CN113068712B - Stabilizing synergist of hypochlorous acid solution and application - Google Patents
Stabilizing synergist of hypochlorous acid solution and application Download PDFInfo
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- CN113068712B CN113068712B CN202110258911.4A CN202110258911A CN113068712B CN 113068712 B CN113068712 B CN 113068712B CN 202110258911 A CN202110258911 A CN 202110258911A CN 113068712 B CN113068712 B CN 113068712B
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- hypochlorous acid
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- acid solution
- dichlorohydantoin
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 26
- ZKLFRQSZDUSMQE-UHFFFAOYSA-N 5,5-dichloroimidazolidine-2,4-dione Chemical compound ClC1(Cl)NC(=O)NC1=O ZKLFRQSZDUSMQE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 20
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 18
- 229920001983 poloxamer Polymers 0.000 claims abstract description 17
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229960000502 poloxamer Drugs 0.000 claims abstract description 16
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000001116 FEMA 4028 Substances 0.000 claims description 9
- 229960004853 betadex Drugs 0.000 claims description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 6
- 239000001433 sodium tartrate Substances 0.000 claims description 6
- 229960002167 sodium tartrate Drugs 0.000 claims description 6
- 235000011004 sodium tartrates Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 46
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000460 chlorine Substances 0.000 abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 abstract description 16
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 11
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 230000002147 killing effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000645 desinfectant Substances 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229940069078 citric acid / sodium citrate Drugs 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- MENYRYNFSIBDQN-UHFFFAOYSA-N 5,5-dibromoimidazolidine-2,4-dione Chemical compound BrC1(Br)NC(=O)NC1=O MENYRYNFSIBDQN-UHFFFAOYSA-N 0.000 description 2
- CTKXFMQHOOWWEB-UHFFFAOYSA-N Ethylene oxide/propylene oxide copolymer Chemical compound CCCOC(C)COCCO CTKXFMQHOOWWEB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001993 poloxamer 188 Polymers 0.000 description 2
- 229940044519 poloxamer 188 Drugs 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- -1 Dichloro hydantoin Chemical compound 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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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
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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Abstract
The invention discloses a stabilization synergist of hypochlorous acid solution and application, which is characterized by being prepared from the following raw materials in parts by mass: 0.001-0.5 part of dichlorohydantoin, 0.1-2 parts of water-soluble cyclodextrin, 0.1-2 parts of poloxamer and 0.05-2 parts of pH value regulator, and during preparation, the raw materials are mixed and ground uniformly to obtain solid powder. According to the invention, dichlorohydantoin, water-soluble cyclodextrin, poloxamer and a pH value regulator are mixed together according to a specific proportion to prepare the stable synergist of the hypochlorous acid solution, so that not only is the solubility of the dichlorohydantoin in the aqueous solution improved, but also the dichlorohydantoin can be wrapped to form an outer package and then slowly released in the aqueous solution, thereby achieving the effects of stabilizing and synergizing the hypochlorous acid solution and effectively keeping the stability of the disinfection and killing capacity of the hypochlorous acid solution. Experiments prove that after the stabilizing synergist with specific content is added into the oxidation-reduction potential water, the available chlorine and the pH value of the hypochlorous acid solution are stable within 12 months.
Description
Technical Field
The invention relates to the technical field of medical sanitation and disinfection, in particular to a stabilizing synergist of hypochlorous acid solution and application thereof.
Background
The existing disinfection systems have some defects, for example, disinfectants such as 84 disinfectant are harmful to human bodies, and the general disinfection process is carried out in the environment where people evacuate. Alcohol disinfectants are relatively safe, but have the disadvantage of being flammable, causing the risk of accidental burning when the concentration in the space is high. In view of this, some relatively safe disinfection systems are currently being developed and sought in the industry.
Hypochlorous acid is a green and safe high-efficiency disinfectant, generally exists in a solution state, is very safe in a disinfection concentration range, and is a broad-spectrum disinfectant. Hypochlorous acid solutions are generally prepared in two ways. One method is an electrolytic process, also known as oxidation-reduction potential (ORP) water, in which an acidic hypochlorous acid aqueous solution, also known as ORP water, is obtained by electrolysis of an aqueous solution containing sodium chloride. The other method is an electroless method, which is formed by mixing and diluting hypochlorite and acid liquor, wherein the pH of the generated hypochlorous acid solution is generally neutral or acidic, and the method has high requirement on water quality. The current electrolysis method is more common. The electrolyzed oxidizing water is a colorless transparent liquid, has a chlorine smell, has an effective chlorine content of 50-200mg/L, and contains hypochlorous acid (HClO) as the main effective component. Oxidation-reduction potential (ORP) water is also called acidic ORP water, acidic electrolyzed water, acidic ionized water, ORP water, strongly acidic electrolyzed water, or the like. Contains low-concentration effective chlorine, has the pH value of 2-3 and the oxidation-reduction potential (ORP) of more than 1100mV, has stronger oxidation capacity and rapid microbial killing effect, and is a novel environment-friendly disinfectant.
