CN114208818B - Iodine-containing disinfectant containing polyol ether and/or cyclic ether and preparation method thereof - Google Patents
Iodine-containing disinfectant containing polyol ether and/or cyclic ether and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an iodine-containing disinfectant containing polyol ether and/or cyclic ether, a preparation method and application thereof. The iodine-containing disinfectant comprises the following components: polyol ether and/or cyclic ether, elemental iodine, iodide, carboxylic acid and water; the polyol ether is an ether formed by capping all of the hydroxyl groups of the polyol with an alkyl group. The disinfectant uses the polyol ether and/or cyclic ether as a solvent, has good component stability, and can be used for disinfecting environments or objects in various forms. The preparation method of the disinfectant comprises the steps of mixing the iodine simple substance, the iodide, the carboxylic acid, the water, the polyol ether and/or the cyclic ether at normal temperature to obtain a uniform solution. The preparation method is simple and low in cost.
Description
Technical Field
The invention belongs to the field of disinfectants, and particularly relates to an iodine-containing disinfectant containing polyol ether and/or cyclic ether with stable component content.
Background
Iodine disinfectants are widely used in various aspects of industrial production and daily life, but the stability of iodine-containing disinfectants is always a very challenging subject. Different methods and strategies for improving the stability have therefore also been proposed for different iodine-containing disinfectants. The main reason for the instability of iodine-containing disinfectants is the active nature of the iodine species. To stabilize elemental iodine, an iodide such as potassium iodide, sodium iodide, etc. is generally added because of the formation of I 3 - The stability of iodine can be obviously improved; such as Lu Geshi iodine solution, has often been used in the past as a disinfectant and sanitizer for emergency disinfection of drinking water. Experiments prove that the iodine solution has better stability and can still maintain higher stability even in accelerated experiments. Or iodide is added into the system at the same timeAnd iodate, such as iodide and iodate added to a system that complexes iodine, can function to some extent to stabilize the iodine disinfectant. The addition of acids to improve the disinfecting properties of iodine-containing disinfectants is also a common method, and includes inorganic acids such as sulfuric acid, phosphoric acid or organic acids such as citric acid, salicylic acid, etc.; however, when an acidic substance such as citric acid is added to an aqueous solution containing potassium iodide and iodine, the stability of the elemental iodine is found to be poor, and it is preliminarily considered that water adversely affects the stability of the elemental iodine in an acidic environment containing citric acid or the like. The use of alcohol as a solvent in the system is also a common means, for example, the iodine tincture or the iodine glycerol is prepared by adding ethanol or glycerol into a disinfectant system, so that the stability of iodine can be effectively improved; along with the increase of alcohol substances, the stability of the iodine simple substance is gradually improved; however, in the system containing a carboxylic acid, the presence of an alcoholic solvent can improve the stability of iodine. However, according to the previous research results of the inventor (see, for example, chinese patent application No. 202011611608.X, chinese patent application No. 202011613375.7, chinese patent application No. 202011634817.6, etc.), in the presence of iodine simple substance, carboxylic acid reacts with alcohol, thereby affecting the stability of carboxylic acid content. For example, in an iodine-containing disinfectant containing citric acid, glycerin, iodine, potassium iodide and water, after long-term standing (even at room temperature), the generation of citric acid glyceride in the product can be detected. The nuclear magnetic and mass spectral data are shown in fig. 1 and fig. 2, respectively. The iodine-containing disinfectant comprising acetic acid, ethanol, iodine, potassium iodide and water as initial components will produce ethyl acetate. The instability of the iodine-containing disinfectant components increases the pressure during production, stocking, storage and transportation, and the disinfection effect fluctuates with the time.
According to the previous research results of the inventor, the solution for solving the problem of the reduction of the content of the carboxylic acid is to add ester substances in balance with acid, alcohol and water in the system or obtain a balance composition of acid, alcohol, water and ester in balance with each other through self esterification reaction, thereby obtaining the system with stable content of the acid (determined by an acid-base titration method) and iodine. Therefore, the methods generally need esterification reaction to be obtained, and the esterification reaction needs a longer time to reach balance (like the long-term iodine-containing disinfectant placed at room temperature is stable after being placed for a long time to generate a certain amount of ester substances); or at a higher temperature, which requires an increase in the reaction temperature, but which has a greater effect on iodine-containing disinfectants. In addition, the methods also need heating equipment, and in the heating process, iodine simple substance volatilizes at high temperature to generate corrosive and acid substances, so that the problem of corrosivity at high temperature also increases the production cost, and brings higher requirements on the safety control of production. Therefore, it is necessary to directly prepare iodine-containing disinfectants containing carboxylic acid, iodine simple substances, iodide and other substances with higher stability at normal temperature.
Disclosure of Invention
Aiming at the problem of unstable component content of disinfectants containing carboxylic acid, iodine simple substances, iodide and alcohol in the prior art, in particular the problem of unstable carboxylic acid content in the system, the invention aims to provide the iodine-containing disinfectant containing polyol ether and/or cyclic ether, which has stable component content.
The invention adopts the following technical scheme to realize the purpose:
an iodine-containing disinfectant comprising a polyol ether and/or a cyclic ether, the iodine-containing disinfectant comprising the components: polyol ether and/or cyclic ether, elementary iodine, iodide, carboxylic acid and water, wherein the polyol ether is an ether with all hydroxyl groups being terminated by alkyl.
More preferably, the iodine-containing disinfectant comprises the following components in percentage by weight:
30 to 98.5 percent of polyol ether and/or cyclic ether, 0.1 to 20 percent of elementary iodine, 0.1 to 15 percent of iodide, 0.1 to 40 percent of carboxylic acid and 1 to 50 percent of water.
More preferably, the iodine-containing disinfectant comprises the following components in percentage by weight:
45 to 98.5 percent of polyol ether and/or cyclic ether, 0.2 to 20 percent of elementary iodine, 0.2 to 15 percent of iodide, 0.2 to 40 percent of carboxylic acid and 1 to 45 percent of water;
more preferably, the iodine-containing disinfectant comprises the following components in percentage by weight:
50 to 95 percent of polyol ether and/or cyclic ether, 0.2 to 20 percent of elementary iodine, 0.2 to 15 percent of iodide, 0.2 to 40 percent of carboxylic acid and 1 to 40 percent of water.
More preferably, the iodine-containing disinfectant comprises the following components in percentage by weight:
50 to 90 percent of polyol ether and/or cyclic ether, 0.5 to 10 percent of elementary iodine, 0.5 to 10 percent of iodide, 2 to 30 percent of carboxylic acid and 5 to 40 percent of water.
