CN112640913A - Iodine-containing disinfectant with long-term component stability and preparation method thereof - Google Patents

Iodine-containing disinfectant with long-term component stability and preparation method thereof Download PDF

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CN112640913A
CN112640913A CN202011613375.7A CN202011613375A CN112640913A CN 112640913 A CN112640913 A CN 112640913A CN 202011613375 A CN202011613375 A CN 202011613375A CN 112640913 A CN112640913 A CN 112640913A
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acid
iodine
iodide
water
solution
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CN112640913B (en
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王振兴
符德文
谭志坚
刘肖娟
赵一阳
黎剑坤
陈艺青
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Foshan Standard Bio Tech Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/12—Iodine, e.g. iodophors; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/02—Acyclic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system

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  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

The invention discloses an iodine-containing disinfectant with long-term component stability, which comprises the following components in parts by weight: 0.1-10% of elementary iodine, 0.1-10% of iodide, 0.1-20% of carboxylic acid, 2-30% of carboxylic ester, 40-80% of alcohol and 5-30% of water, wherein the iodide is composed of iodine negative ions and hydrogen ions, metal cations or ammonium ions or quaternary ammonium ions. The content of each component in the iodine-containing disinfectant does not change obviously even after long-term storage, and the iodine-containing disinfectant can maintain a higher shelf life so as to meet the quality standard.

Description

Iodine-containing disinfectant with long-term component stability and preparation method thereof
Technical Field
The invention belongs to the field of disinfectants, and particularly relates to an iodine-containing disinfectant with long-term component stability.
Background
The repeated occurrence of food safety events, the spread of diseases of people and livestock, the development of large-scale cultivation and the continuous strengthening of the medication concept of 'prevention over treatment' of people are urgently needed, and a green safe disinfectant for improving the feeding environment and preventing diseases is urgently needed, so that the disinfectant not only can effectively kill viruses, but also has no stress effect on the livestock, the poultry and aquatic products.
Elemental iodine has been found for over two centuries, while the use of iodine for germicidal disinfection has been a century ago and numerous iodine-containing disinfectants have been developed. The iodine-containing disinfectant has the advantages of wide antimicrobial spectrum, low tissue toxicity and wide application; the sterilization and disinfection range relates to clinical, sanitary, daily life, livestock and poultry breeding, aquaculture, public places, drinking water and the like; iodine sterilization and disinfection products of different types, different formulations and different efficacies are widely applied to various practical occasions, such as disinfection of human skin, wound surface, mucosal surface, surgical instruments, pond water and drinking water, sanitary treatment of tableware and the like.
Particularly, the iodine can show more excellent disinfection and sterilization effects under the coordination of some substances which are acidic and have certain disinfection and sterilization effects. For example, citric acid (also known as citric acid), salicylic acid, and the like are commonly used as iodine disinfectants. As the Chinese invention patent application number: 201010163683.4, the title of the invention "citric acid iodine disinfectant and preparation method" discloses a citric acid iodine disinfectant; chinese invention patent application no: 201010163672.6, the invention discloses a salicylic acid iodine disinfectant and a preparation method thereof, which all have good disinfection and sterilization effects.
In order to improve the disinfection and sterilization effect of the iodine-containing disinfectant, alcohol substances can be further added. For example, ethanol, which can be used as a disinfectant by itself, has a mechanism of disinfection that a certain concentration of ethanol can denature proteins in bacteria; and the ethanol can make the disinfectant more easily dispersed on the surface of the object to be disinfected, thereby improving the disinfection effect.
On the other hand, due to the problem of solubility of elemental iodine, the iodine-containing disinfectants are generally prepared by dissolving elemental iodine in a solution of iodide to promote the dissolution of elemental iodine. Such as potassium iodide, the dissolution rate and the dissolution amount of iodine can be greatly promoted by the aqueous solution of the potassium iodide, and the mechanism is I2+I-＝I3 -And I is3 -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. Since potassium iodide and other substances generally have a high solubility in water, a solution of potassium iodide and other substances is usually accelerated by adding an appropriate amount of water in order to dissolve the potassium iodide and other substances.
The existing iodine-containing disinfectant containing organic acid generally contains elementary iodine, iodide, water, alcohol and carboxylic acid, and the formula has a good disinfection and sterilization effect; but at the same time, the composition of the iodine-containing disinfectant product is changed after the iodine-containing disinfectant product is stored for a long time, which is mainly shown in that the content of elemental iodine and/or the content of carboxylic acid are reduced, the integral stability of the formula is influenced, and the fluctuation of the disinfection and sterilization effect to a certain extent is also caused. Therefore, the formula with longer storage stability, particularly the formula with longer stability for the content of elemental iodine and the content of acid, has more practical significance for the production, storage, transportation and use of the iodine-containing disinfectant.
Disclosure of Invention
The invention aims to provide a novel disinfectant with long-term component stability, which has the characteristics of wide bactericidal spectrum, strong bactericidal capacity, high action speed, good stability, safety to people and animals and low environmental pollution degree, and particularly has long-term component stability, and the component stability and the disinfection and sterilization effect are not influenced even after long-term storage or obvious temperature change.
The invention adopts the following technical scheme to realize the purpose:
an iodine-containing disinfectant with long-term component stability, which comprises the following components by mass: 0.1-10% of elementary iodine, 0.1-10% of iodide, 0.1-20% of carboxylic acid, 2-30% of carboxylic ester, 40-80% of alcohol and 5-30% of water, wherein the iodide is composed of iodine negative ions and hydrogen ions or metal cations or ammonium ions or quaternary ammonium ions.
The composition may also include reactants resulting from the interaction of the components (e.g., iodic acid or its salts, or possibly iodinated products of the above organic materials, etc.), but in a total amount not exceeding 2% of the total formulation; the possible generation of iodic acid or iodate does not exceed 2 percent of the total mass of elemental iodine and iodide in the system, so the influence on the stability of the formula is small.
