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CN112120017B - Nano slow-release gel bactericide and preparation method thereof - Google Patents

Nano slow-release gel bactericide and preparation method thereof Download PDF

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Publication number
CN112120017B
CN112120017B CN202010777548.2A CN202010777548A CN112120017B CN 112120017 B CN112120017 B CN 112120017B CN 202010777548 A CN202010777548 A CN 202010777548A CN 112120017 B CN112120017 B CN 112120017B
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slow
release
chlorine dioxide
release gel
nano
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CN112120017A (en
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朱立丹
肖鹏飞
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Beijing Neatrition Technology Co ltd
Yijingxing Shandong Technology Co ltd
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Beijing Neatrition Technology Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

The invention provides a nano slow-release gel bactericide and a preparation method thereof. The nano slow-release gel bactericide comprises independent chlorine dioxide slow-release gel and an acid-excited slow-release ball; the chlorine dioxide slow-release gel comprises a carbon-based nano coating structure and a slow-release gel body; the carbon-based nano coating structure comprises a chlorine dioxide precursor substance and a carbon-based nano coating material for coating the chlorine dioxide precursor substance; the acid-excited sustained-release ball comprises low-molecular-weight polyethylene glycol and an acidic substance. The nano slow-release gel bactericide can greatly prolong the service time, has excellent slow-release effect and sterilizing effect, and is suitable for various places which are not suitable for spraying a disinfectant in a large area.