Preferably, the above polyols are selected from one or more of the following polyols:
1) A polyol having the following general formula (I):
C n H 2n+2-x (OH) x (I) Wherein n =2 to 10, x =2 to 8,
wherein the polyhydric alcohol represented by the general formula (I) is selected from ethylene glycol (CH) 2 OHCH 2 OH, n =2,x = 2), propylene glycol (CH) 2 OHCH 2 CH 2 OH, n =3,x = 2), butanediol (CH) 2 OHCH 2 CH 2 CH 2 OH, n =4,x = 2), pentanediol (CH) 2 OHCH 2 CH 2 CH 2 CH 2 OH, n =5,x = 2), hexylene glycol (CH) 2 OHCH 2 CH 2 CH 2 CH 2 CH 2 OH, n =6, x = 2), glycerol (also known as glycerol, CH) 2 OHCHOHCH 2 OH, n =3,x = 3), butanetetraol (CH) 2 OHCHOHCHOHCH 2 OH, n =4, x = 4), pentanol (CH) 2 OHCHOHCHOHCHOHCH 2 OH, n =5,x = 5), hexanol (CH) 2 OHCHOHCHOHCHOHCHOHCH 2 OH, n =6,x = 6), heptanediol (CH) 2 OHCHOHCHOHCHOHCHOHCHOHCH 2 OH, n =7, x = 7), pentaerythritol ((CH) 2 OH) 4 C, n =5, x = 4); decanediol CH 2 OH(CH 2 ) 8 CH 2 OH, n =10, x = 2);
2) A polyether-containing polyol having the following general formula (II):
HO[C m H 2m O] y h (II), wherein m =2 to 6, y =2 to 100; and in the same molecule may be compounds formed with structures having different m, and the sum of the number of repeating units having each different m structure is equal to y),
wherein the ether-containing polyol represented by the general formula (II) is selected from diethylene glycol (also called diethylene glycol, which means a material obtained by condensing two ethylene glycols and removing one water, HOCH 2 CH 2 OCH 2 CH 2 OH, m =2,y = 2), triethylene glycol dimer (also known as triethylene glycol, meaning a material obtained by condensing three ethylene glycols to remove two water, and similar materials may be denoted as X condensed (X + 1) ethylene glycol, wherein X denotes the removal of a few water, and X +1 denotes a material obtained by condensing X +1 ethylene glycol, X +1=y; HOCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH, m =2, y = 3), pentaethylene tetraglycol (also called pentaethylene glycol, which means a substance obtained by condensing five ethylene glycols to remove four water); HOCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OH, m =2,y = 5), dipropylene glycol (also called dipropylene glycol, meaning a substance formed by condensation of two propylene glycols with removal of one water, CH 2 OHCH 2 CH 2 OCH 2 CH 2 CH 2 OH, m =3,y = 2), tripropylene glycol (also referred to as tripropylene glycol, meaning a substance formed by the condensation of three propylene glycols to remove two water atoms, CH 2 OHCH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OH, m =3, y = 3), and a dibutylene glycol (also called dibutylene glycol, meaning a substance formed by condensation of two butylene glycols to remove one water, CH 2 OHCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OH, m =4,y = 2), and dipentanediol (also referred to as dipentanediol, which represents a substance formed by condensation of two pentanediol diols and removal of one water, CH 2 OHCH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 OH, m =5, y = 2), monoethylene glycol propylene glycol (HOCH) 2 CH 2 OCH 2 CH 2 CH 2 OH, denotes a compound formed by the condensation of an ethylene glycol and a propylene glycol with the elimination of water, where m 1 ＝2，y 1 ＝1，m 2 ＝3，y 2 ＝1，y＝y 1 +y 2 = 2);
3) A polyol having the following general formula (III):
HO[C L H 2L-A (OH) A O] z h (III), wherein L = 3-8, A = 1- (L-2), z = 2-10,
wherein the polyol represented by the general formula (III) is selected from diglycerol (or diglycerol, and the like), HOCH 2 CH(OH)CH 2 OCH 2 CH(OH)CH 2 OH, where L =3, A =1, z = 2), glycerol trimer (also known as triglycerol, polyglycerol-3, triglycerol, etc., HOCH 2 CH(OH)CH 2 OCH 2 CH(OH)CH 2 OCH 2 CH(OH)CH 2 OH, where L =3, A =1, z = 3), dipentaerythritol (also known as dipentaerythritol, di (poly) pentaerythritol, etc., HOCH 2 C(CH 2 OH) 2 CH 2 OCH 2 C(CH 2 OH) 2 CH 2 OH, here L =5, A =2, z = 2), dipentaerythritol (HOCH) 2 (CHOH) 3 CH 2 OCH 2 (CHOH) 3 CH 2 OH, where L =5,a =3,z = 2); and
4) A polyol having the following general formula (IV):
C 6 H 12 O 6 (IV)。
wherein the polyol represented by the general formula (IV) is selected from the group consisting of inositol (also called inositol,
)。
more preferably, the above general formula (II), HO [ C m H 2m O] y In H, m =2 to 6, y =2 to 10.
Preferably, the above alkyl is selected from C 1～5 An alkyl group.
Preferably, C is as defined above 1～5 The alkyl is selected from one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
More preferably, C is 1～5 The alkyl group is selected from one or more of methyl, ethyl and propyl.
Preferably, when the polyhydric alcohol is selected from the polyhydric alcohols represented by the general formula (I), the polyhydric alcohol ether is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, glycerol tri-methyl ether, butane tetra-methyl ether, pentane pentaol penta-methyl ether, hexane hexaol hexa-methyl ether and heptane heptaol hepta-methyl ether; when the polyhydric alcohol is selected from the group consisting of the polyether polyols represented by the general formula (II), the polyhydric alcohol ether is preferably selected from the group consisting of diethylene glycol dimethyl ether (also referred to as diethylene glycol dimethyl ether, i.e., an ether obtained by condensation of two ethylene glycols and then termination of both ends with a methyl group, and so on), diethylene glycol diethyl ether, diethylene glycol dipropylene ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether (also referred to as triethylene glycol dimethyl ether, i.e., an ether obtained by condensation of three ethylene glycols and then termination of both ends with a methyl group, and so on), triethylene glycol diethyl ether, triethylene glycol dipropyl ether, tetraethylene glycol dimethyl ether (also referred to as tetraethylene glycol dimethyl ether, and so on), tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dimethyl ether (also referred to as pentaethylene glycol dimethyl ether, i.e., an ether obtained by condensation of four ethylene glycols and then termination of both ends with a methyl group, and so on), tetraethylene glycol diethyl ether, pentaethylene glycol dimethyl ether, hepta glycol dimethyl ether (also referred to as pentaethylene glycol dimethyl ether, i.e., an ethylene glycol dimethyl ether obtained by condensation of five ethylene glycols and so on), ethylene glycol dimethyl ether obtained by condensation of both ends with a methyl group, hepta ethylene glycol dimethyl ether, and so on), hepta ethylene glycol dimethyl ether (also referred to as ethylene glycol dimethyl ether), hepta ethylene glycol dimethyl ether, and so on), hepta ethylene glycol dimethyl ether obtained by condensation of seven, and so on), ether formed by terminating hydroxyl groups at both ends with methyl groups, and so on), nonaethylene glycol monomethyl ether (also referred to as nonaethylene glycol dimethyl ether, that is, ether formed by terminating hydroxyl groups at both ends with methyl groups after condensation of nine ethylene glycols, and so on), dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, pentapropylene glycol dimethyl ether, and heptapropylene glycol dimethyl ether; when the polyhydric alcohol is selected from polyhydric alcohols shown in a general formula (III), the polyhydric alcohol ether is one or more selected from diglycerol tetramethyl ether, tripropylene glycol pentamethyl ether, polyglycerol-4 hexamethyl ether, polyglycerol-4 hexaethyl ether, polyglycerol-4 hexapropyl ether, polyglycerol-5 heptamethyl ether and polyglycerol-5 heptaethyl ether; when the polyhydric alcohol is selected from the polyhydric alcohols shown in the general formula (IV), the polyhydric alcohol ether is selected from one or more of hexamethylene hexaol hexa methyl ether, hexamethylene hexaol hexa ethyl ether or glycerol polyether-7-tri methyl ether, glycerol polyether-7-tri ethyl ether and glycerol polyether-7-tri propyl ether.