Preferably, the iodine-containing disinfectant comprises the following components in percentage by mass: 0.5-4% of elementary iodine, 0.5-5% of iodide, 0.1-20% of carboxylic acid, 5-30% of carboxylic ester, 40-70% of alcohol and 5-25% of water.
More preferably, the iodine-containing disinfectant comprises the following components in percentage by mass: 1-3% of elementary iodine, 1-3% of iodide, 0.1-15% of carboxylic acid, 5-25% of carboxylic ester, 48-65% of alcohol and 8-22% of water.
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 above-mentioned mono-quaternary ammonium iodide salt is selected from one or more mixtures of octadecyl trimethyl ammonium iodide, hexadecyl trimethyl ammonium iodide, tetradecyl trimethyl ammonium iodide, dodecyl trimethyl ammonium iodide, decyl trimethyl ammonium iodide, octyl trimethyl ammonium iodide, benzyl trimethyl ammonium iodide and tetrabutyl ammonium iodide.
Preferably, the carboxylic acid is selected from one or more of citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentanedioic acid, 1,3, 5-cyclohexanetricarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid, and gallic acid.
More preferably, the carboxylic acid is selected from one or more of acetic acid, citric acid, salicylic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid and 1,3, 5-cyclohexanetricarboxylic acid.
Preferably, the alcohol is selected from alcohol with less than 10 carbon atoms in the molecule, polyethylene glycol 200 and polyethylene glycol 300.
Preferably, the 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.
More preferably, the alcohol is selected from the group consisting of ethanol, n-propanol, ethylene glycol, diethylene glycol, triethylene 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 the group consisting of citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentanetricacid, 1,3, 5-cyclohexanetricarboxylic acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid or gallic acid in combination with one or more carboxylic esters of 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, salicylic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid or 1,3, 5-cyclohexanetricarboxylic acid in admixture with one or more carboxylic acid esters of ethanol, n-propanol, diethylene glycol, triethylene glycol, glycerol or pentaerythritol.
The invention also provides a preparation method of the iodine-containing disinfectant, which comprises the following steps:
(1) dissolving iodide in water, alcohol or the mixed solution of water and alcohol, and dissolving simple substance iodine in the iodide solution to obtain a solution containing iodide and simple substance iodine;
(2) dissolving carboxylic acid and carboxylic ester in water, alcohol or a mixed solution of water and alcohol to prepare a solution containing the carboxylic acid and the carboxylic ester;
(3) mixing the solution of the step (2) with the solution of the step (1);
(4) and (4) adding the rest water into the mixed solution obtained in the step (3) and uniformly mixing to obtain the iodine-containing disinfectant.
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 also provides a preparation method of the iodine-containing disinfectant, which comprises the following steps:
(1) dissolving iodide in water, alcohol or a mixed solution of water and alcohol, and then dissolving elementary iodine in the iodide solution to prepare a solution containing iodide and elementary iodine;
(2) dissolving carboxylic acid in water, alcohol or water-alcohol mixed solvent;
(3) dissolving carboxylic ester in the carboxylic acid solution in the step (2), and mixing with the solution containing iodide and elemental iodine in the step (1); or
Dissolving carboxylic ester in water, alcohol or a mixed solution of water and alcohol, mixing with the solution of acid in the step (2), and finally mixing with the solution containing iodide and elemental iodine in the step (1);
(4) and (4) adding the rest water into the mixed solution obtained in the step (3) and uniformly mixing.
The preparation method of the iodine-containing disinfectant can also be used for mixing the raw materials according to the principle of solubility of the raw materials in a reasonable preparation sequence.
Preferably, in the above preparation method, one or some of the components are selected to be used in a part of the amount, and then the rest part is added.
The iodine-containing disinfectant with long-term component stability can be directly used for disinfection, and can also be diluted by water for disinfection. When the disinfectant is diluted by water and used for disinfection, the disinfectant can be directly added into water to be diluted for dilution, preferably 50-1000 times, and disinfection can be carried out by soaking, spraying and other modes.
Compared with the prior art, the method has the following beneficial effects:
the components of the iodine-containing disinfectant form a balanced system, particularly the components of acid, alcohol, water and ester in the system and the components of the components are mutually contained and interacted under the condition of the amount of the components, and the iodine-containing disinfectant has long-term stability. Even after long-term storage or obvious temperature change, the composition content does not change obviously, and the shelf life is longer. Compared with a system without ester as a stabilizer, the stability of the ester stabilizer is obviously improved under the conditions of the addition amount and the formula proportion of the ester stabilizer.
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)-Unless otherwise specified in this application, iodine anions are all referred to as I-) With hydrogen ions, metal cations or ammonium ions or quaternary ammonium ions. Can use XIyWherein X represents a hydrogen ion, a metal cation or an ammonium ion or a quaternary ammonium ion, and I represents an iodide anion (I)-) And y represents the number of charges carried by a hydrogen ion or a metal cation or an ammonium or quaternary ammonium ion.
In the description of the present invention, "monoquaternary ammonium iodide" refers to an iodide composed of a monoquaternary ammonium cation and an iodide anion, 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 long-term component stability comprises the following components: 1) elemental iodine, 2) iodine anion (I)-) And iodide consisting of hydrogen ions or metal cations or ammonium ions or quaternary ammonium ions, 3) carboxylic acid, 4) alcohol, 5) carboxylic ester and 6) water. The iodine-containing disinfectant also comprises reactants generated by the interaction of the components (such as iodic acid or salt thereof, or possible iodo products of the above organic raw materials, and the like), but the total amount of the reactants does not exceed 2 percent of the total amount of the formula; the possible generation of iodic acid or iodate (calculated by iodic acid) is not more than 2 percent of the total mass of elemental iodine and iodide in the system, so that the possible generation of iodic acid compounds has less influence on the stability of the formula.