Description

Nano slow-release gel bactericide and preparation method thereof
Technical Field
The invention relates to a bactericide, in particular to a slow-release gel bactericide and a preparation method thereof.
Background
Chlorine dioxide (ClO) 2 ) Is a gas from yellow green to orange yellow, and is a safe and nontoxic green disinfectant which is internationally recognized. The bactericidal performance of chlorine dioxide lies in that it can release nascent oxygen and hypochlorous acid molecule when it is contacted with microbe, and has good adsorptivity and penetrability for microbial cell, and can effectively oxidize the enzyme containing sulfur radical in cell, destroy enzyme system, at the same time make amino acid in protein be oxidized and decomposed, and quickly control microbial protein synthesis so as to attain the effect of inhibiting growth of bacteria or killing bacteria, and has good killing action for spore, virus, algae, fungi, iron blood bacteria and sulfate reducing bacteria, etc. and has no influence on cell structure of higher animals.
With the outbreak of new coronavirus in the early 2020, the disinfection and sterilization become normal. Large-scale spraying of alcohol and 84 disinfectants has a limited range of action and cannot kill all viruses in the environment. It can only act on the surface of an object for a short time, and can not meet the time required by disinfection, and the disinfection effect can not be achieved. Meanwhile, alcohol, 84 disinfectant and the like can bring potential safety hazards. The chlorine dioxide has good disinfection effect and no toxicity to human bodies, and is the first choice for disinfection. Because the chlorine dioxide has active chemical property and is not stable, although the chlorine dioxide aqueous solution which is not easy to volatilize and decompose is prepared, the release period of the activated liquid chlorine dioxide is short, and the transportation, the storage and the use are inconvenient.
Therefore, there is an urgent need for a sterilizing product that is not harmful to the human body and can maintain the sterilizing effect continuously.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a nano sustained-release gel that is harmless to human body and can continuously sterilize, and the slow release of reactive chlorine dioxide is realized by nano slurry-coating technology, so as to achieve the purpose of continuous sterilization.
According to one aspect of the invention, a nano sustained-release gel bactericide is provided, which comprises independent chlorine dioxide sustained-release gel and acidic excitation sustained-release balls;
the chlorine dioxide slow-release gel comprises a carbon-based nano coating structure and a slow-release gel body;
the carbon-based nano coating structure comprises a chlorine dioxide precursor substance and a carbon-based nano coating material for coating the chlorine dioxide precursor substance;
the acid-excited sustained-release ball comprises low-molecular-weight polyethylene glycol and an acidic substance.
Preferably, the chlorine dioxide slow-release gel and the acid-excited slow-release ball are mixed in a mass ratio of 100 (1-8) before use.
Preferably, the sustained release gel comprises a polymeric water absorbent resin and a high molecular weight polyethylene glycol.
Preferably, the chlorine dioxide precursor is sodium chlorite and the acidic substance is selected from one or more of citric acid, oxalic acid, tartaric acid and hydrochloric acid.
Preferably, the carbon-based nano-coating material is nano-chitosan.
Preferably, the high molecular water absorbent resin is polyacrylic resin.
According to another aspect of the present invention, a method for preparing a nano sustained-release gel bactericide comprises the steps of:
dispersing a carbon-based nano slurry coating material in water to form a slurry coating system;
adding a chlorine dioxide precursor substance into the slurry coating system, and uniformly mixing to obtain mixed slurry;
adding high-molecular water-absorbing resin and high-molecular polyethylene glycol into the mixed slurry to form chlorine dioxide slow-release gel;
preparing the low molecular weight polyethylene glycol and acidic substances into an acidic excitation slow release ball;
the chlorine dioxide slow release gel is mixed with the acid-excited slow release ball before use.
Preferably, the high molecular weight polyethylene glycol is PEG4000 and the low molecular weight polyethylene glycol is PEG1000.
Specifically, according to the nano slow-release gel bactericide provided by the invention, the coating layer of the carbon-based nano coating material is formed on the surface of the chlorine dioxide precursor substance, and then the gel formed by the macromolecular water-absorbent resin is formed outside the coating structure, so that the formed chlorine dioxide slow-release gel can promote the chlorine dioxide to be slowly released when being mixed with the acidic excitation slow-release ball, the using time can be greatly prolonged, the nano slow-release gel bactericide has excellent slow-release effect and sterilization effect, and is suitable for various places where large-area disinfectant spraying is not suitable.
Drawings
Further objects, features and advantages of the present invention will become apparent from the following description of embodiments of the invention, with reference to the accompanying drawings, in which:
fig. 1 shows the release profiles of the germicides according to example 1 and comparative example 1.
Detailed Description
The nano slow-release gel bactericide provided by the invention comprises independent chlorine dioxide slow-release gel and an acid-excited slow-release ball, wherein the mass ratio of the chlorine dioxide slow-release gel to the acid-excited slow-release ball is preferably 100 (1-8), and more preferably 100.
The chlorine dioxide slow-release gel comprises a carbon-based nano coating structure and a slow-release gel body coating the carbon-based nano coating structure. The carbon-based nano coating structure comprises a chlorine dioxide precursor substance and a carbon-based nano coating material coating the chlorine dioxide precursor substance. The carbon-based nano-coating material can be nano-chitosan, and the average particle size of the carbon-based nano-coating material can be 0.8-1.5nm. The chlorine dioxide precursor material may be a material that is capable of being converted to chlorine dioxide upon stimulation by an acidic material, and may be, for example, sodium chlorite.
The acid-excited slow-release ball can slowly release chlorine dioxide gas generated by converting chlorine dioxide precursor substances.
The slow release gel is formed by taking high molecular water-absorbing resin as a gel and taking high molecular weight polyethylene glycol as a stabilizer. The high molecular water absorption resin can be polyacrylic resin, preferably polyacrylic resin with number average molecular weight of 8000-15000. The high molecular weight polyethylene glycol may have a number average molecular weight of 3500-4500, preferably PEG4000.
The slow-release gel further forms a gel on the outer surface of the carbon-based nano-coating structure, so that the release speed of chlorine dioxide gas generated by the chlorine dioxide precursor substance coated in the carbon-based nano-coating structure is further delayed, and the duration of the bactericidal activity is longer.
The acid-excited slow-release ball comprises low-molecular-weight polyethylene glycol and an acidic substance. The low molecular weight polyethylene glycol may have a number average molecular weight of 800 to 1050, preferably PEG1000.
The acidic substance is an acidic substance which can react with the chlorine dioxide precursor substance to generate chlorine dioxide, and can be one or more of citric acid, oxalic acid, tartaric acid and hydrochloric acid, preferably citric acid.
The chlorine dioxide slow-release gel and the acid-activated slow-release ball are mixed before use, and are preferably mixed in a mass ratio of 100 (1-8), such as 100. Chlorine dioxide precursor species (e.g., sodium chlorite) and acidic species (e.g., citric acid) are reactants that generate gaseous chlorine dioxide at room temperature.
The invention also provides a method for preparing the nano slow-release gel bactericide, which comprises the following steps:
dispersing a carbon-based nano slurry coating material in water to form a slurry coating system;
adding a chlorine dioxide precursor substance into the slurry coating system, and uniformly mixing to obtain mixed slurry;
adding high molecular water-absorbing resin and high molecular polyethylene glycol into the mixed slurry to form chlorine dioxide slow-release gel (namely colloid to be excited);
preparing the low molecular weight polyethylene glycol and acidic substances into an acidic excitation slow release ball;
the chlorine dioxide slow-release gel is mixed with the acid-excited slow-release ball before use.
According to a specific embodiment, the gel bactericide is prepared from the following raw materials in percentage by mass: 5-8% of sodium chlorite, 3-5% of citric acid, 7-10% of high molecular water-absorbing resin, 0.5-2% of carbon-based nano-slurry-coating material, 2-5% of high molecular weight polyethylene glycol, 3-6% of low molecular weight polyethylene glycol and the balance of deionized water.
The preparation method of the nano slow-release gel bactericide is simple, namely, the acid-excited slow-release ball is placed immediately, and the prepared gel is placed at room temperature in an open manner, so that the effect of slowly releasing chlorine dioxide to sterilize air can be realized, and the service life of the bactericide can be greatly prolonged. The product has simple preparation and use methods, good chlorine dioxide slow-release effect and sterilization effect, and is suitable for various places such as offices, schools, communities, automobiles and the like which are not suitable for large-area spraying of disinfectants.
The present invention is further illustrated by the following examples, but is not limited thereto.
Example 1
(1) Dissolving 0.8g of nano chitosan in 20g of deionized water, adding 5g of sodium chlorite, and uniformly stirring to form a nano slow-release coating system;
(2) uniformly mixing 7g of polyacrylic resin and 3g of PEG4000 in 54g of water, adding the mixture into a nano slow-release coating system, and uniformly stirring again to form chlorine dioxide slow-release gel;
(3) fully mixing 5g of citric acid with 5.2g of PEG1000 to form acid-excited sustained-release gel spheres;
(4) subpackaging and sealing respectively to obtain the finished product;
(5) when in use, the acidic excited sustained-release gel ball is placed into the chlorine dioxide sustained-release gel to activate the chlorine dioxide sustained-release gel.
Example 2
(1) Dissolving 2g of nano chitosan in 35g of deionized water, adding 8g of sodium chlorite, and uniformly stirring to form a nano slow-release slurry coating system;
(2) uniformly mixing 8g of polyacrylic resin and 5g of PEG4000 in 44g of water, adding the mixture into the nano slow-release slurry coating system, and uniformly stirring again to form chlorine dioxide slow-release gel;
(3) fully mixing 3g of citric acid and 3g of PEG1000 to form acidic excitation slow-release gel spheres;
(4) subpackaging and sealing respectively to obtain the finished product;
(5) when in use, the acidic excitation slow-release gel ball is placed into the chlorine dioxide slow-release gel to activate the chlorine dioxide slow-release gel.
Example 3
(1) Dissolving 1.3g of nano chitosan in 28g of deionized water, adding 6.5g of sodium chlorite, and uniformly stirring to form a nano slow-release coating system;
(2) uniformly mixing 9g of polyacrylic resin and 4g of PEG4000 in 42.7g of water, adding the mixture into a nano slow-release coating system, and uniformly stirring again to form chlorine dioxide slow-release gel;
(3) fully mixing 4g of citric acid with 4.5g of PEG1000 to form an acidic-excited sustained-release gel ball;
(4) subpackaging and sealing respectively to obtain the finished product;
(5) when in use, the acidic excitation slow-release gel ball is placed into the chlorine dioxide slow-release gel to activate the chlorine dioxide slow-release gel.
Comparative example 1
(1) Adding 5g of sodium chlorite into 20g of deionized water, and uniformly stirring to form a sodium chlorite solution;
(2) uniformly mixing 7g of polyacrylic resin and 3g of PEG4000 in 54.8g of water, adding the mixture into the system, and uniformly stirring again;
(3) fully mixing 5g of citric acid with 5.2g of PEG1000 to form an acidic excitation slow-release ball;
(4) subpackaging and sealing respectively to obtain the finished product;
(5) when in use, the acid-excited slow-release ball is placed in a gel system to activate the chlorine dioxide slow-release gel.
Chlorine dioxide concentration and release time tests were performed on the chlorine dioxide sustained-release gels prepared in example 1 and comparative example 1 above, and the results are shown in fig. 1.
The test method comprises the following steps: at 5m 3 Closed air chamberAnd detecting the concentration of chlorine dioxide in the air in the room.
As can be seen from fig. 1, the gel biocide according to example 1 (series 1) has a significantly longer release time and thus a longer effective time than the biocide according to comparative example 1 (series 2).
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims (1)