More preferably, the above polyol ether is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether.
Preferably, the above cyclic ether has the following formula C b H 2b O d Wherein b =2 to 18, d = 1- (integer part of b/2).
Preferably, the cyclic ether does not contain a hydroxyl group.
Preferably, the cyclic ether is selected from one or more of tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 18-crown (ether) -6, 15-crown (ether) -5 and 12-crown (ether) -4.
More preferably, the cyclic ether is selected from one or more of tetrahydrofuran, tetrahydropyran, 1,4-dioxane.
Preferably, the carboxylic acid is selected from citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3,5-pentanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid, malic acid, gallic acid, tartaric acid, p-toluenesulfonic acid or mixtures thereof;
more preferably, the carboxylic acid is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, salicylic acid, 1,3,5-pentanedioic acid and 1,3,5-cyclohexanetrioic acid;
preferably, the iodide is selected from one or more of hydrogen iodide, lithium iodide, potassium iodide, sodium iodide, strontium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide or a quaternary ammonium iodide salt, a diquaternary ammonium iodide salt, a triquaternary ammonium iodide salt, a polyquaternary ammonium iodide salt and a hyperbranched quaternary ammonium iodide salt.
More preferably, the iodide is selected from potassium iodide and/or sodium iodide.
Preferably, the above-mentioned mono-quaternary ammonium iodide salt is selected from one or more of cetyltrimethylammonium iodide, tetradecyltrimethylammonium iodide, dodecyltrimethylammonium iodide, decyltrimethylammonium iodide, benzyltrimethylammonium iodide and tetrabutylammonium iodide.
In another aspect, the invention provides a method for preparing the iodine-containing disinfectant containing polyol ether and/or cyclic ether, which is prepared by mixing the components together according to the principle of easy dissolution.
Preferably, the preparation method comprises the following steps:
(1) Dissolving iodide in water, adding iodine into the solution to dissolve,
(2) Dissolving carboxylic acid with water and/or polyol ether and/or cyclic ether, mixing with the above aqueous solution containing iodide and iodine,
(3) The remaining polyol ether and/or cyclic ether or water is added.
The invention also provides a use method of the iodine-containing disinfectant containing the polyol ether and/or the cyclic ether, which comprises the step of directly coating or spraying the iodine-containing disinfectant on an object to be disinfected or soaking the object to be disinfected for disinfection, or carrying out disinfection operation after diluting the iodine-containing disinfectant with water or a solvent in a certain proportion.
In a further aspect, the present invention provides the use of an iodine-containing disinfectant comprising a polyol ether and/or a cyclic ether as described above, the iodine-containing disinfectant of the present invention being useful for general environmental disinfection (e.g., feedlots), product disinfection (e.g., utilities), and wound or post-surgical suture disinfection.
The iodine disinfectant containing the polyol ether and/or the cyclic ether uses the polyol ether and/or the cyclic ether to replace the common ethanol as a solvent of the iodine disinfectant, thereby fundamentally eliminating the possibility of esterification reaction between carboxylic acid and alcohol substances under the action of iodine simple substances, obtaining the effect of obviously stabilizing the carboxylic acid, and in the iodine disinfectant system, the contents of the iodine simple substances and iodide are relatively stable.
In addition, the iodine-containing disinfectant containing the polyol ether and/or the cyclic ether can be prepared at normal temperature, the production cost is low, and the preparation method is simple.
Drawings
Fig. 1 is a nuclear magnetic spectrum of an iodine-containing disinfectant containing citric acid, glycerin, elemental iodine, potassium iodide and water after being left at room temperature for a long period of time (about 1 year and half). From this spectrum it can be seen that glycerol and monoglycerides of citric acid are present in the product. Glycerol: 3.46ppm, 3.52ppm, 3.66ppm. Citric acid monoglyceride: 2.72ppm, 2.81ppm, 2.98ppm, 3.85ppm, 4.04ppm, 4.11ppm.
Fig. 2 is a mass spectrum of an iodine-containing disinfectant containing citric acid, glycerin, iodine, potassium iodide and water after being left at room temperature for a long period of time (about 1 year and half). From this spectrum, it can be seen that glycerin (91 is its characteristic peak), iodine (127 is its characteristic peak), citric acid monoglyceride (265 is its characteristic peak), citric acid (191 is its characteristic peak), citric acid diglyceride (339 is its characteristic peak), and citric acid triglyceride (413 is its characteristic peak) are present in the product.
Detailed Description
The inventor of the application finds that in a conventional disinfectant containing carboxylic acid, iodine, iodide and ethanol, the presence of iodine can catalyze esterification reaction of carboxylic acid and alcohol, and the alcohol is an important factor influencing instability of components of the disinfectant due to reduction of the content of the carboxylic acid under the condition of the presence of the carboxylic acid and a small amount of water. Although the inventor's previous research shows that the iodine-containing disinfectant with stable components can be obtained by sufficiently reacting carboxylic acid and alcohol in the system under the condition of iodine simple substance catalysis to reach esterification reaction equilibrium, the process needs a long time (such as long-term standing at room temperature), or the esterification reaction process needs to be accelerated by heating. However, it is generally not feasible to achieve stability by standing at room temperature for a long period of time, which consumes a lot of time, greatly reduces the rate of transfer and the efficiency of use of the equipment, and is disadvantageous to the production process. The esterification process can be accelerated by adopting a heating mode, the time for reaching the equilibrium can be greatly reduced, but the process needs heating operation, and the volatilization of iodine and acidic substances in the heating process puts more strict requirements on the corrosion resistance of equipment. Therefore, the iodine-containing disinfectant with more stable composition can be prepared at normal temperature, and the preparation method has more practical significance. According to the reason that the iodine disinfectant is unstable, theoretically, if no alcohol substance reacting with the carboxylic acid exists in the disinfectant, the esterification reaction of the carboxylic acid can be inhibited or even eliminated, and the stability of the carboxylic acid is improved. However, the added substance should not have any significant effect on the iodine, potassium iodide, etc., or the iodine, iodide, carboxylic acid, etc. should not have any significant effect on the added substance. Therefore, based on the research on the iodine-containing disinfectant, the inventor finds that the polyol ether and/or cyclic ether which do not have esterification reaction with carboxylic acid can achieve ideal effect as the solvent of the iodine-containing disinfectant through a large number of experiments. The present invention has been completed on the basis of this finding.