The elementary iodine in the iodine-containing disinfectant is a main component with the disinfection effect. In order to keep better disinfection and sterilization effects and better storage stability, the mass percentage of the elemental iodine in the iodine-containing disinfectant is 0.1-10%, more preferably 0.5-4%, and still more preferably 1-3%.
The iodide in the iodine-containing disinfectant is a cosolvent of iodine, so that the dissolving amount of the iodine is increased, and the dissolving speed of the iodine is increased. Because the solubility of elemental iodine in water is very low, in order to improve the solubility of elemental iodine in aqueous solution and increase the dissolution rate, which is beneficial to the preparation process, iodide is generally required to be added as a cosolvent. Because of I in solution-The presence of (A) promotes I2+I-＝I3 -Of the reaction of (a) and (b), and I3 -The iodine is more soluble, so that the solubility of the elemental iodine in water is greatly improved and even higher than that of the elemental iodine in ethanol. For example, potassium iodide can be dissolved in water or ethanol, and iodine is added into the solution of potassium iodide, so that the iodine can be more easily dissolved and dispersed in the system; the ammonium iodide can also be directly dissolved in alcohol, and also can be dissolved in water, or can also be dissolved in a mixed solvent of water and ethanol, and the iodine can be added into the solution to quickly dissolve the elemental iodine, and the dissolving amount is large.
In addition, the iodide plays a role in stabilizing the content of elemental iodine, in addition to improving the solubility of elemental iodine in an aqueous system or an alcohol solvent system.
In the present invention, the iodide is selected from iodides that are readily soluble in water and/or alcohol, for example, potassium iodide, sodium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide, or quaternary ammonium iodide salt.
When iodide XIyWhen it represents a quaternary ammonium iodide salt, 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. For example, y is equal to 1, then a quaternary ammonium salt is represented; y is equal to 2, then the quaternary ammonium salt is represented, and the quaternary ammonium salt contains two quaternary ammonium structures; y is equal to 3 and represents a tri-quaternary ammonium salt containing three quaternary ammonium structures; and so on. In the present invention, y is preferably 5 or less. Iodide XI2Can represent double quaternary ammonium iodide (iodide consisting of double quaternary ammonium radical ion and iodine negative ion, wherein the double quaternary ammonium radical ion contains two quaternary ammonium structures), iodide XI3Can represent tri-quaternary ammonium iodide salt, iodide XIy(y is an integer greater than 3) represents a polyquaternary ammonium iodide salt or a hyperbranched quaternary ammonium iodide salt. The quaternary ammonium iodide salt of the present invention may also be a single quaternary ammonium iodide salt or a combination thereof or a combination of different types of quaternary ammonium iodide salts of the above plural types of quaternary ammonium salts.
Iodide XI represents a monoquaternary ammonium iodide salt (iodide of a monoquaternary ammonium ion with an iodide anion). In a preferred embodiment of the invention, the quaternary ammonium iodide salt is R1R2R3R4N+I-Wherein R is1R2R3R4N+Represents a single quaternary ammonium cation, 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 iodine-containing disinfectant, an acidic medium environment is mainly provided by carboxylic acid, so that the disinfection and sterilization effects of iodine are improved; and the disinfectant has certain disinfection and sterilization functions, so that the disinfection and sterilization effects of the disinfectant are further improved. Although inorganic acids such as sulfuric acid, phosphoric acid and the like can also play a role in maintaining the acidic environment of the system, carboxylic acids are selected from the iodine-containing disinfectants of the invention in consideration of biocompatibility, use safety and the like, because the carboxylic acids are milder in nature and better in biocompatibility than the inorganic acids, and iodine can play a more excellent disinfection and sterilization effect in an acidic medium environment, so that the effect of adding one to two is achieved.
In the description of the present invention, the carboxylic acid is selected from organic carboxylic acids having a certain water solubility and/or alcohol and/or ester solubility, including but not limited to citric acid (citric acid), salicylic acid (o-hydroxybenzoic acid), benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic 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, n-butyric acid, lactic acid, gallic acid or binary or polybasic mixtures thereof;
from the viewpoint of water solubility, alcohol solubility, and acidity and its own sterilizing effect, acetic acid, citric acid, salicylic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid, and 1,3, 5-cyclohexanetricarboxylic acid are more preferable.
The carboxylic ester in the iodine-containing disinfectant is mainly used as a stabilizing agent of carboxylic acid, so that the stability of the content of the carboxylic acid in a system is maintained, and the effect of maintaining the pH stability of the system is achieved. The carboxylic acid ester component is also a difference between the iodine disinfectant formulations of the present invention and conventional iodine disinfectant formulations. The carboxylic acid ester in the iodine-containing disinfectant of the present invention is preferably a carboxylic acid ester formed from a carboxylic acid used in the iodine-containing disinfectant and an alcohol used in the iodine-containing disinfectant.
The inventor finds that the effective contents of carboxylic acid and alcohol in an iodine-containing disinfectant system are reduced due to esterification reaction of alcohol and carboxylic acid in the iodine-containing disinfectant, and the reduction of the content of the carboxylic acid influences the pH value of the system, which further influences the content of elemental iodine. The inventors have found that the decrease in elemental iodine content is mainly due to the reversible reaction of iodine with water:
Figure BDA0002875611900000081
or
Figure BDA0002875611900000082
The change of the pH of the system and the change of the water amount cause the equilibrium reaction to move rightwards to compensate the trend of the reduction of the acid content and the increase of the water amount, and the process can cause the reduction of the content of the elementary iodine. And the reduction of the content of the elemental iodine directly influences the disinfection and sterilization effect of the whole disinfectant. In the range of the components and the proportion thereof, the amount of water is relatively small, and the amount of alcohols, esters and the like is relatively large, so that the amount of change of the iodine content of the system caused by the reaction is small, and in actual tests, the iodine content and the change of iodide can be controlled within 5 percent, which is also an important reason for controlling the amount of small water and large amount of alcohol and/or ester.