The acidic electrolyzed oxidizing water has the biggest defects of instability, short time-efficiency and instability under normal conditions, can be automatically decomposed into tap water, is not suitable for long-term storage, and is preferably prepared at present. The acidic oxidation potential water is unstable and has a close relationship with the generation mechanism and the generation components thereof. Hypochlorous acid is unstable and is affected by many factors, and the hypochlorous acid solution is easily converted into chlorine gas under the condition that the pH is less than 4. At pH above 7, hypochlorous acid solutions readily convert to sodium hypochlorite solutions. The pH value of the electrolyzed oxidizing water is generally lower than 3, so that the solution forms chlorine loss under the storage condition, hypochlorous acid in the system is slowly decomposed and converted into chlorine, and the chlorine is slowly evaporated and lost, because the disinfection capability of the whole system is reduced along with the increase of the storage time. Since electrolyzed oxidizing water is unstable in properties and cannot be stored for a long period of time, it is generally prepared on site by a machine. For applications in the medical and health field, continuous generators are mainly used, are generally manufactured on site, and are currently used and supplied like tap water without dilution.
In order to improve the stability of hypochlorous acid in oxidation-reduction potential water, several methods have been developed. Such as stabilizers and pH adjusters. The pH value is adjusted to a range of 4 to 6 by a pH regulator to prevent decomposition and conversion of hypochlorous acid. However, the increase in pH is generally accompanied by a decrease in oxidation-reduction potential, and it is difficult for the stabilizer to eventually prevent the decrease in available chlorine content in oxidation-reduction potential water after long-term storage.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a stable synergist which can maintain the long-term killing effect of hypochlorous acid solution and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme.
The stabilizing synergist for the hypochlorous acid solution is characterized by being capable of releasing hypochlorous acid in the hypochlorous acid solution for a long time and prepared from the following raw materials in parts by mass: 0.001-0.5 part of dichlorohydantoin, 0.1-2 parts of water-soluble cyclodextrin, 0.1-2 parts of poloxamer and 0.05-2 parts of pH value regulator, and during preparation, the raw materials are mixed and ground uniformly to obtain solid powder.
More preferably, the stabilizing synergist is prepared from the following raw materials in parts by mass: 0.01-0.1 part of dichlorohydantoin, 0.5-1 part of water-soluble cyclodextrin, 0.5-1 part of poloxamer and 0.1-0.3 part of pH value regulator.
More preferably, the cyclodextrin is water-soluble cyclodextrin, including hydroxypropyl-beta-cyclodextrin, sulfobutyl-beta-cyclodextrin and the like.
More preferably, the pH adjuster is a mixture of citric acid and sodium citrate or a mixture of tartaric acid and sodium tartrate, which is dissolved in a solution to form a buffer solution.
The invention also provides application of the stable synergist of the hypochlorous acid solution, which is characterized in that the solid powder is added into oxidation-reduction potential water; after the solid powder is added, hypochlorous acid can be released in the oxidation-reduction potential water for a long time, and then stable oxidation-reduction potential water is obtained.
More preferably, the solid powder is added in an amount of 0.3 to 7wt% in the oxidation-reduction potential water, and the hypochlorous acid content in the oxidation-reduction potential water is maintained not to decrease for one year.
More preferably, the oxidative reductive potential water has a hypochlorous acid concentration of 20-200ppm and a pH of 2 to 7.
More preferably, when the solid powder is added to the oxidation-reduction potential water, the oxidation-reduction potential water is added to a light-shielding stirring container, and then the solid powder is added while stirring, so that the solid powder is gradually dissolved to obtain a transparent solution.
More preferably, the transparent solution is transferred from the light-shielding stirring container to a light-shielding plastic container and stored at room temperature.
The beneficial effects of the invention are: the stable synergist of the hypochlorous acid solution is prepared by mixing dichlorohydantoin, water-soluble cyclodextrin, poloxamer and a pH value regulator together according to a specific proportion, not only the solubility of the dichlorohydantoin in the aqueous solution is improved, but also the dichlorohydantoin can be wrapped, and then the mixture is slowly released in the aqueous solution, so that the effects of stabilizing and synergizing the hypochlorous acid solution are achieved, and the stability of the disinfection and killing capacity of the hypochlorous acid solution is effectively kept. Experiments prove that after the stabilizing synergist with specific content is added into the oxidation-reduction potential water, the available chlorine and the pH value of the hypochlorous acid solution are stable within 12 months. Particularly, the stabilizing synergist has the effect of slowly releasing hypochlorous acid, so that the duration of the killing capacity can be effectively prolonged in the actual killing process.
