CN112244009A - Gel type chlorine dioxide sustained release agent and preparation method thereof - Google Patents
Gel type chlorine dioxide sustained release agent and preparation method thereof Download PDFInfo
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- CN112244009A CN112244009A CN202011060101.XA CN202011060101A CN112244009A CN 112244009 A CN112244009 A CN 112244009A CN 202011060101 A CN202011060101 A CN 202011060101A CN 112244009 A CN112244009 A CN 112244009A
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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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N25/08—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 solids as carriers or diluents
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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
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
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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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Abstract
The invention relates to a gel type chlorine dioxide slow release agent and a preparation method thereof, aiming at solving the defects of unstable chlorine dioxide gas, short preservation time of a disinfection product and the like in the prior art, and the gel system comprises: the invention relates to a chlorite aqueous solution, a gel, graphene oxide, a pH regulator and an activating agent, wherein the graphene oxide is used as a chlorine dioxide gas regulator, and the more excellent adsorption performance and the oxygen-containing functional group on the surface of the graphene oxide are utilized to be in synergistic action with the gel, so that the reaction of the chlorine dioxide gas is similar to that of an ultra-miniature chemical processing plant, a chlorine dioxide balance system with continuous volatilization and continuous supplement is established, the chlorine dioxide gas is continuously released, various bacteria and viruses in the air are killed, the air is purified, no secondary pollution is caused, and the price is low.
Description
Technical Field
The invention relates to the technical field of gel disinfectants, in particular to a gel type chlorine dioxide slow-release agent and a preparation method thereof.
Background
Chlorine dioxide (ClO)2) Is a fourth generation disinfectant recognized in the world, is a yellow green gas at normal temperature, is easy to dissolve in water, and has the solubility 5 times that of chlorine at room temperature. It is composed of a chlorine atom and two oxygen atoms, the outer electronic layer has 19 electrons, and is one of few compounds completely in the form of monomer free radicals in nature, so that the chlorine dioxide dissolved in water as gas is a bactericide with real effect, and its sterilization mechanism is different from acid and phenol, etc., and can only make protein denature, and is also different from chlorination action of chlorine-containing disinfectant, and only can make microorganism lose activity. Chlorine dioxide is a strong oxidant, electrode potential E01.95V, has strong oxidizing property, and contains chlorine 52.6% and Cl4+To Cl-The effective chlorine content of the chlorine dioxide is 52.6% by 5 to 263%, namely the oxidation disinfection sterilization capacity of the chlorine dioxide is 2.63 times of that of chlorine, and the sterilization mechanism is that amino acid in microbial protein is oxidized and decomposed to cause amino acid chain breakage and protein loss of function, so that the microbes are killed, meanwhile, the protein is not denatured in the sterilization process, no influence is caused on animal cells, and carcinogenic, teratogenic and carcinogenic substances are not generated. However, since chlorine dioxide gas is unstable, long-term storage and long-distance distribution thereof have been the most difficult problems to solve. On the other hand, with the continuous improvement of living standard of people, the requirements on living environment and air quality are higher and higher due to the enhancement of health consciousness. But pollution of home decoration and modern office facilities, building decoration materials such as plywood materials, adhesives, coatings and the like can continuously release a lot of toxic and harmful gases, indoor planktonic bacteria are increased due to the use of an air conditioning system, and all the gases cause serious harm to human health, so that a disinfection product which is nontoxic and harmless to human bodies, continuously plays the functions of sterilization, disinfection and peculiar smell removal under the condition of not influencing normal work and study and thoroughly improves the air quality of living spaces of people is urgently needed in the market.
Disclosure of Invention
The gel system of the invention ensures that the reaction of the chlorine dioxide gas is similar to an ultra-micro chemical processing plant, establishes a chlorine dioxide balance system with continuous volatilization and continuous supplement, can continuously release the chlorine dioxide gas, kills various bacteria and viruses in the air, purifies the air, has no secondary pollution, and has low price.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides a gel-type chlorine dioxide sustained release agent, comprising: chlorite aqueous solution, gel, graphene oxide, pH regulator and activator.
Graphene Oxide (GO) holds graphene sheets together by pi-pi stacking and hydrogen bonding, has a three-dimensional (3D) porous network and a developed interpenetrating pore structure. The special two-dimensional plane structure and the pi-pi conjugate system of the composite lead the composite to have higher mechanical strength, higher specific surface area and better adsorption property and thermal property; in addition, oxygen-containing functional groups on the surface of the graphene oxide, such as carbonyl, hydroxyl, carboxyl and the like, can enable the graphene oxide to have better interface interaction through chemical bonds or hydrogen bonds, can form a stable colloidal dispersion system in water, and improves the mechanical property and stability of the hydrogel.
