CN116019124B - High-efficiency chlorine dioxide disinfectant and production method thereof - Google Patents

High-efficiency chlorine dioxide disinfectant and production method thereof Download PDF

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CN116019124B
CN116019124B CN202310125547.3A CN202310125547A CN116019124B CN 116019124 B CN116019124 B CN 116019124B CN 202310125547 A CN202310125547 A CN 202310125547A CN 116019124 B CN116019124 B CN 116019124B
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chlorine dioxide
dioxide disinfectant
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CN116019124A (en
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侯博
陈小平
侯臣
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Shandong Huashi Pharmaceutical Co ltd
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Abstract

The invention discloses a high-efficiency chlorine dioxide disinfectant and a production method thereof, belonging to the technical field of disinfectants, wherein the chlorine dioxide disinfectant comprises the following raw materials in parts by mass: 35-40 parts of sodium chlorite, 25-35 parts of epoxy succinic acid, 10-15 parts of sulfanilic acid, 4-6 parts of a thickening agent, 1-1.5 parts of a dispersing agent, 0.8-1.2 parts of sodium hydroxide, 40-50 parts of a modified immobilization carrier, 1-2 parts of boron trifluoride diethyl ether, 2.5-5 parts of dialdehyde chitosan and 100 parts of deionized water. According to the invention, the modified immobilization carrier is used for carrying out pressurized impregnation adsorption on sodium chlorite, and the dialdehyde chitosan is further embedded and immobilized by combining a gel method and a chemical crosslinking effect, so that the slow-release solid chlorine dioxide disinfectant is prepared, the chlorine dioxide component can be released stably and slowly, the disinfection and antibacterial effects can be effectively exerted for a long time, and the storage time and the service time are long.