Drawings
FIG. 1 shows the molecular structure of dichlorohydantoin.
Detailed Description
The following further describes the embodiments of the present invention, so that the technical solutions and the advantages thereof of the present invention are more clear and definite. The following description of the embodiments is exemplary in nature and is in no way intended to limit the invention.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
The invention adopts a method of supplementing a stabilizing synergist into a hypochlorous acid solution to improve the long-term stability of the hypochlorous acid solution. Herein, the stabilizing synergist means a substance which releases hypochlorous acid into an aqueous solution slowly and for a long period of time. Because the dibromohydantoin is a substance which can release hypochlorous acid when dissolved in water, the dibromohydantoin is used for designing a stable synergist which can release hypochlorous acid for a long time. The stable synergist is added into the hypochlorous acid solution such as acidic oxidation potential water to play a role in synergism, although the effective components of the hypochlorous acid in the acidic oxidation potential water are reduced along with the increase of the storage time, the stable synergist can continuously release the hypochlorous acid to supplement the reduced hypochlorous acid in the acidic oxidation potential water, so that the total content of the hypochlorous acid is not reduced, the synergism effect is achieved, and the hypochlorous acid content of the system is kept stable for a long time.
Dichlorohydantoin is known as 1, 3-dichloro-5, 5-dimethylhydantoin, the chemical name of which is 1, 3-dichloro-5, 5-dimethylhydantoin (the molecular formula is shown in figure 1), is white powder, is slightly soluble in water and has slight pungent odor. Hydrolysis in water forms mainly hypochlorous acid, which slowly releases chlorine as hypochlorous acid, and is easily decomposed at a pH of > 9.
Dichloro hydantoin is an insoluble substance with low solubility. How to improve the solubility and long-term stability of dichlorohydantoin is a difficult problem. The invention adopts the cyclodextrin and the poloxamer for compounding and wrapping, on one hand, the solubility of the dichlorohydantoin in water is increased, and on the other hand, the slow hypochlorous acid release performance of the dichlorohydantoin is effectively increased. The dichlorohydantoin-cyclodextrin-poloxamer are compounded to form an excellent hypochlorous acid stabilizing synergist. The water-soluble organic acid-base compound is characterized by being capable of better dissolving in water, releasing hypochlorous acid for a long time, and supplementing the hypochlorous acid which is decomposed unstably in acidic oxidation potential water for a long time. Compared with the prior hypochlorous acid stabilizer system, the invention has the advantages of releasing new hypochlorous acid components for a long time and keeping the hypochlorous acid content in the hypochlorous acid solution system from being reduced.
In the present invention, the hypochlorous acid solution mainly comprises: acid oxidation-reduction potential water, dichlorohydantoin, cyclodextrin, poloxamer and a pH value regulator.
In the present invention, the pH of the electrolyzed oxidizing water is about 2 to 7, and the hypochlorous acid concentration is 20 to 200ppm. The weight percentage of the electrolyzed oxidizing water is 93.5-99.749%.
When the synergistic stabilizer is actually prepared, 0.001-0.5 part, preferably 0.01-0.1 part of dichlorohydantoin is prepared by mass; 0.1-2 parts of cyclodextrin, preferably 0.5-1 part; 0.1-2 parts of poloxamer, preferably 0.5-1 part; the pH value regulator is 0.05-2 parts, preferably 0.1-0.3 part.
Wherein the cyclodextrin is water soluble cyclodextrin of various types, has hollow structure, and can wrap dichlorohydantoin molecules, including beta-cyclodextrin, hydroxypropyl-beta-cyclodextrin, sulfobutyl-beta-cyclodextrin and the like.
Poloxamers include, for example, poloxamer 804 and poloxamer 188, which, in combination with cyclodextrin, act as a solubilizing agent for dichlorohydantoin.
The pH regulator has the function of stabilizing the pH value of the system and mainly comprises citric acid/sodium citrate, tartaric acid/sodium tartrate and the like.
Example 1.
0.1 g of beta-cyclodextrin, 0.1 g of poloxamer 804, 0.001 g of dichlorohydantoin and 0.05 g of citric acid/sodium citrate (the weight ratio of the two components is 1). Transferring the solution from the light-proof stirring container into a light-proof plastic container, and storing at normal temperature.
Example 2.
0.5 g of hydroxypropyl-beta-cyclodextrin, 0.8 g of poloxamer 188, 0.1 g of dichlorohydantoin and 0.5 g of tartaric acid/sodium tartrate (the weight ratio of the two components is 2. Transferring the solution from the light-proof stirring container into a light-proof plastic container, and storing at normal temperature.