On the other hand, in the esterification reaction, the reaction degree is large under the conditions of less water and more alcohol, and the instability (mainly, the decrease) of the carboxylic acid content becomes a main cause of the system instability.
In the reaction for obtaining an esterification product by the reaction of an acid and an alcohol, a water-carrying agent is generally used so that the esterification reaction proceeds in the direction of ester formation, because the reaction is a reversible reaction, and the water produced by the reaction is reduced so that the equilibrium shifts in the direction of ester formation and water formation. The equation for the esterification reaction can be simply expressed as:
Figure BDA0002875611900000083
in this reversible reaction, when the contents of the carboxylic acid and the alcohol are high and the contents of the ester are low or no ester is contained, the reaction equilibrium shifts in the direction of producing the ester and water, and when the contents of the ester are high and the contents of the carboxylic acid and the alcohol are low, the reaction equilibrium shifts in the direction of producing the carboxylic acid and the alcohol. This is the main reason for the reduction in carboxylic acid content in disinfectant systems containing only alcohol and carboxylic acid and no ester. Although the presence of water reduces the degree of esterification to some extent, the absence of esters tends to reduce the carboxylic acid content. Although the reaction of acid and alcohol to generate ester has higher activation energy and is difficult to occur in the absence of a catalyst, the activation energy of the reaction is greatly reduced in the presence of the catalyst, and the disinfection component, elemental iodine, is the catalyst capable of catalyzing the esterification reaction. Therefore, in the iodine disinfectant system containing alcohol and carboxylic acid, the alcohol and the carboxylic acid can react to generate ester at ambient temperature under the catalysis of the disinfectant component, namely the elemental iodine, so that the content of the carboxylic acid is reduced. Therefore, in the iodine-containing disinfectant, the principle that the ester can stabilize the content of the components in the formula of the iodine-containing disinfectant is that the addition of the ester enables the esterification reaction among acid, alcohol and water in the system to be basically balanced, so that the content of carboxylic acid and alcohol in the formula of the iodine-containing disinfectant is not changed, or the balance moving trend or degree of the esterification reaction is reduced, so that the reduction of the content of carboxylic acid and alcohol in the formula of the iodine-containing disinfectant is greatly inhibited, and the stability of the components of the system is obviously improved. The content of carboxylic acid being stable, i.e. H in the system+The content is stable, which will further reduce the amount of change in the iodine content.
According to the above-mentioned reversible esterification reaction, although theoretically, the amount of carboxylic ester should be calculated from the equilibrium constant of the esterification reaction of carboxylic acid and alcohol under the condition of iodine catalysis at ambient temperature, the amount of carboxylic acid and the amount of alcohol, the inventors found that in the disinfectant formulation of the present invention, in the case where the water content is 5-30% and the alcohol content is 40-80%, the ester can achieve a good effect of stabilizing the iodine content and carboxylic acid within the range of 2-30%, and the stability is remarkably better than that of the disinfectant without the addition of ester.
Further preferably, the amount of the carboxylic acid ester to be added is an amount which satisfies the corresponding esterification equilibrium with the carboxylic acid, alcohol and water in the system.
Elemental iodine has been reported as a catalyst for the reaction of carboxylic acids and alcohols to esters. Elemental iodine has been reported as a mild Lewis acid to catalyze the esterification and transesterification of carboxylic acids with alcohols, as described in K.Ramalinga, P.Vijayalakshmi, T.N.B.Kaimal.A. mil and effective method for esterification and transesterification of by iodine [ J ] Tetrahedron Letters,2002,43: 879-. However, the reaction of generating ester by catalyzing carboxylic acid and alcohol with elementary iodine and iodide ion at lower temperature is not reported. According to the studies of iodine-containing disinfectant formulations by the inventors, the esterification reaction of carboxylic acid and alcohol can occur even at room temperature in the presence of elemental iodine and iodide, as shown by the decrease in carboxylic acid content, and this process is accelerated to some extent with increasing temperature. The inventor surprisingly found that the addition of the ester to the iodine-containing disinfectant can enable the reaction of the carboxylic acid and the alcohol to generate the ester to reach a relative equilibrium state or more approach the equilibrium state of the esterification reaction in the disinfectant system, so that the contents of the carboxylic acid, the alcohol, the ester and the water in the disinfectant system are relatively stable, and the variation of each component is greatly reduced. Even if the ambient temperature changes, the balance of the esterification reaction in the disinfectant system slightly shifts, but the shift of the balance can still keep the variation of the composition of the iodine-containing disinfectant system in a very low range and meet the standard of product stability.
In addition, the esterification reaction reported in the above-mentioned document is determined by the esterification reaction concerned in the document, and the change of the content of iodine itself is not discussed at all, only considering the esterification reaction using iodine as a catalyst. In addition, in order to improve the yield of the ester and the conversion rate of the acid, water is not additionally added into the reaction system, and generally, a water-carrying agent is often added as the operation of the esterification reaction, so that the water content in the system is reduced, and the degree of the esterification reaction is improved. This is in contrast to the need to also include a certain amount of water in the present formulation. Therefore, the document does not suggest anything about the present invention, and the use of esterification reaction to keep the content of each component of the iodine-containing disinfectant of the present invention stable is found in the formulation research of the iodine-containing disinfectant carried out by the inventor, and the above-mentioned components are all indispensable components of the formulation of the iodine-containing disinfectant, and the amount of each component has a good stabilizing effect within the range defined by the present invention.
When the ester in the formula of the iodine-containing disinfectant is actually used, the ester is diluted, and hydrolysis reaction of the ester (namely, the balance of esterification reaction is moved leftwards) can occur along with the increase of water content, so that a small amount of carboxylic acid and alcohol are generated, and although the degree is not large, the ester also has positive effect on the disinfection and sterilization effects to a certain degree.