1. The nanometer slow-release gel bactericide is characterized by comprising independent chlorine dioxide slow-release gel and an acid-excited slow-release ball;
the chlorine dioxide slow-release gel comprises a carbon-based nano coating structure and a slow-release gel body;
the carbon-based nano coating structure comprises a chlorine dioxide precursor substance and a carbon-based nano coating material for coating the chlorine dioxide precursor substance;
the acid-excited slow-release ball comprises low-molecular-weight polyethylene glycol and an acidic substance;
the chlorine dioxide slow-release gel and the acid-excited slow-release ball are mixed according to the mass ratio of 100 (1-8) before use; the slow release gel comprises high molecular water-absorbent resin and high molecular weight polyethylene glycol;
the low molecular weight polyethylene glycol is PEG1000;
the high molecular weight polyethylene glycol is PEG4000;
the carbon-based nano-sized material is nano chitosan, and the macromolecular water-absorbing resin is polyacrylic resin with the molecular weight of 8000-15000;
the method for preparing the nano slow-release gel bactericide comprises the following steps:
dispersing a carbon-based nano slurry coating material in water to form a slurry coating system;
adding a chlorine dioxide precursor substance into the slurry coating system, and uniformly mixing to obtain mixed slurry;
adding high-molecular water-absorbing resin and high-molecular polyethylene glycol into the mixed slurry to form chlorine dioxide slow-release gel;
preparing the low molecular weight polyethylene glycol and acidic substances into an acidic excitation slow release ball; the chlorine dioxide precursor substance is sodium chlorite, and the acidic substance is citric acid;
the nano slow-release gel bactericide is prepared from the following raw materials in percentage by mass: 5-8% of sodium chlorite, 3-5% of citric acid, 7-10% of high molecular water-absorbing resin, 0.5-2% of carbon-based nano-slurry-coating material, 2-5% of high molecular weight polyethylene glycol, 3-6% of low molecular weight polyethylene glycol and the balance of deionized water.
CN202010777548.2A 2020-08-05 2020-08-05 Nano slow-release gel bactericide and preparation method thereof Active CN112120017B (en)

