent of iodide (calculated by cetyl trimethyl ammonium iodide), 37.0 percent of acetic acid, 29.2 percent of ethyl acetate, 13 percent of ethanol and 16.5 percent of water.

6.4, testing the contents of the elementary iodine, the iodide and the carboxylic acid of the disinfectant at room temperature according to the detection methods of the elementary iodine, the iodide and the carboxylic acid, wherein the contents of the elementary iodine, the iodide and the carboxylic acid of the disinfectant are respectively as follows: 2.4%, 2.14%, 35.9%; compared with the originally prepared disinfectant, the change rates of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 2.04%, 2.39% and 2.71%, all less than 5%, and meet the product stability standard.

Example 7:

7.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

8% of elementary iodine, 5% of Gemini quaternary ammonium iodide (diquaternary ammonium iodide) N, N, N ', N ' -tetramethyl-N, N ' -didodecyl-1, 2-ethanediammonium iodide, 60% of ethyl acetate and 27% of water.

7.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking a small amount of about 150g of water, adding 50g of the bis-quaternary ammonium iodide salt for dissolving, adding 80g of elemental iodine, adding the balance of about 120g of water after the iodine is completely dissolved, and finally adding 600g of ethyl acetate to obtain a disinfectant raw material solution; and heating the raw material liquid to 80 ℃, stirring and reacting for 8 hours, and cooling to ensure that the reaction reaches a balanced state, thereby obtaining the iodine-containing disinfectant with stable components.

7.3 the iodine simple substance, the iodide and the acetic acid in the iodine-containing disinfectant prepared by the method 7.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is as follows: 7.92 percent of elementary iodine, 5.09 percent of iodide (calculated as N, N, N ', N ' -tetramethyl-N, N ' -didodecyl-1, 2-ethanediammonium iodide), 25.1 percent of carboxylic acid (calculated as acetic acid),

7.4, testing the contents of the elementary iodine, the iodide and the carboxylic acid of the disinfectant at room temperature according to the detection methods of the elementary iodine, the iodide and the carboxylic acid, wherein the contents of the elementary iodine, the iodide and the carboxylic acid of the disinfectant are respectively as follows: 7.9%, 5.10%, 24.9%; compared with the originally prepared disinfectant, the change rates of the simple substance iodine, the carboxylic acid and the iodide of the disinfectant after the accelerated stabilization experiment are respectively 0.25%, 0.20% and 0.80%, and are all less than 5%, so that the product stability standard is met.

Example 8

8.1 the raw material components for preparing the iodine-containing disinfectant and the dosage thereof are as follows:

20% of acetic acid, 2% of elemental iodine, 3% of potassium iodide, 60% of ethanol and 15% of water.

8.2 taking 1000g of raw material liquid as an example, the preparation method comprises the following steps:

taking a small amount of water of about 25g, adding 30g of potassium iodide for dissolving, and then adding 20g of elementary iodine to completely dissolve the iodine to obtain an A8 solution; dissolving 200g of acetic acid in 600g of ethanol to obtain a B8 solution; adding the B8 solution into the A8 solution under stirring, and adding the rest 125g of water under stirring to obtain a uniform solution, namely disinfectant raw material solution; the raw material liquid is stirred and reacted for 8 hours at the temperature of 80 ℃, and then the material liquid is placed and cooled, so that the iodine-containing disinfectant with long-term component stability is obtained.

8.3 the iodine simple substance, the iodide and the acetic acid in the iodine-containing disinfectant prepared by the method 8.2 are measured according to the detection method of the simple substance iodine, the iodide and the carboxylic acid, and the result is as follows: 1.94% of elementary iodine, 3.08% of iodide (calculated as potassium iodide) and 7.5% of carboxylic acid (calculated as acetic acid).

8.4, testing the contents of the elementary iodine, the iodide and the carboxylic acid of the disinfectant at room temperature according to the detection methods of the elementary iodine, the iodide and the carboxylic acid, wherein the contents of the elementary iodine, the iodide and the carboxylic acid of the disinfectant are respectively as follows: 1.92%, 3.12% and 7.42%; compared with the originally prepared disinfectant, the change rates of the elemental iodine, the iodide and the carboxylic acid of the disinfectant after the accelerated stabilization experiment are respectively as follows: 1.03%, 1.30% and 1.07%, all less than 5%, and meets the product stability standard.