In the invention, the excellent adsorption performance of graphene oxide is utilized to improve the storage stability of chlorine dioxide in a gel system, oxygen-containing functional groups (carbonyl, hydroxyl, carboxyl and the like) in the graphene oxide and hydroxyl, amino, carboxyl and other groups in the gel form hydrogen bonds, and the synergistic effect of the two can effectively control the chlorine dioxide to be stably released at low concentration. The graphene oxide, the gelling agent and the water are mixed to form a three-dimensional gel structure. In addition, the oxygen-containing functional group in the graphene oxide enables the graphene oxide to have better hydrophilicity, and a stable colloidal dispersion system can be formed in water.
Further, the mass content of the graphene oxide is 1-4%. If the content of the graphene oxide is too high, the adsorption effect of the chlorine dioxide is too strong, so that the slow-release concentration is reduced, and only bacteriostasis can be performed, and sterilization cannot be performed; if the content is too small, the slow release is too fast, resulting in too short storage time.
Further, the gel type chlorine dioxide slow release agent comprises the following components in percentage by mass:
wherein the sum of the mass percentages of the components is equal to 100%, and the mass concentration of the chlorite aqueous solution is 1-4%.
Further, the gel type chlorine dioxide slow release agent also comprises a chlorine dioxide aqueous solution stabilizer.
Further, the gel type chlorine dioxide slow release agent comprises the following components in percentage by mass:
wherein the sum of the mass percentages of the components is equal to 100%, and the mass concentration of the chlorite aqueous solution is 1-4%.
Further preferably, the gel type chlorine dioxide slow release agent comprises the following components in percentage by mass:
wherein the sum of the mass percentages of the components is equal to 100%, and the mass concentration of the chlorite aqueous solution is 1-4%.
Further, the chlorite is at least one of sodium chlorite, calcium chlorite, magnesium chlorite, potassium chlorite and barium chlorite.
Further, the gel is at least one of sodium alginate, sodium carboxymethylcellulose, polyacrylic resin, polyacrylamide resin and modified starch; sodium alginate is preferred.
Further, the pH regulator is at least one of sodium citrate, sodium acetate, sodium tartrate and sodium borate.
Further, the chlorine dioxide aqueous solution stabilizer is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
Further, the activating agent is at least one of sodium dihydrogen phosphate, acetic acid, oxalic acid, phosphoric acid, citric acid, tartaric acid, arsenic acid, formic acid and boric acid.
In another aspect, the present invention provides a method for preparing the gel-type chlorine dioxide sustained release agent, including: adding a gel, graphene oxide, an activating agent, a pH regulator and optionally a chlorine dioxide aqueous solution stabilizer into a chlorite aqueous solution, and uniformly stirring to obtain the gel type chlorine dioxide slow-release agent.
Wherein the gel, activator, pH regulator, chlorite and chlorine dioxide aqueous solution stabilizer are of the types described above.
Further, the mass concentration of the chlorite aqueous solution is 1-4%, for example: 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, etc.
Further, the dosage of each component is as follows based on 100 parts of the total mass of the system: 65-85 parts of chlorite aqueous solution, 5-15 parts of gel, 1-4 parts of graphene oxide, 6-11 parts of pH regulator and 2-5 parts of activator.
Further preferably, before the reaction, a chlorine dioxide aqueous solution stabilizer is added to the chlorite aqueous solution, wherein the chlorine dioxide aqueous solution stabilizer is at least one of sodium hydroxide, potassium hydroxide and ammonia water. The chlorite aqueous solution is unstable and is easy to generate chlorine dioxide gas, and the alkaline compound is added to play a role in stabilizing the chlorine dioxide aqueous solution.
Further, the amount of the chlorine dioxide aqueous solution stabilizer is 0.01-0.05 part by total mass of the system, and within the range, the chlorite aqueous solution is alkaline and can effectively stabilize chlorine dioxide.
The invention has the beneficial effects that:
according to the invention, the special two-dimensional planar structure and the pi-pi conjugate system of the graphene oxide are utilized, so that the graphene oxide has excellent chlorine dioxide gas adsorption capacity, the oxygen-containing functional groups in the graphene oxide are combined with the gelling agent through hydrogen bonds to form a cross-linked structure, the storage performance of the chlorine dioxide gas can be improved through the cross-linked structure and the adsorption effect, the volatilization of the chlorine dioxide is reduced, the stability of the chlorine dioxide in the gel is improved, the release time of the gel is prolonged, and the release concentration of the chlorine dioxide in the gel is effectively controlled.
Definition of terms
Unless otherwise specified, the solvent of the solution in the present invention is "deionized water".
All ranges cited herein are inclusive, unless expressly stated to the contrary.