The "polyol ether" in the present invention means a substance having two or more alcoholic hydroxyl groups (also referred to as "polyol") in which all of the alcoholic hydroxyl groups are etherified (for example, all of the hydroxyl groups are capped with alkyl groups), and a carboxylic acid is not easily reacted therewith, so that the stability of the carboxylic acid in a disinfectant can be greatly improved. Simple ethers such as methylethyl ether, diethyl ether can in principle also perform a similar function, but are not suitable for use in the present invention due to problems with their volatility and anaesthetic properties and possible water solubility. The polyol ether has relatively high water solubility and carboxylic acid dissolving property due to more ether bonds, has relatively high boiling point, low normal-temperature volatility and high lightning, and can be used as a solvent in the iodine-containing disinfectant for improving the stability of carboxylic acid in the iodine-containing disinfectant.
The "polyol ethers" mentioned in the present invention are, although slightly similar in name to the "polyether polyols" in the iodine complexes of polyether polyols mentioned in the prior art, substances of different structures and completely different in their effects. The polyol ethers of the present invention preferably have a molecular weight of less than 1000, more preferably less than 500, and even more preferably less than 300. These molecules have a relatively short chain and do not readily form stable complexes with iodine. The polyether polyol in the prior art has alcohol hydroxyl groups besides ether bonds, has larger molecular weight, can generate complex reaction with iodine simple substances to generate complex or loose combination because of specific bond angles and structural phases, reduces the content of free iodine simple substances, and further plays a role in stabilizing the iodine simple substances, but can still generate esterification reaction with carboxylic acid in iodine-containing disinfectants due to the existence of hydroxyl groups (the polyether polyol also belongs to alcohols). The polyol ethers used in the present invention have only ether linkages, do not contain alcoholic hydroxyl groups, and do not substantially react with carboxylic acids to form esters. Although the ether linkage of the polyol ethers of the present invention has the property of hydrolyzing under acid conditions to form an alcohol, the carboxylic acids of the present invention are organic acids which are generally weak in acidity and are not sufficient to catalyze the ether hydrolysis reaction, and the probability of such reaction occurring even in the presence of elemental iodine is low. In addition, the reaction of the ether and the hydroiodic acid can be carried out under the condition of high concentration of the hydroiodic acid, and the concentration condition of the hydroiodic acid in the iodine-containing disinfectant of the invention is not enough to meet the reaction condition. Polyol ethers may therefore be used to stabilize the iodine-containing disinfectants of the present invention.
In addition, the polyol end capping in the present invention employs an ether bond end capping rather than an ester bond end capping used, because as explained in the previous patent application (application No. 202011611608. X), hydrolysis and exchange reaction of an ester bond occurs in the presence of iodine simple substance of the ester bond, and thus the polyol end capped with an ester bond is likely to undergo hydrolysis and the like to affect the stability of the system unless in an equilibrium state.
The main reason for instability of carboxylic acid in iodine-containing disinfectants containing alcohol is that the carboxylic acid and alcohol are subjected to esterification reaction under the catalysis of iodine simple substance. If the alcoholic hydroxyl group in the polyalcohol ether is only partially etherified, although the content of the alcoholic hydroxyl group participating in the reaction can be greatly reduced, so that the influence of the esterification reaction is relieved, the esterification reaction can be always carried out, therefore, the polyalcohol ether of the invention is preferably the ether formed by etherifying and capping all the hydroxyl groups of the polyalcohol, so that the esterification reaction can not occur, and when the ether is used as a solvent in the iodine-containing disinfectant, the carboxylic acid can be stabilized. Preferred groups for capping the polyol are alkyl groups. For reasons of solubility, the alkyl group is preferably an alkyl group having less than 5 carbon atoms, i.e. a C1-C5 alkyl group. The C1-C5 alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
Polyols that form the polyol ethers of the present invention include, but are not limited to: 1) A polyol having the general formula (I): c n H 2n+2-x (OH) x (I) (wherein n =2 to 10, x =2 to 8), the general structure representing an aliphatic polyhydric alcohol including a structure containing x alcoholic hydroxyl groups in the molecule, such as ethylene glycol, glycerin, and the like; 2) A polyether-containing polyol having the general formula (II): HO [ C ] m H 2m O] y H (II) (wherein m =2 to 6, y =2 to 100, and y is more preferably 2 to 10); represents an ether-containing diol structure containing y-1 ether bonds in the molecule; in the same molecule, there may be rational compounds formed by structures having different m, and the sum of the number of repeating units having each different m structure is equal to y, e.g. it may beStructures with identical repeating units, e.g. HOCH 2 CH 2 OCH 2 CH 2 OH, or may have a structure of different repeating units such as HO [ CH ] 2 CH 2 O] 2 [CH 2 CH 2 CH 2 O] 4 H; 3) A polyol having the general formula (III): HO [ C ] L H 2L-A (OH) A O] z H (III) (wherein L =3 to 8, a =1 to (L-2), and z =2 to 10), the structure may represent that alcoholic hydroxyl groups may be contained in the structure in addition to the alcoholic hydroxyl groups at both ends, and ether bonds are included in the molecule; and 4) a polyol having the general formula (IV): c 6 H 12 O 6 (IV)。
The polyhydric alcohol represented by the above general formula (I) includes, but is not limited to, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerol, erythritol, pentadiol, hexylene glycol, heptanediol, pentaerythritol, and decylene glycol. The ether-containing polyol represented by the above general formula (II) includes, but is not limited to, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, dibutylene glycol, dipentamethylene glycol, and propyleneglycol. The polyhydric alcohol represented by the above general formula (III) includes, but is not limited to, diglycerol, triglycerol, tetrapolyglycerol (polyglycerin-4), pentapolyglycerol (polyglycerin-5), dipentaerythritol, and dipentaerythritol. The polyhydric alcohol represented by the above general formula (IV) includes, but is not limited to, cyclohexanehexol.
The polyol ethers include, but are not limited to, polyol ethers formed from polyols represented by the general formula (I): ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, glycerol monomethyl ether, erythritol monomethyl ether, pentadecanol pentamethyl ether, hexol hexa methyl ether and heptanol hepta methyl ether; polyol ethers formed from polyether polyols of the general formula (II): diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropylene ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, pentaethylene glycol dimethyl ether, pentaethylene glycol diethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, pentapropylene glycol dimethyl ether, hexapropylene glycol dimethyl ether; polyol ethers formed from polyols of the general formula (III): diglycerol tetramethyl ether, tripropylene glycol pentamethyl ether, polyglycerol-4 hexa-methyl ether, polyglycerol-4 hexa-ethyl ether, polyglycerol-4 hexa-propyl ether, polyglycerol-5 hepta-methyl ether, polyglycerol-5 hepta-ethyl ether, etc.; polyol ethers formed from polyols having the general formula (IV): hexa (cyclohexylol) hexa (methyl ether) and hexa (cyclohexylol) hexa (ethyl ether).
The "cyclic ethers" referred to in this invention, like the above-mentioned polyol ethers, do not contain hydroxyl groups and therefore do not react with the carboxylic acids in the iodine-containing disinfectants. When the cyclic ether is used as solvent in iodine-containing disinfectant, it can stabilize carboxylic acid. Cyclic ethers useful in the present invention include, but are not limited to, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 18-crown (ether) -6, 15-crown (ether) -5, 12-crown (ether) -4. Such as tetrahydrofuran, may be a cyclic ether formed from 1,4-butanediol; 1,4-dioxane can be two cyclic ethers of 1,2-ethylene glycol; the 18-crown-6 may be a cyclic ether obtained by end-to-end connection of 6 ethylene glycols.