The alcohol in the iodine-containing disinfectant can be used as a solvent for dissolving acid and ester, iodine and iodide, and has certain disinfection and sterilization functions. More importantly, the alcohol is matched with other components to stabilize the content of the elemental iodine and inhibit the content of the elemental iodine from decreasing. Since, as a result of formulation studies, the inventors have surprisingly found that in comparative disinfectant formulations without alcohol, a decrease in elemental iodine content occurs simultaneously with an increase in iodide ion content, which severely affects the stability of the disinfectant product and the subsequent disinfecting and sterilizing effect. The mechanism by which alcohol inhibits the reduction of elemental iodine and the increase of iodide ions in the disinfectant formulation of the present invention is not well understood (this decrease in iodine and increase in potassium iodide content is not common in iodine-containing disinfectants, as described in Nixian, Wangqingfen, Liulinging, Caulifa, Chenglanshai. uncertainty analysis and stability study of iodine tincture content (J) pharmaceutical services and research, 20(3): 188-charge 192,201, see 192 page table 3), presumably is a result of interaction with other components in the system, such as acids, esters, etc., in the presence of alcohol. In summary, alcohol is critical in the formulation of the disinfectant with long term component stability, and this effect, which has not been revealed by previous literature, is an important innovation in the formulation of the present application.
Alcohols having greater water solubility and greater acid, ester solubility are preferred in the present invention. For example, alcohols having less than 10 carbons in the molecule, polyethylene glycol 200, polyethylene glycol 300. 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, pentaerythritol, benzyl alcohol, or mixtures thereof; 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 solution with long-term stability, methanol is not selected as the composition of the formula in the invention in consideration of the toxicity of methanol.
On one hand, the water in the iodine-containing disinfectant is used as a solvent for dissolving iodide, so that the dissolving amount and the dissolving speed of the elemental iodine are further improved. On the other hand, the balance of the esterification reaction is balanced, because the existence of a certain amount of water enables the balance of the reaction of the carboxylic acid and the alcohol to generate the ester to be maintained at a certain level, so that the disinfectant system can play a role in stabilizing the acid content of the component without adding a large amount of ester substances. The inventor finds that the content of iodine is obviously more stable when the amount of water is controlled to be 5-30%, particularly 5-25%, because the content of iodine is obviously changed due to the reaction of iodine and water when the amount of water is higher, the stability of the product of the elemental iodine is influenced; when the amount of water is too low, alcohol and carboxylic acid can be catalyzed by elemental iodine to generate carboxylic ester, so that the carboxylic acid content of the system is increased, and the content of elemental iodine is influenced.
The components in the iodine-containing disinfectant of the invention are mutually interacted and mutually coupled, which is indispensable. Under the condition of the substances and the proportion of each component, a complex and delicate balance system is obtained, and the components are mutually contained and interacted, so that the novel iodine-containing disinfectant with long-term stability is obtained. The composition of the system can not be obviously changed even after long-term placement, and the high shelf life can be maintained so as to meet the requirement of quality standard. Under the condition of temperature change, the buffering balance system of the iodine-containing disinfectant can change towards a certain direction, but the change is self-limiting, namely the variable is limited, and the content of each component of the disinfectant can be slightly changed even if the disinfectant is in a high-temperature state for a long time, so that the stable standard of product quality is met; more importantly, even after high temperature conditions (such as long-term transportation, such as summer shipping, etc.), the iodine-containing disinfectant of the present invention has a slight change in composition (which still fully satisfies the quality requirements), and then returns to the required storage conditions, the balance of the reversible reaction of the disinfectant system shifts such that the disinfectant composition returns substantially to the original state, resulting in a long-term product composition stability.
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: the product is precisely measured and weighed with 10ml, and is placed in an iodine bottle and titrated by sodium thiosulfate titration solution (0.1mol/L) until the solution is colorless. The elemental iodine content was calculated as follows: na (Na)2S2O3+I2＝Na2S4O6+2NaI. If the acid is poorly soluble in water, a suitable amount of ethanol may be added prior to titration.
Carboxylic acid: the acid amount of the system is determined by acid-base titration (the acid content is calculated by the added carboxylic acid, if a plurality of carboxylic acids exist in the system, the acid amount is calculated by a specified carboxylic acid) 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, weighing, placing in an iodine bottle, adding 10ml of water, adding 20ml of hydrochloric acid, titrating to yellow by using potassium iodate titration solution (0.05mol/L), adding 5ml of trichloromethane, continuing to titrate, and simultaneously strongly shaking until the 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 the titration, an appropriate amount of ethanol may be added before the titration to prevent precipitation. Calculated as potassium iodide, is not specified.
Example 1:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
2.0 percent of citric acid, 2.0 percent of elementary iodine, 1.5 percent of potassium iodide, 70.0 percent of ethanol, 8.0 percent of diethyl citrate and 16.5 percent of water.
Taking 1000g of disinfectant 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 A1 solution; dissolving 20g of citric acid and 80g of diethyl citrate in 700g of ethanol to obtain a B1 solution; adding the B1 solution into the A1 solution under stirring, fully stirring, and adding the balance of 140g of water under stirring to obtain a uniform solution.
Example 2:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
3.0 percent of citric acid, 2.0 percent of elementary iodine, 3.0 percent of sodium iodide, 65 percent of ethanol, 5.0 percent of citric acid monoethyl ester, 5.0 percent of diethyl citrate, 1.0 percent of triethyl citrate and 16 percent of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 25g, adding 30g of sodium iodide for dissolving, and then adding 20g of elementary iodine to completely dissolve the iodine to obtain an A2 solution; then dissolving 30g of citric acid, 50g of monoethyl citrate, 50g of diethyl citrate and 10g of triethyl citrate in 650g of ethanol to obtain a B2 solution; adding the B2 solution into the A2 solution under stirring, fully stirring, and adding 135g of the balance water under stirring to obtain a uniform solution.