The term "at least one" is used herein to describe the elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
The numbers in this disclosure are approximate, regardless of whether the word "about" or "approximately" is used. The numerical value of the number may have differences of 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a number with a value of N is disclosed, any number with a value of N +/-1%, N +/-2%, N +/-3%, N +/-5%, N +/-7%, N +/-8% or N +/-10% is explicitly disclosed, wherein "+/-" means plus or minus, and a range between N-10% and N + 10% is also disclosed.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of elements, and the 75 th version of the handbook of chemistry and Physics, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific section is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
Detailed Description
The following description is of the preferred embodiment of the present invention only, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Example 1
(1) Weighing 70g of sodium chlorite aqueous solution with the mass concentration of 2% and 0.04g of sodium hydroxide, and uniformly mixing and stirring to obtain an agent A aqueous solution;
(2) weighing 7.12g of sodium carboxymethylcellulose, 2g of graphene oxide, 6.5g of sodium citrate and 2.9g of citric acid, and uniformly mixing to obtain a B agent solid;
(3) and adding the solid of the agent B into the aqueous solution of the agent A, and uniformly stirring to obtain the gel type chlorine dioxide slow release agent.
Examples 2 to 5 and comparative examples 1 to 2
The preparation methods of examples 2 to 5 and comparative examples 1 to 2 were the same as in example 1, the amounts of the raw materials were as shown in table 1, and in comparative example 2, diatomaceous earth was used instead of graphene oxide.
TABLE 1
Performance testing
The storage stability and the effective time of the gel type chlorine dioxide slow release agent are tested. The test results are shown in Table 2.
(1) Storage stability: preparing five samples according to each formula, sealing and placing at normal temperature, unsealing and testing the slow release time of chlorine dioxide in 3 rd, 6 th, 12 th, 24 th and 30 th months, wherein the longest storage time when the slow release time exceeds 1 month is the storage stability time;
(2) the slow release duration is as follows: taking the prepared sample, and directly testing the slow release time of the chlorine dioxide.
TABLE 2
| Numbering | Storage stability/month | Duration of sustained Release/d |
| Example 1 | 24 | 138 |
| Example 2 | 24 | 120 |
| Example 3 | 24 | 160 |
| Example 4 | 24 | 150 |
| Example 5 | 24 | 145 |
| Comparative example 1 | <12 | 20 |
| Comparative example 2 | <12 | 30 |
As can be seen from table 2, the storage stabilizer and the sustained-release duration of the gel product of the embodiment of the present invention are significantly superior to those of the comparative example, because the graphene oxide applied to the conventional gel system has the functions of adsorbing chlorine dioxide and controlling the stable release of chlorine dioxide.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A gel type chlorine dioxide slow release agent is characterized by comprising: chlorite aqueous solution, gel, graphene oxide, pH regulator and activator.
2. The gel-type chlorine dioxide slow-release agent according to claim 1, which comprises the following components in percentage by mass:
wherein the sum of the mass percentages of the components is equal to 100%, and the mass concentration of the chlorite aqueous solution is 1-4%.
3. The gel-type chlorine dioxide slow-release agent according to claim 1, further comprising a chlorine dioxide aqueous solution stabilizer.
4. The gel-type chlorine dioxide slow-release agent according to claim 3, wherein the gel-type chlorine dioxide slow-release agent comprises the following components in percentage by mass:
wherein the sum of the mass percentages of the components is equal to 100%, and the mass concentration of the chlorite aqueous solution is 1-4%.
5. The gel-type chlorine dioxide slow release agent according to any one of claims 1 to 4, wherein the chlorite is at least one of sodium chlorite, calcium chlorite, magnesium chlorite, potassium chlorite and barium chlorite.
6. The gel-type chlorine dioxide slow-release agent according to any one of claims 1 to 4, wherein the gel is at least one of sodium alginate, sodium carboxymethyl cellulose, polyacrylic resin, polyacrylamide resin and modified starch.
7. A gel-type chlorine dioxide sustained-release agent according to any one of claims 1 to 4, wherein the pH regulator is at least one of sodium citrate, sodium acetate, sodium tartrate and sodium borate.
8. The gel-type chlorine dioxide sustained-release agent according to claim 3 or 4, wherein the chlorine dioxide aqueous solution stabilizer is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
9. The gel-type chlorine dioxide slow-release agent according to any one of claims 1 to 4, wherein the activating agent is at least one of sodium dihydrogen phosphate, acetic acid, oxalic acid, phosphoric acid, citric acid, tartaric acid, arsenic acid, formic acid and boric acid.
10. A method for preparing the gel-type chlorine dioxide slow-release agent according to any one of claims 1 to 9, comprising: adding the gel, the graphene oxide, the activator, the pH regulator and optionally the chlorine dioxide aqueous solution stabilizer into the chlorite aqueous solution, and uniformly stirring to obtain the gel type chlorine dioxide slow-release agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011060101.XA CN112244009A (en) | 2020-09-30 | 2020-09-30 | Gel type chlorine dioxide sustained release agent and preparation method thereof |
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| CN202011060101.XA CN112244009A (en) | 2020-09-30 | 2020-09-30 | Gel type chlorine dioxide sustained release agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113396901A (en) * | 2021-06-25 | 2021-09-17 | 新乡市康大消毒剂有限公司 | Gel for slowly releasing chlorine dioxide and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113396901A (en) * | 2021-06-25 | 2021-09-17 | 新乡市康大消毒剂有限公司 | Gel for slowly releasing chlorine dioxide and preparation method thereof |
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