Comparing the results of example 8 with those of example 3, we can see that the results after the two experiments are stabilized are similar, the change of the iodine simple substance and the potassium iodide is not very different, and the two experiments can be basically considered as consistent within the error range; however, for the change of the acid content, for example 8, ethyl acetate was not added to the starting material, and the acid content change amount was reduced by 62.5% with respect to the acetic acid added; in contrast, in example 3, since 15% of ethyl acetate was added to the starting raw material, the decrease in acetic acid was significantly suppressed by 26% from the amount of acetic acid initially added; when an ester in equilibrium with the system components is added, the rate of change of the added acid can be made low, and a product that can satisfy the long-term stability of the components can be obtained. However, it can be seen from the above results that the addition of ester always serves to stabilize the decrease of carboxylic acid in the system with ester compared to the system without ester, and if the amount of carboxylic acid is stabilized, as in the case of the cold-splicing process, the component content is substantially maintained without significant change; for systems where no specific equilibrium state is known, the addition of ester is not just the amount of ester that the system can stabilize, but if added, it is always more stable than if not added.

Comparative example 1

Three samples (preparation without iodine complex) of a commercially available iodine-containing disinfectant, in which the labeled iodine content was 2.0% and the acid content was 10%, were taken and subjected to a stability test, and the carboxylic acid content (all acids were normalized to the acetic acid content), the iodine content, and the iodide (all iodides were normalized to the potassium iodide content) content were measured before the stability test, and then an accelerated test was carried out with reference to the above conditions of the test for accelerated stability at 80 ℃ and the carboxylic acid content (all acids were normalized to the acetic acid content), the iodine content, and the iodide (all iodides were normalized to the potassium iodide content) content were measured after 10 cycles.

The specific results are as follows:

as can be seen from the table, the content of each component in the iodine-containing disinfectant sold in the market is greatly changed, particularly the content of acid is up to 66% at most and 13.5% at least; the iodine content is 33 percent at most and 1.6 percent at least; the iodine ion (calculated as potassium iodide, compared with the originally determined iodide) can reach 66% at the maximum and 2.5% at the minimum. Moreover, the difference between the actually measured component content before acceleration and the labeled amount is not large between the iodine-containing disinfectant with the number 1 and the iodine-containing disinfectant with the number 2 because the iodine-containing disinfectant with the number 2 is away from the factory shortly after the time interval; for the iodine-containing disinfectant of number 1, the change in iodine content and iodide after acceleration is relatively small, but the change in carboxylic acid content is very large; for the iodine-containing disinfectant of number 2, although the change of the acid content after acceleration is not obvious, the change of the elemental iodine and the iodide is large; for the iodine-containing disinfectant of sample No. 3 which has a long time before leaving factory, the content test value before acceleration is different from the marked amount, particularly, the acid content is obviously lower than the indicated amount, the acid content is still greatly reduced after acceleration, but compared with the iodine-containing disinfectant of sample No. 1, the acid change amount is slightly lower, but the difference is very large compared with the marked amount, and is about 57 percent lower. The above commercial products were not analyzed in detail, but they were estimated according to the previous research results of the inventors on the disinfectant in relation to the amount of water and the amount of alcohols in the system. The iodine-containing disinfectant with the number 1 is likely to have less water and more alcohols; the opposite is true for the iodine containing disinfectant of number 2, which may be a lower alcohol species and a higher water amount; the iodine-containing disinfectant for No. 3 may be similar to the iodine-containing disinfectant for No. 1, but because it has been shipped for a while, the acid content has decreased to some extent during storage at room temperature, but has not yet reached equilibrium, thus causing a further decrease in the acid content after the accelerated test.

The above results also illustrate the inventive and effective use of the disinfectant and method of preparation of the present application.

The method for measuring the disinfection and sterilization effects of the iodine-containing disinfectant formula specifically refers to the method described in patent No. CN201010163683.4 (title of the invention: iodine citrate disinfectant and 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 the stock solution of the disinfectant according to the iodine content measured during preparation (0 day) at 20 ℃ according to the effective iodine content of 100mg/L after dilution, wherein the diluent acts on escherichia coli and staphylococcus aureus for 3min respectively, and the sterilization logarithm value is more than or equal to 5.0; diluting stock solution of disinfectant according to iodine content measured in preparation (0 day) with effective iodine content of 500mg/L, wherein the diluted solution acts on Bacillus subtilis black variant spore for 5min, and bactericidal logarithm value is not less than 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.