Example 3:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
7.5% of acetic acid, 3.0% of elementary iodine, 3.0% of ammonium iodide, 49% of ethanol, 18.5% of ethyl acetate and 19% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 40g, adding 30g of ammonium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A3 solution; dissolving 75g of acetic acid and 185g of ethyl acetate in 490g of ethanol to obtain a B3 solution; adding the B3 solution into the A3 solution under stirring, fully stirring, and adding the balance of water of about 150g under stirring to obtain a uniform solution.
Example 4:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
10% of acetic acid, 2% of elemental iodine, 1.0% of tetrabutylammonium iodide, 55% of n-propanol, 20% of n-propyl acetate and 12% of water.
Taking 1000g of disinfectant 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 iodine to obtain an A4 solution; dissolving 100g of acetic acid and 200g of n-propyl acetate in 550g of n-propanol to obtain a B4 solution; adding the B4 solution into the A4 solution under stirring, fully stirring, and adding the balance of 95g of water under stirring to obtain a uniform solution.
Example 5:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
5% of salicylic acid, 3% of elemental iodine, 2% of potassium iodide, 75% of ethanol, 5% of ethyl salicylate and 10% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 25g, adding 20g of potassium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A5 solution; then 50g of salicylic acid and 50g of ethyl salicylate are dissolved in 750g of ethanol to obtain B5 solution; adding the B5 solution into the A5 solution under stirring, fully stirring, and adding the balance of 75g of water under stirring to obtain a uniform solution.
Example 6:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
5% of citric acid, 3% of elementary iodine, 2% of potassium iodide, 48% of ethanol, 10% of citric acid monoethyl ester, 10% of diethyl citrate and 22% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 25g, adding 20g of potassium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A6 solution; dissolving 50g of citric acid, 100g of citric acid monoethyl ester and 100g of diethyl citrate in 480g of ethanol to obtain a B6 solution; adding the B6 solution into the A6 solution under stirring, fully stirring, and adding the balance of 195g of water under stirring to obtain a uniform solution.
Example 7:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
10% of citric acid, 2% of acetic acid, 3% of elementary iodine, 2% of potassium iodide, 55% of ethanol, 10% of diethyl citrate, 10% of ethyl acetate and 8% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 25g, adding 20g of potassium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A7 solution; dissolving 100g of citric acid, 20g of acetic acid, 100g of diethyl citrate and 100g of ethyl acetate in 550g of ethanol to obtain a B7 solution; adding the B7 solution into the A7 solution under stirring, fully stirring, and adding the balance of 55g of water under stirring to obtain a uniform solution.
Example 8:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
10% of benzoic acid, 3% of elementary iodine, 2% of potassium iodide, 1% of hexadecyl trimethyl ammonium iodide, 60% of n-propyl alcohol, 10% of n-propyl benzoate and 14% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 35g, adding 20g of potassium iodide and 10g of hexadecyl trimethyl ammonium iodide for dissolving, and then adding 30g of simple substance iodine to completely dissolve the iodine to obtain an A8 solution; dissolving 100g of benzoic acid and 100g of n-propyl benzoate in 600g of n-propanol to obtain a B8 solution; adding the B8 solution into the A8 solution under stirring, fully stirring, and adding the balance of 105g of water under stirring to obtain a uniform solution.
Example 9:
the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
2% of citric acid, 2% of elemental iodine, 3% of potassium iodide, 60% of glycerol, 8% of citric acid monoglyceride, 5% of citric acid diglyceride and 20% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 25g, adding 30g of potassium iodide, and then adding 20g of elementary iodine to completely dissolve the iodine to obtain an A9 solution; dissolving 20g of citric acid in 100g of water, adding 600g of glycerol, and dissolving 80g of citric acid monoglyceride and 50g of citric acid diglyceride in the mixture to obtain a B9 solution; adding the B9 solution into the A9 solution under stirring, fully stirring, and adding the balance of 75g of water under stirring to obtain a uniform solution.
Example 10: the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
7.5% of acetic acid, 3.0% of elementary iodine, 3.0% of ammonium iodide, 49% of ethanol, 12.5% of ethyl acetate and 25% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 40g, adding 30g of ammonium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A10 solution; dissolving 75g of acetic acid and 125g of ethyl acetate in 490g of ethanol to obtain a B10 solution; adding the B10 solution into the A10 solution under stirring, fully stirring, and adding the balance of water of about 210g under stirring to obtain a uniform solution.
Example 11: the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
7.5% of acetic acid, 3.0% of elementary iodine, 3.0% of ammonium iodide, 49% of ethanol, 24% of ethyl acetate and 13.5% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 40g, adding 30g of ammonium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A11 solution; dissolving 75g of acetic acid and 240g of ethyl acetate in 490g of ethanol to obtain a B11 solution; adding the B11 solution into the A11 solution under stirring, fully stirring, and adding about 95g of the balance water under stirring to obtain a uniform solution.
Example 12: the iodine-containing disinfectant with long-term component stability comprises the following components in percentage by weight:
7.5% of acetic acid, 3.0% of elementary iodine, 3.0% of ammonium iodide, 49% of ethanol, 25.5% of ethyl acetate and 12.0% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 40g, adding 30g of ammonium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain an A12 solution; dissolving 75g of acetic acid and 255g of ethyl acetate in 490g of ethanol to obtain a B12 solution; adding the B12 solution into the A12 solution under stirring, fully stirring, and adding the rest water of about 80g under stirring to obtain a uniform solution.
Comparative example 1:
the iodine-containing disinfectant comprises the following components in parts by weight:
10% of citric acid, 2% of elemental iodine, 1.5% of potassium iodide, 70% of ethanol and 16.5% of water.
Taking 1000g of disinfectant 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 A1-1 solution; dissolving 100g of citric acid in 700g of ethanol to obtain a B1-1 solution; adding the B1-1 solution into the A1-1 solution under stirring, fully stirring, and adding the balance of 140g of water under stirring to obtain a uniform solution.