The relatively low amount of water and the relatively high amount of polyol ether and/or cyclic ether in the iodine-containing disinfectant system of the present invention is beneficial in stabilizing the carboxylic acid content of the system. In a preferred embodiment of the present invention, the iodine disinfectant comprising a polyol ether and/or a cyclic ether comprises the components (in weight percent): 45 to 98.5 percent of polyol ether and/or cyclic ether, 0.2 to 20 percent of elementary iodine, 0.2 to 15 percent of iodide, 0.2 to 40 percent of carboxylic acid and 1 to 45 percent of water. Further optimizing the water content to be 1-30%.
In order to further enhance the disinfecting effect of iodine-containing disinfectants, acids are usually added thereto, although inorganic acids such as sulfuric acid, phosphoric acid and the like are also commonly used for iodine-containing disinfectants, such as iodic acid mixed solution (trade name: baisheng-30) TM 、Biocid-30 TM ). In the system, a large amount of phosphoric acid and sulfuric acid maintains a low pH (pH is less than 0) of the system, so that the system has high stability (the stability of the system is greatly related to the complexation of iodine) and has strong disinfection and sterilization effects; however, a large amount of more acidic inorganic acids also cause greater irritation to the human and animal bodies. In the present invention, an organic acid is preferably added, and a carboxylic acid is more preferably added. The carboxylic acids preferably include, but are not limited to, citric acid, salicylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,3,5-pentanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid, malic acid, gallic acid, tartaric acid, p-toluenesulfonic acid.
The disinfectant comprises iodide, and on one hand, the iodide is used as a cosolvent of iodine simple substances to promote the dissolution of the iodine simple substances, so that the preparation process is convenient; on the other hand, the iodide has the effect of stabilizing the iodine simple substance, the content change of the iodine simple substance is obvious on the occasions without the iodide or with less iodide amount, and the stability of the iodine simple substance is improved along with the increase of the iodide to a certain extent. Iodide is therefore added to most iodine-containing disinfectants. The reason why iodide can stabilize elemental iodine may be that it can react with iodine in a complicated manner, for example, elemental iodine reacts with iodide ions to form I 3 - 、I 5 - 、I 7 - Carrying out disproportionation reaction on iodine in the presence of water to generate iodide ions and iodate ions; the iodide ions undergo a redox reaction with an oxidizing agent (e.g., air, oxygen), or both. In summary, addition of a certain amount of iodide to the reaction systemIs effective, especially in water-containing systems.
The iodide includes, but is not limited to, hydrogen iodide, lithium iodide, potassium iodide, sodium iodide, rubidium iodide, strontium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide or a monoquaternary ammonium iodide salt (in the present invention, a monoquaternary ammonium iodide salt means an iodide composed of a monoquaternary ammonium ion and an iodide ion, and hereinafter, a diquaternary ammonium iodide salt, a triquaternary ammonium iodide salt, a polyquaternary ammonium iodide salt or a hyperbranched quaternary ammonium iodide salt is defined similarly), a diquaternary ammonium iodide salt, a triquaternary ammonium iodide salt, a polyquaternary ammonium iodide salt or a hyperbranched quaternary ammonium iodide salt.
The monoquaternary ammonium iodide salts include, but are not limited to, hexadecyltrimethylammonium iodide, tetradecyltrimethylammonium iodide, dodecyltrimethylammonium iodide, decyltrimethylammonium iodide, benzyltrimethylammonium iodide, tetrabutylammonium iodide.
The proportion by weight of iodide in the iodine-containing disinfectant system is preferably from 0.1 to 15%. The mole number of the iodine is preferably selected according to the addition amount of the iodine: the molar ratio of iodide is 1; further optimized to 1:1-1:3. The stability of the iodine simple substance and the iodine ions in the range is relatively higher, which is beneficial to the stability of the components.
In a preferred embodiment, the iodine-containing disinfectants of the present invention comprise the components: 45 to 95 percent of polyol ether and/or cyclic ether, 0.2 to 20 percent of elementary iodine, 0.2 to 15 percent of iodide, 0.2 to 40 percent of carboxylic acid and 1 to 45 percent of water. In another preferred embodiment, the iodine-containing disinfectants of the present invention comprise the components: 50 to 90 percent of polyol ether and/or cyclic ether, 0.5 to 10 percent of elementary iodine, 0.5 to 10 percent of iodide, 2 to 30 percent of carboxylic acid and 5 to 40 percent of water; in another preferred embodiment, the iodine-containing disinfectants of the present invention comprise the components: 51-80% of polyol ether and/or cyclic ether, 0.5-5% of elementary iodine, 0.5-15% of iodide, 5-20% of carboxylic acid and 5-30% of water.
Unlike previous patent applications (e.g., chinese patent application nos. 202011611608.X, 202011613375.7, 202011634817.6, etc.) that use esters of carboxylic acids and alcohols to balance the composition, the present application uses polyol ethers and/or cyclic ethers that do not react with carboxylic acids as solvents instead of ethanol. The formulation of the present application does not require any particular operation such as heating, and can be carried out at normal temperature and pressure, and the process of accelerating dissolution of a specific composition can be carried out at a temperature higher than room temperature, but preferably at ambient temperature.
The preparation method of the iodine-containing disinfectant prepares the materials into solution according to the principle of mutual dissolution, and then mixes the solution. For example, the iodide may be dissolved in water, the iodine simple substance may be dissolved in the iodide solution, the acid may be dissolved in water or polyol ether and/or cyclic ether solvent, the above-mentioned feed liquids may be mixed, and the residual solvent may be added to a predetermined amount.
In conclusion, the iodine-containing disinfectant does not have the phenomenon that the content of carboxylic acid is changed due to esterification reaction, so that the stability of the carboxylic acid in a disinfectant system can be greatly improved. Under the condition of the formulation composition of the iodine-containing disinfectant, the contents of iodine simple substances and iodide can also have higher stability, so that a product with more stable integral composition is obtained.
The iodine-containing disinfectant can be directly used for disinfection, and can also be used after being diluted by water according to a specific proportion, and the disinfection method comprises but is not limited to disinfection by soaking an object to be disinfected, spraying or smearing the object to be disinfected on the surface of the object to be disinfected, and the like.
The preparation method of the iodine-containing disinfectant can be directly prepared at normal temperature, does not need heating operation, is more convenient to operate, does not need complicated and accurately set feeding sequence and process, has consistent component content of disinfectant products in different batches, and is suitable for industrial mass production. The iodine disinfectant has stable components, and has stable disinfection and sterilization effects because the contents of simple substance iodine, carboxylic acid and other components are kept stable after long-term storage.
In the description of the present invention, "plural" means two or more.
The invention will be further illustrated with reference to the following specific examples. The specific embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and an operation process are given. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions. Unless otherwise indicated, ratios and percentages are by weight.