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CN112970776B (en) * 2021-02-04 2023-04-07 延瑞堂有限责任公司 Low-temperature disinfectant for object surface, preparation method and application thereof
CN113197221B (en) * 2021-05-14 2021-12-31 天津清科环保科技有限公司 Sol-gel slow-release chlorine dioxide gel and preparation method thereof

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US20100136112A1 (en) * 2005-06-15 2010-06-03 Martin Roy W Oxidizing composition including a gel layer
CN109645113A (en) * 2019-03-01 2019-04-19 上海海洋大学 A kind of fresh-keeping gel of chlorine dioxide slow-release and its preparation method and application
CN110574764A (en) * 2019-08-23 2019-12-17 银河环保科技(天津)有限公司 Slow-release chlorine dioxide gel powder and preparation method thereof
CN110947017A (en) * 2019-12-11 2020-04-03 韶关学院 Slow-release chlorine dioxide solid gel and preparation method and application thereof
CN111466406A (en) * 2020-04-29 2020-07-31 北京青鸿福科技有限公司 Contact type binary chlorine dioxide slow-release gel and preparation method thereof

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Address after: Building 1, Yard 2, Yongjie South Road, Haidian District, Beijing, 100094

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Patentee after: Yijingxing (Shandong) Technology Co.,Ltd.

Address before: N8101, floor 1, building 1, yard 33, Dijin Road, Haidian District, Beijing 100095

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