Comparative example 2:
the iodine-containing disinfectant comprises the following components in parts by weight:
10% of citric acid, 2% of elementary iodine, 1.5% of potassium iodide, 70% of ethanol and 16.5% of diethyl citrate.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking 400g of ethanol, adding 15g of potassium iodide for dissolving, and then adding 20g of elemental iodine for dissolving to obtain A2-2 solution; dissolving 100g of citric acid and 165g of diethyl citrate in 250g of ethanol to obtain a B2-2 solution; adding the B2-2 solution into the A2-2 solution under stirring, fully stirring, and adding the balance of about 50g of ethanol under stirring to obtain a uniform solution.
Comparative example 3:
the iodine-containing disinfectant comprises the following components in parts by weight:
10% of citric acid, 2% of elementary iodine, 1.5% of potassium iodide, 70% of water and 16.5% of diethyl citrate.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking 25g of water, adding 15g of potassium iodide for dissolution, and then adding 20g of elemental iodine for dissolution to obtain A3-3 solution; dissolving 100g of citric acid in 500g of water, and then adding 165g of diethyl citrate to dissolve the citric acid to obtain a B3-3 solution; adding the B3-3 solution into the A3-3 solution under stirring, fully stirring, and adding the balance of 175g of water under stirring to obtain a uniform solution.
Comparative example 4:
the iodine-containing disinfectant comprises the following components in parts by weight:
10% of citric acid, 2% of elementary iodine, 1.5% of potassium iodide and 86.5% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking 25g of water, adding 15g of potassium iodide for dissolution, and then adding 20g of elemental iodine for dissolution to obtain A4-4 solution; then dissolving 100g of citric acid in 500g of water to obtain a B4-4 solution; adding the B4-4 solution into the A4-4 solution under stirring, fully stirring, and adding the balance of 340g of water under stirring to obtain a uniform solution.
Comparative example 5:
the iodine-containing disinfectant comprises the following components in parts by weight:
10% of citric acid, 2% of elementary iodine, 1.5% of potassium iodide and 86.5% of ethanol.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking 200g of ethanol, adding 20g of elemental iodine, and then adding 15g of potassium iodide to dissolve the elemental iodine to obtain A5-5 solution; dissolving 100g of citric acid in 500g of ethanol to obtain a B5-5 solution; adding the B5-5 solution into the A5-5 solution under stirring, fully stirring, and adding the balance of 165g of ethanol under stirring to obtain a uniform solution.
Comparative example 6:
the iodine-containing disinfectant comprises the following components in parts by weight:
7.5% of acetic acid, 3.0% of elementary iodine, 3.0% of ammonium iodide, 49% of ethanol, 1% of ethyl acetate and 36.5% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of water of about 40g, adding 30g of ammonium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve the iodine to obtain A6-6 solution; dissolving 75g of acetic acid and 10g of ethyl acetate in 490g of ethanol to obtain a B6-6 solution; adding the B6-6 solution into the A6-6 solution under stirring, fully stirring, and adding about 325g of the balance water under stirring to obtain a uniform solution.
Comparative example 7:
the iodine-containing disinfectant comprises the following components in parts by weight:
7.5% of acetic acid, 3.0% of elementary iodine, 3.0% of ammonium iodide, 49% of ethanol, 36.5% of ethyl acetate and 1% of water.
Taking 1000g of disinfectant as an example, the preparation method comprises the following steps:
taking a small amount of ethanol of about 300g, adding 30g of ammonium iodide for dissolving, and then adding 30g of elementary iodine to completely dissolve iodine to obtain A7-7 solution; dissolving 75g of acetic acid and 365g of ethyl acetate in 190g of ethanol to obtain a B7-7 solution; adding the B7-7 solution into the A7-7 solution under stirring, fully stirring, and adding about 10g of water under stirring to obtain a uniform solution.
And (3) stability testing:
stability tests were performed on the disinfectant formulation compositions prepared in examples 1-12 and comparative examples 1-7 above:
the test is carried out by adopting an accelerated experiment method, the disinfectant is placed in a hydrothermal reaction kettle in a closed manner, the hydrothermal reaction kettle is placed in a constant-temperature drying box, timing is started, the temperature is increased to 80 ℃ within 2 hours, timing is started when the temperature is increased to 80 ℃, heat preservation is carried out for 8 hours, then heating is stopped, the temperature is naturally reduced to room temperature along with a furnace, a period is set as 24 hours from the start of timing, and then the process is continuously repeated 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, after the 1 st cycle (called as 1 day) and after the 10 th cycle (called as 10 days) respectively. See tables 1 and 2, respectively, for specific results. According to the previous experimental results it was shown that one cycle (1 day) corresponds approximately to 2.5 months of storage at room temperature and 10 cycles corresponds approximately to 2 years.
TABLE 1 stability test results for disinfectants prepared in examples 1-12
Figure BDA0002875611900000191
Figure BDA0002875611900000201
Note: a: the carboxylic acid content is calculated as citric acid; since the starting materials and/or possible reaction products contain monoethylene citrate and/or diethylene citrate, which contains carboxyl groups, the calculation is performed by normalizing the carboxyl groups in the ethylene citrate to citric acid;
b: the carboxylic acid is calculated as acetic acid;
c: the carboxylic acid is calculated as salicylic acid;
d: the carboxylic acid is calculated as citric acid; since the starting materials and/or possible reaction products contain monoethylene citrate and/or diethylene citrate, which contains carboxyl groups, the calculation is performed by normalizing the carboxyl groups in the ethylene citrate to citric acid; acetic acid was also normalized to citric acid for calculation;
e: iodide is calculated as potassium iodide;
f: the carboxylic acid is calculated as benzoic acid;
g: the carboxylic acid content is calculated as citric acid; because the raw material and/or the possible reaction product contains citric acid monoglyceride (C)9H14O9) And/or diglycerol citrate (C)12H20O11) Which contains carboxyl groups, and thus the calculation was performed by normalizing the carboxyl groups in the citric acid glyceride to citric acid.