The detection methods of elemental iodine, acid, iodide in the following examples are as follows:
elemental iodine: accurately weighing 10ml of iodine-containing disinfectant, weighing, placing in an iodine bottle, and titrating with sodium thiosulfate titration solution (0.1 mol/L) until the solution is colorless. The elemental iodine content was calculated according to the following formula: na (Na) 2 S 2 O 3 +I 2 ＝Na 2 S 4 O 6 + 2 NaI. 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 (if a plurality of acids exist, calculated by a certain substance containing 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 (1 mol/L) until the color of the system turns pink, and calculating the content of carboxylic acid.
Iodide: precisely measuring 10ml of iodine-containing disinfectant, weighing, placing in an iodine bottle, adding 10ml of water, adding 20ml of hydrochloric acid, titrating to yellow by using potassium iodate titration solution (0.05 mol/L), adding 5ml of trichloromethane, continuing to titrate, and strongly shaking until the purple of a trichloromethane layer disappears to indicate an end point. Removing the content of the elementary iodine to obtain the content of iodide. If precipitation occurs due to the solubility of the acid during the titration, an appropriate amount of ethanol may be added before the titration to prevent precipitation. The calculation based on the potassium iodide content is not particularly specified.
And (3) stability testing:
the stability tests in the following examples were carried out by means of accelerated tests. The method specifically comprises the following steps: and (2) sealing the disinfectant in a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature drying box, starting timing, heating to 80 ℃ within 2 hours, starting to count the heat preservation time of 80 ℃ by heating to 80 ℃, preserving the heat for 8 hours, then stopping heating, naturally cooling to room temperature along with the furnace until the time is 24 hours from the start of timing, and then continuously repeating the process for 10 cycles. The contents of elemental iodine, iodide and carboxylic acid were measured by sampling before accelerated tests were carried out (referred to as 0 day) and after cycles of 3,5 and 10 days (referred to as 3,5 and 10 days), respectively, after the disinfectant was prepared. And simultaneously compared with a comparative test using ethanol or glycerol. One cycle (1 day) of iodine-containing disinfectant in this test corresponds approximately to 2.5 months of storage at room temperature, with 10 cycles approximately corresponding to 2 years.
Example 1:
1.1 the iodine-containing disinfectant using diethylene glycol dimethyl ether as solvent comprises the following components:
10g of iodine simple substance, 8.0g of potassium iodide, 75g of water, 50g of citric acid, and the volume of diethylene glycol dimethyl ether is determined, and 500mL is prepared.
1.2 the iodine-containing disinfectant preparation method comprises the following steps:
dissolving 8.0g of potassium iodide in 8.0g of water, and then adding 10g of elemental iodine to dissolve the potassium iodide to obtain an iodine-containing solution a1; weighing the residual 67.0g of water, adding 50g of citric acid to dissolve the water, and then adding 100g of diethylene glycol dimethyl ether to obtain a mixed solution b1; then the solution a1 is added into the solution b1, stirred, and then the rest diethylene glycol dimethyl ether is added to 500mL and mixed evenly. The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 1 below.
Comparative example 1-1:
1-1.1 composition of iodine-containing disinfectant using ethanol as solvent:
10g of iodine simple substance, 8.0g of potassium iodide, 75g of water, 50g of citric acid and ethanol for constant volume, and 500mL of the total solution is prepared.
1-1.2 preparation method of iodine-containing disinfectant:
dissolving 8.0g of potassium iodide in 8.0g of water, and then adding 10g of elemental iodine to dissolve to obtain a11; weighing the residual 67g of water, adding 50g of citric acid to dissolve the residual 67g of water, and then adding 100g of ethanol to obtain b11; then adding a11 into b11, stirring uniformly, then adding the residual ethanol to 500mL, and mixing uniformly.
The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 1 below.
TABLE 1 stability test results of iodine-containing disinfectants prepared in example 1 and comparative examples 1-1
From the stability test results of the embodiment 1 and the comparative embodiment 1-1, the acid content in the iodine-containing disinfectant of the comparative embodiment 1-1 is obviously reduced, and the acid content in the iodine-containing disinfectant of the embodiment 1 is not obviously changed, which shows that the use of the methyl-terminated polyol diethylene glycol dimethyl ether can effectively control the reduction of the carboxylic acid content, can obviously play a role in stabilizing the carboxylic acid content, and provides a basis for the overall stability of the disinfectant. Under the water quantity, the contents of iodine simple substance and potassium iodide are stable. In comparative example 1-1, the iodine content slightly increased and the potassium iodide content slightly decreased, and it is supposed that a small amount of iodine ions was present to form elemental iodine.
Example 2:
2.1 the iodine-containing disinfectant using diethylene glycol dimethyl ether as solvent comprises the following components:
the total volume of the solution was 500mL, wherein the solution was composed of elemental iodine 10g, potassium iodide 7.5g, water 100g, citric acid 50g, and diethylene glycol dimethyl ether (about 377.5 g).
2.2 the preparation method of the iodine-containing disinfectant comprises the following steps:
dissolving 7.5g of potassium iodide in 7.5g of water, and then adding 10g of elemental iodine to dissolve to obtain a2; weighing the residual 92.5g of water, adding 50g of citric acid to dissolve the residual water, then adding 100g of diethylene glycol dimethyl ether, and uniformly mixing to obtain b2; then adding the a2 into the b2, stirring and mixing uniformly, then supplementing the residual diethylene glycol dimethyl ether to 500mL, and stirring uniformly.
The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 2 below.
TABLE 2 stability test results for iodine-containing disinfectants prepared in example 2
| Acceleration time/day | Iodine simple substance/%) | Potassium iodide/%) | Carboxylic acid/%) |
| 0 | 1.98 | 1.64 | 9.92 |
| 3 | 1.95 | 1.65 | 9.93 |
| 5 | 1.94 | 1.65 | 9.93 |
| 10 | 1.94 | 1.66 | 9.94 |
Example 3:
3.1 the iodine-containing disinfectant using ethylene glycol diethyl ether as solvent comprises the following components:
10g of iodine simple substance, 7.5g of potassium iodide, 100g of water, 50g of citric acid and ethylene glycol diethyl ether, wherein the volume is constant, and 500mL of the total is prepared.
3.2 the preparation method of the iodine-containing disinfectant comprises the following steps:
dissolving 7.5g of potassium iodide in 7.5g of water, and then adding 10g of elementary iodine to dissolve to obtain a3; weighing the residual 92.5g of water, adding 50g of citric acid to dissolve the residual water, then adding 100g of ethylene glycol diethyl ether, and uniformly mixing to obtain b3; and adding the a3 into the b3, uniformly stirring, adding the rest ethylene glycol diethyl ether to 500mL, and uniformly stirring.
The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 3 below.
TABLE 3 stability test results for iodine-containing disinfectants prepared in example 3
| Acceleration time/day | Iodine simple substance/%) | Potassium iodide/%) | Carboxylic acid/%) |
| 0 | 2.01 | 1.54 | 10.04 |
| 3 | 1.98 | 1.56 | 9.99 |
| 5 | 1.96 | 1.58 | 10.02 |
| 10 | 1.97 | 1.56 | 10.10 |
Example 4:
4.1 composition of iodine-containing disinfectant using glycol dimethyl ether as solvent:
10g of iodine simple substance, 7.5g of potassium iodide, 100g of water, 50g of citric acid and 500mL of ethylene glycol dimethyl ether with constant volume are prepared.