Example 3.
1 g of sulfobutyl-beta-cyclodextrin, 1 g of poloxamer 804, 0.01 g of dichlorohydantoin and 1 g of citric acid/sodium citrate (the weight ratio of the two components is 2: 1) are mixed and ground uniformly to obtain solid powder, 96.99 g of acidic oxidizing water (the hypochlorous acid content is 50 ppm) is added into a closed lightproof container, the obtained solid powder is added under the condition of slow magnetic stirring, and the powder is gradually dissolved to obtain a transparent solution. Transferring the solution from the lightproof stirring container into a lightproof plastic container, and storing at normal temperature.
Example 4.
1.5 g of beta-cyclodextrin, 0.5 g of poloxamer 804, 0.3 g of dichlorohydantoin and 0.3 g of tartaric acid/sodium tartrate (the weight ratio of the two components is 1.2. Transferring the solution from the light-proof stirring container into a light-proof plastic container, and storing at normal temperature.
Example 5.
2 g of beta-cyclodextrin, 2 g of poloxamer 804, 0.5 g of dichlorohydantoin and 2 g of tartaric acid/sodium tartrate (two components 2: 1) are mixed and ground uniformly to obtain solid powder, 93.5 g of acidic oxidizing water (with hypochlorous acid content of 200 ppm) is added into a closed lightproof container, the obtained solid powder is added under the condition of slow magnetic stirring, and the powder is gradually dissolved to obtain a transparent solution. Transferring the solution from the light-proof stirring container into a light-proof plastic container, and storing at normal temperature.
To better demonstrate the technical effects of the present invention, the following accelerated aging tests were performed on the transparent solutions provided in examples 1 to 5, respectively. The chlorine content and the pH of the solution were tested for time change after 14 days of storage at 54 ℃ in a closed environment. The available chlorine content was determined by a chlorine content test paper in combination with titration, and the pH was measured by a pH meter, the results of which are shown in table 1.
Table 1 shows the changes in effective chlorine and pH at 54 ℃ in the hypochlorous acid solutions prepared in examples 1 to 5
As can be seen from Table 1, the available chlorine of the hypochlorous acid solutions provided in examples 1 to 5 did not decrease during accelerated aging, and the pH was stable for 12 months. During the aging test, the available chlorine content increased first and then gradually remained stable, and did not decrease by 14 months after accelerated aging for 14 days. According to the 'disinfection technical code' of the Ministry of health, the stabilizer can be estimated to be up to 12 months, and has remarkable stability. Meanwhile, the pH value is stable and basically kept stable, and the difference between the initial pH value and the final pH value is not more than 0.5.
Therefore, the solid powder formed by the technology can be used for the synergism of the hypochlorous acid solution, and the hypochlorous acid content in the hypochlorous acid solution is stable for a long time. The long-term stable hypochlorous acid solution formed by the invention can be used for safe disinfection of families, public spaces, automobiles, hospitals and communities, and the hypochlorous acid solution has the characteristics of low toxicity, high efficiency and safety and can be used for harmless disinfection and spraying when people exist.
It will be appreciated by those skilled in the art from the foregoing description of construction and principles that the invention is not limited to the specific embodiments described above, and that modifications and substitutions based on the teachings of the art may be made without departing from the scope of the invention as defined by the appended claims and their equivalents. The details not described in the detailed description are prior art or common general knowledge.
Claims (2)
1. The stabilizing synergist for the hypochlorous acid solution is characterized by being capable of releasing hypochlorous acid in the hypochlorous acid solution for a long time and prepared from the following raw materials in parts by mass: 0.001-0.5 part of dichlorohydantoin, 0.1-2 parts of water-soluble cyclodextrin, 0.1-2 parts of poloxamer and 0.05-2 parts of pH value regulator, and during preparation, the raw materials are mixed and ground uniformly to obtain solid powder;
the cyclodextrin is water-soluble cyclodextrin, comprising: one or more of beta-cyclodextrin, hydroxypropyl-beta-cyclodextrin and sulfobutyl-beta-cyclodextrin;
the pH value regulator is a mixture of citric acid and sodium citrate or a mixture of tartaric acid and sodium tartrate;
when the solid powder is applied, the solid powder is added into oxidation-reduction potential water, the addition amount of the solid powder is 0.3-7wt%, the hypochlorous acid concentration of the oxidation-reduction potential water is 20-200ppm, and the pH value is 2-7.
2. The stabilizing synergist for hypochlorous acid solution according to claim 1, which is prepared from the following raw materials in parts by mass: 0.01-0.1 part of dichlorohydantoin, 0.5-1 part of water-soluble cyclodextrin, 0.5-1 part of poloxamer and 0.1-0.3 part of pH value regulator.
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