TABLE 2 stability test results of the disinfectants prepared in comparative examples 1-7
Figure BDA0002875611900000202
Figure BDA0002875611900000211
Note: h: the carboxylic acid content is calculated as citric acid; since the starting materials and/or possible reaction products contain monoethylene citrate and/or diethylene citrate, which contains carboxyl groups, the calculation is performed by normalizing the carboxyl groups in the ethylene citrate to citric acid;
i: the carboxylic acid is calculated as acetic acid;
from the results in table 1, it can be seen that the disinfectant prepared in examples 1-9 of the present invention has very small content variation of the components, i.e., iodine, iodide and carboxylic acid, on the 0 th day, the 1 st day and the 10 th day, and can maintain relatively stable results, and the fluctuation of the content of iodine, i.e., iodine, and iodide is within 3%, mostly within 2%; the content of carboxylic acid is changed within 6 percent, most of the carboxylic acid is within 4 percent or even lower; the above results correspond approximately to the results of a2 year room temperature storage, and the general requirements for the quality of the disinfectant content can be met. As can be seen from comparison between examples 3 and 10 to 12, in example 3, the amount of the acid change was very small because the amount of the ester added was in equilibrium with the other components; in examples 10 to 12, since the amount of the added carboxylic ester is slightly deviated from the equilibrium state as compared with example 3, the change with respect to the carboxylic acid is slightly large, but it is still satisfied that the change rate is within 10%. It is stated that the stability of the content of disinfectant can be significantly improved within the claimed ranges of both ester and water content.
From the results in Table 2, it can be seen from comparative examples 1-5 that the change in elemental iodine and/or iodide or carboxylic acid is large for any of the above-described comparative tests in which the components are absent. For comparative example 1, no ester substance was present in the system, and the stability test result is mainly represented by the decrease of the carboxylic acid content, because no citric acid ethyl ester substance was added in the system, so that the reaction degree of the acid and the alcohol to form ester is larger, and the decrease amount of the carboxylic acid is represented as higher; meanwhile, because the water content is low, the variation of the iodine simple substance and the iodide is low; for comparative example 2, although the ester was added, no water was present in the system, causing esterification, which is also shown by a decrease in carboxylic acid content; for comparative example 3, since the system has a large water content and does not contain alcohol, although carboxylic ester is added to the system, the decrease of iodine content and the increase of iodide content are shown, and in addition, since the raw material does not contain alcohol, the hydrolysis of ester substances is caused, and the increase of acid content is shown; comparative example 4 contained no alcohol but a larger amount of water and thus was mainly represented by a decrease in the iodine content and an increase in the iodide content; the carboxylic acid content test results were slightly elevated, which may be related to disproportionation reactions as the iodine content decreased:
Figure BDA0002875611900000212
since sodium hydroxide titration was used at the time of the test, a small amount of hydrogen ions generated was calculated as carboxylic acid, resulting in a slight improvement in the carboxylic acid test results. For comparative example 5, since it contained a large amount of ethanol and did not contain water, it was shownThe carboxylic acid was decreased at a higher ratio than in comparative example 1, and the changes of iodine and iodide were also small.
For comparative examples 6 and 7, the water content and/or carboxylic acid content were not within the range claimed, and thus the acid content thereof was significantly changed to 40% or more, as compared with examples 3 and 10 to 12, further showing that the amount of ester added and the water content were within the ranges as required to significantly suppress the change in carboxylic acid content.
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 iodine-containing 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.

Claims (10)

1. An iodine-containing disinfectant with long-term component stability, which is characterized by comprising the following components in percentage by weight:
0.1 to 10 percent of elementary iodine, 0.1 to 10 percent of iodide, 0.1 to 20 percent of carboxylic acid, 2 to 30 percent of carboxylic ester, 40 to 80 percent of alcohol and 5 to 30 percent of water,
wherein the iodide is composed of iodine negative ions and hydrogen ions or metal cations or ammonium ions or quaternary ammonium ions.
2. The iodine-containing disinfectant as claimed in claim 1, wherein the iodine-containing disinfectant comprises the following components in weight content: 0.5-4% of elementary iodine, 0.5-5% of iodide, 0.1-20% of carboxylic acid, 5-30% of carboxylic ester, 40-70% of alcohol and 5-25% of water.
3. 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.
4. Iodine-containing disinfectant according to claim 3 wherein said mono-quaternary ammonium iodide salt is selected from the group consisting of mixtures of one or more of octadecyl trimethyl ammonium iodide, hexadecyl trimethyl ammonium iodide, tetradecyl trimethyl ammonium iodide, dodecyl trimethyl ammonium iodide, decyl trimethyl ammonium iodide, octyl trimethyl ammonium iodide, benzyl trimethyl ammonium iodide and tetrabutyl ammonium iodide.
5. Iodine-containing disinfectant according to claim 1 or 2, wherein said carboxylic acid is selected from the group consisting of citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid, 1,3, 5-cyclohexanetricarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid and gallic acid.
6. Iodine-containing disinfectant according to claim 1 or 2, wherein said alcohol is selected from the group consisting of alcohols having less than 10 carbon atoms in the molecule, polyethylene glycol 200, polyethylene glycol 300.
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 citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3, 5-pentaric acid, 1,3, 5-cyclohexanetricarboxylic acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid or gallic acid in combination with one or more alcohols selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol and pentaerythritol.
10. The method of producing an iodine-containing disinfectant as set forth in any one of claims 1 to 9, characterized in that the production method comprises the steps of:
(1) dissolving iodide in water, alcohol or the mixed solution of water and alcohol, and dissolving simple substance iodine in the iodide solution to obtain a solution containing iodide and simple substance iodine;
(2) dissolving carboxylic acid and carboxylic ester in water, alcohol or the mixed solution of water and alcohol to prepare a solution containing carboxylic acid and ester;
(3) mixing the solution of the step (2) with the solution of the step (1);
(4) and (4) adding the rest water into the mixed solution obtained in the step (3) and uniformly mixing to obtain the iodine-containing disinfectant.
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