4.2 the preparation method of the iodine-containing disinfectant comprises the following steps:
dissolving 7.5g of potassium iodide in 7.5g of water, and then adding 10g of elementary iodine to dissolve to obtain a4; weighing the residual 92.5g of water, adding 50g of citric acid to dissolve the water, then adding 100g of ethylene glycol dimethyl ether, and uniformly mixing to obtain b4; and b4 is added into the a4, the mixture is stirred uniformly, and then the residual glycol dimethyl ether is added to 500mL, and the mixture is stirred uniformly.
The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 4 below.
TABLE 4 stability test results for iodine-containing disinfectants prepared in example 4
| Acceleration time/day | Iodine simple substance/%) | Potassium iodide/%) | Carboxylic acid/%) |
| 0 | 2.05 | 1.49 | 9.95 |
| 3 | 2.03 | 1.52 | 9.99 |
| 5 | 1.99 | 1.54 | 10.03 |
| 10 | 1.99 | 1.55 | 10.05 |
Example 5:
5.1 the composition of the iodine-containing disinfectant using the tetraethylene glycol dimethyl ether as the solvent is as follows:
10g of iodine simple substance, 7.5g of potassium iodide, 150g of water, 50g of citric acid and 500mL of tetraethylene glycol dimethyl ether are prepared in total.
5.2 the preparation method of the iodine-containing disinfectant comprises the following steps:
dissolving 7.5g of potassium iodide in 7.5g of water, and then adding 10g of elementary iodine to dissolve to obtain a5; weighing the residual 142.5g of water, adding 50g of citric acid to dissolve the water, then adding 100g of tetraethylene glycol dimethyl ether, and uniformly mixing to obtain b5; and adding the a5 into the b5, uniformly stirring, adding the rest tetraethylene glycol dimethyl ether to 500mL, and uniformly stirring.
The prepared iodine-containing disinfectants were subjected to the above stability test, and the results of the stability test are shown in table 5 below.
TABLE 5 stability test results for iodine-containing disinfectants prepared in example 5
| Acceleration time/day | Iodine simple substance/%) | Potassium iodide/%) | Carboxylic acid/%) |
| 0 | 2.02 | 1.49 | 10.02 |
| 3 | 1.98 | 1.55 | 9.99 |
| 5 | 1.93 | 1.60 | 10.08 |
| 10 | 1.85 | 1.64 | 10.25 |
Example 6:
6.1 the iodine disinfectant using the tetraethylene glycol dimethyl ether and the ethylene glycol diethyl ether as the mixed solvent comprises the following components:
10g of iodine simple substance, 5g of potassium iodide, 2.5g of sodium iodide, 100g of water, 40g of citric acid, 10g of acetic acid, 200g of tetraethylene glycol dimethyl ether and ethylene glycol diethyl ether are prepared to a constant volume, and the total volume is 500mL.
6.2 the preparation method of the iodine-containing disinfectant comprises the following steps:
dissolving 5g of potassium iodide and 2.5g of sodium iodide in 7.5g of water, and then adding 10g of elemental iodine to dissolve to obtain a6; weighing the residual 142.5g of water, adding 40g of citric acid and 10g of acetic acid to dissolve the water, then adding 200g of tetraethylene glycol dimethyl ether, and uniformly mixing to obtain b6; and then adding the a6 into the b6, stirring uniformly, then adding ethylene glycol diethyl ether to 500mL, and mixing uniformly.
The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 6 below.
TABLE 6 stability test results for iodine-containing disinfectants prepared in example 6
| Acceleration time/day | Iodine simple substance/%) | Potassium iodide/%) Note that | Carboxylic acid/%) Note that |
| 0 | 2.10 | 1.55 | 9.94 |
| 3 | 2.03 | 1.66 | 9.92 |
| 5 | 1.98 | 1.74 | 10.01 |
| 10 | 1.95 | 1.74 | 10.05 |
Note: iodide is calculated as potassium iodide; the carboxylic acid being calculated as citric acid
Example 7:
7.1 the composition of the iodine-containing disinfectant using dipropylene glycol dimethyl ether as a solvent is as follows:
the total volume of the preparation is 500mL, wherein the preparation comprises 10g of iodine, 7.5g of potassium iodide, 150g of water, 50g of citric acid and 277.5g of dipropylene glycol dimethyl ether.
7.2 the preparation method of the iodine-containing disinfectant comprises the following steps:
dissolving 7.5g of potassium iodide in 7.5g of water, and then adding 10g of elemental iodine to dissolve to obtain a7; weighing the residual 142.5g of water, adding 50g of citric acid for dissolving, then adding 100g of dipropylene glycol dimethyl ether, and uniformly mixing to obtain b7; then a7 is added into b7 and stirred evenly, and then the rest dipropylene glycol dimethyl ether is added to 500mL and stirred evenly.
The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 7 below.
TABLE 7 stability test results for iodine-containing disinfectants prepared in example 7
| Acceleration time/day | Iodine simple substance/%) | Potassium iodide/%) | Carboxylic acid-％ |
| 0 | 1.97 | 1.64 | 9.86 |
| 3 | 1.95 | 1.66 | 9.87 |
| 5 | 1.93 | 1.67 | 9.92 |
| 10 | 1.91 | 1.72 | 9.95 |
As can be seen from the above tables 2 to 7, the iodine-containing disinfectants prepared in examples 2 to 7 have comparative stability, which indicates that the polyol ether indeed has the effect of stabilizing the content of each component of the iodine-containing disinfectants.
Example 8:
8.1 composition of iodine-containing disinfectant using tetrahydrofuran as solvent:
the total volume of the solution is 500mL, wherein the solution comprises 10g of iodine, 2.5g of potassium iodide, 2.5g of ammonium iodide, 2.5g of sodium iodide, 150g of water, 60g of citric acid and about 260g of tetrahydrofuran.
8.2 the preparation method of the iodine-containing disinfectant comprises the following steps:
dissolving 2.5g of potassium iodide, 2.5g of ammonium iodide and 2.5g of sodium iodide in 10g of water, and then adding 10g of elemental iodine to dissolve to obtain a8; weighing the residual 140g of water, adding 60g of citric acid to dissolve the residual 140g of water, then adding 100g of tetrahydrofuran, and uniformly mixing to obtain b8; then a8 is added into b8, the mixture is stirred uniformly, and then the rest tetrahydrofuran is added to 500mL and stirred uniformly.
The prepared iodine-containing disinfectant was subjected to the above stability test, and the results of the stability test are shown in table 8 below.
TABLE 8 stability test results for iodine-containing disinfectants prepared in example 8
| Acceleration time/day | Iodine simple substance/%) | Potassium iodide/%) | Carboxylic acid/%) |
| 0 | 1.98 | 1.62 | 11.85 |
| 3 | 1.96 | 1.64 | 11.86 |
| 5 | 1.94 | 1.67 | 11.94 |
| 10 | 1.92 | 1.68 | 11.97 |
As can be seen from the above tables 2 to 8, the iodine-containing disinfectants prepared in examples 2 to 8 have comparative stability, which indicates that the polyol ether indeed has the effect of stabilizing the content of each component of the iodine-containing disinfectants.
The method for measuring the disinfection and sterilization effects of the iodine-containing disinfectant formula specifically refers to the method described in the invention patent application No. CN201010163683.4 (the name of the invention is citric acid iodine disinfectant and the preparation method thereof).
The iodine-containing disinfectants of examples 1 to 8 of the invention have the following bactericidal effects:
the experimental results show that: diluting stock solution of disinfectant at 20 deg.C according to iodine content measured during preparation or before hot storage (0 day), wherein the effective iodine content after dilution is 100mg/L, the diluent acts on Escherichia coli and Staphylococcus aureus for 3min, and the sterilization logarithm value is not less than 5.0; diluting stock solution of disinfectant according to iodine content measured during preparation or before hot storage (0 day), wherein the effective iodine content after dilution is 500mg/L, the diluent acts on black variant spore of Bacillus subtilis for 5min, and the sterilization 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 the newly-prepared disinfectant (0 day).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting 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 containing polyol ether and/or cyclic ether, which is characterized by comprising the following components in percentage by weight:
the iodine-containing disinfectant comprises the following components in percentage by weight:
45 to 95 percent of polyol ether and/or cyclic ether, 0.2 to 20 percent of elemental iodine, 0.2 to 15 percent of iodide, 0.2 to 40 percent of carboxylic acid and 1 to 45 percent of water,
the polyol ether is an ether formed by capping all the alcoholic hydroxyl groups of the polyol with alkyl groups;
the polyol is selected from one or more of the following polyols:
1) A polyol having the following general formula (I):
C n H 2n+2-x (OH) x (I) Wherein n =2 to 10, x =2 to 8,
2) A polyether-containing polyol having the following general formula (II):
HO[C m H 2m O] y h (II), wherein m =2 to 6,y =2 to 10; and in the same molecule can be compounds formed with structures of different m, and the sum of the number of repeating units with each structure of different m is equal to y;
3) A polyol having the following general formula (III):
HO[C L H 2L-A (OH) A O] z h (III), wherein L =3 to 8, A =1 to (L-2), z =2 to 10, and
4) A polyol having the following general formula (IV):
C 6 H 12 O 6 （IV）；
the cyclic ether has the following general formula C b H 2b O d Wherein b =2 to 18,d =1 to (integer part of b/2), and the cyclic ether does not contain a hydroxyl group,
the alkyl is selected from C 1~5 An alkyl group.
2. Iodine-containing disinfectant comprising a polyol ether and/or a cyclic ether according to claim 1, wherein C is 1~5 The alkyl group is selected from one or more of methyl, ethyl and propyl.
3. The iodine containing disinfectant comprising polyol ethers and/or cyclic ethers as claimed in claim 1, wherein said polyol of formula (I) is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerol, erythritol, pentadiol, hexylene glycol, heptanediol, pentaerythritol, decanediol; and/or
The polyether-containing polyol shown in the general formula (II) is selected from diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, dibutylene glycol, dipentamethylene glycol and propylene glycol; and/or
The polyhydric alcohol shown in the general formula (III) is selected from diglycerol, triglycerol, tetrapolyglycerol, pentapolyglycerol, dipentaerythritol and dipentaerythritol; and/or
The polyhydric alcohol shown in the general formula (IV) is selected from inositol.
4. Iodine containing disinfectant comprising polyol ethers and/or cyclic ethers according to claim 1, wherein said polyol ethers are selected from one or more of the following polyol ethers:
1) Polyol ethers formed from polyols of the general formula (I): ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, glycerol monomethyl ether, tetratol dimethyl ether, pentaol pentamethyl ether, hexaol hexamethyl ether and heptanol heptamethyl ether;
2) Polyol ethers formed from polyether polyols of the general formula (II): diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropylene ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, pentaethylene glycol dimethyl ether, pentaethylene glycol diethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, pentapropylene glycol dimethyl ether, hexapropylene glycol dimethyl ether;
3) Polyol ethers formed from polyols of the general formula (III): diglycerol tetramethyl ether, tripropylene glycol pentamethyl ether, polyglycerol-4-hexa methyl ether, polyglycerol-4-hexa ethyl ether, polyglycerol-4-hexa propyl ether, polyglycerol-5-hepta methyl ether and polyglycerol-5-hepta ethyl ether;
4) Polyol ethers formed from polyols having the general formula (IV): cyclohexylhexaol hexa methyl ether, cyclohexylhexaol hexa ethyl ether.
5. The iodine containing disinfectant comprising a polyol ether and/or a cyclic ether as claimed in claim 1, wherein said cyclic ether is selected from one or more of tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 18-crown (ether) -6 and 15-crown (ether) -5 and 12-crown (ether) -4.
6. The iodine containing disinfectant comprising a polyol ether and/or a cyclic ether according to claim 1, 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-pentanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formic acid, acetic acid, propionic acid, n-butyric acid, lactic acid, malic acid, gallic acid, tartaric acid, p-toluenesulfonic acid and mixtures thereof.
7. The iodine containing disinfectant comprising a polyol ether and/or a cyclic ether as claimed in claim 6, wherein said carboxylic acid is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, salicylic acid, 1,3,5-pentricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid.
8. The iodine containing disinfectant comprising a polyhydric alcohol ether and/or a cyclic ether according to claim 1 wherein said iodide is selected from one or more of the group consisting of hydrogen iodide, lithium iodide, potassium iodide, sodium iodide, strontium iodide, zinc iodide, calcium iodide, magnesium iodide, ferrous iodide, ammonium iodide or a mono-quaternary ammonium iodide salt, a bis-quaternary ammonium iodide salt, a tri-quaternary ammonium iodide salt, a poly-quaternary ammonium iodide salt and a hyperbranched quaternary ammonium iodide salt.
9. A method of preparing an iodine containing disinfectant comprising a polyol ether and/or a cyclic ether according to any of the claims 1-8, characterised in that the method of preparation is performed by mixing the components together according to the principle of easy dissolution.
10. The method of manufacturing according to claim 9, comprising the steps of:
(1) Dissolving iodide in water, adding iodine into the solution to dissolve,
(2) Dissolving carboxylic acid with water and/or polyalcohol ether and/or cyclic ether, mixing with the above aqueous solution containing iodide and iodine,
(3) The remaining polyol ether and/or cyclic ether or water is added.
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| GB923114A (en) * | 1960-08-08 | 1963-04-10 | W C Evans & Company Eccles Ltd | Quaternary ammonium compounds for stabilising iodophors |
| GB962955A (en) * | 1961-09-25 | 1964-07-08 | Bendix Corp | Germicidal solutions containing iodine |
| HUP1000362A2 (en) * | 2010-07-12 | 2012-11-28 | Egis Gyogyszergyar Nyrt | Antiseptic and disinfecting compositions having reduced iodine content |
| JP2012126655A (en) * | 2010-12-13 | 2012-07-05 | Sumika Enviro-Science Co Ltd | Biocide formulation |
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