Description

High-efficiency chlorine dioxide disinfectant and production method thereof
Technical Field
The invention belongs to the technical field of disinfectants, and in particular relates to a high-efficiency chlorine dioxide disinfectant and a production method thereof.
Background
Chlorine dioxide disinfectant is internationally recognized as a high-efficiency disinfectant, and can kill microorganisms including bacterial propagules, bacterial spores, fungi, mycobacteria, viruses and the like without generating drug resistance. After the chlorine dioxide contacts with microorganism, the strong oxidizing substances such as nascent oxygen and hypochlorous acid molecules are released, and negative electrons or electron donating groups such as sulfhydryl enzyme or sulfide and nitride in the cells are attacked, so that the sulfhydryl enzyme is deactivated, protein synthesis is inhibited, and the aim of sterilization is achieved.
The slow-release chlorine dioxide is a solid or semisolid product capable of slowly releasing chlorine dioxide gas, compared with a chlorine dioxide water solution, the slow-release chlorine dioxide water solution overcomes the problems of poor stability and easy burst release of chlorine dioxide, is easier to store and transport, and can meet the requirements of long-acting disinfection. Therefore, development of slow-release chlorine dioxide has become one of the research hotspots in the disinfectant field. For example, the invention patent with publication number of CN113396901B discloses a gel for slowly releasing chlorine dioxide and a preparation method thereof, wherein maltodextrin, cellulose hydroxypropyl methyl ether, sodium magnesium silicate, hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer, sodium chlorite, solid organic acid and the like are used for preparing the gel for slowly releasing chlorine dioxide; for example, the invention patent with publication number of CN114403157B discloses a bi-component gel slow-release chlorine dioxide disinfectant, a preparation method and application thereof, wherein gelatin, chlorite, alkaline compound, preservative, water and 2-acrylamide-2-methylpropanesulfonic acid are used for preparing the slow-release chlorine dioxide disinfectant; the invention patent with publication number of CN110250199B discloses a chlorine dioxide disinfectant containing supported solid acid, a preparation method and application thereof, wherein concentrated hydrochloric acid, a template agent, attapulgite and tetraethoxysilane are utilized to prepare a composite carrier, solid acid is further supported, and the composite carrier is finely ground and sieved with chlorite, a drying agent, a foaming agent, an accelerator and a lubricant and then mixed to obtain the chlorine dioxide disinfectant containing supported solid acid. Therefore, how to develop a novel slow-release chlorine dioxide with long-acting controlled release and high-efficient antibacterial effect has important significance.
In addition, the related technical content of preparing the chlorine dioxide disinfectant by using epoxy succinic acid and sulfanilic acid as acid activators has not been reported in the prior patent or literature, and the technology is still blank in the field of domestic and foreign chlorine dioxide synthesis.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-efficiency chlorine dioxide disinfectant and a production method thereof.
The technical scheme of the invention is summarized as follows:
the efficient chlorine dioxide disinfectant comprises the following raw materials in parts by mass:
35-40 parts of sodium chlorite
25-35 parts of epoxy succinic acid
10-15 parts of sulfanilic acid
4-6 parts of thickening agent
1 to 1.5 parts of dispersant
0.8-1.2 parts of sodium hydroxide
40-50 parts of modified immobilization carrier
Boron trifluoride diethyl etherate 1-2 parts
2.5-5 parts of dialdehyde chitosan
100 parts of deionized water;
the preparation method of the modified immobilization carrier comprises the following steps: adding octaepoxy cage-type silsesquioxane and isocyanate propyl triethoxysilane into tetrahydrofuran, stirring for dissolving, adding tertiary amine catalyst and immobilized carrier with average particle size of 150-500nm, performing ultrasonic dispersion, stirring in water bath at 55-65deg.C for reaction for 1-3 hr, filtering, and rotary evaporating to remove tetrahydrofuran to obtain modified immobilized carrier.
Further, the dosage proportion of the octaepoxy cage-type silsesquioxane, the isocyanate propyltriethoxysilane, the tetrahydrofuran, the tertiary amine catalyst and the immobilized carrier is (0.1-0.15) g (0.05-0.1) g (5-8) mL (0.01-0.02) g and 1g.
Further, the tertiary amine catalyst is one or more of bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, triethylenediamine and triethylamine.
Further, the thickener is one or two of lithium magnesium silicate and sodium magnesium silicate.
Further, the dispersing agent is one or more of sodium metasilicate pentahydrate, lithium metasilicate pentahydrate and potassium metasilicate pentahydrate.
Further, the immobilization carrier is one or more of oxide aerogel, zeolite molecular sieve and MOFs material.
Further, the oxide aerogel is one or more of zirconia aerogel, alumina aerogel and silica aerogel.
Further, the zeolite molecular sieve is one or more of ZSM-5 type zeolite molecular sieve, beta-25 type zeolite molecular sieve, beta-60 type zeolite molecular sieve and SAPO-11 type zeolite molecular sieve.
Further, the MOFs material is one or more of a UIO-66 material, a ZIF-8 material and an MIL-125 material.
The invention further provides a production method of the efficient chlorine dioxide disinfectant, which comprises the following steps:
s1: adding sodium chlorite into deionized water, stirring and dissolving, adding a thickening agent, a dispersing agent and a modified immobilized carrier, performing ultrasonic dispersion, and performing pressurized impregnation and adsorption for 15-30min under the pressure of 0.4-0.5MPa to obtain a mixed suspension;
s2: adding epoxy succinic acid, sulfanilic acid and sodium hydroxide into the mixed suspension, stirring and mixing, adding boron trifluoride diethyl etherate and dialdehyde chitosan, and stirring and reacting for 1h at 20-30 ℃ to obtain gel suspension;
s3: and (3) drying the gel suspension in vacuum at 30-50 ℃ to obtain the high-efficiency chlorine dioxide disinfectant.
The invention has the beneficial effects that:
1. the invention firstly takes epoxy succinic acid and sulfanilic acid as acid activators and sodium chlorite as a chlorine dioxide matrix to jointly react to prepare chlorine dioxide, and the reaction equation is as follows:
Figure SMS_1
sodium epoxy succinate and p-aminobenzenesulfonate produced by reactionThe sodium sulfate has complexation, can chelate heavy metal ions to form a stable metal complex, further achieves the effects of removing heavy metal ions and inhibiting scale and releasing slowly, and meanwhile, the sodium sulfanilate/sulfanilate also has antibacterial and sterilizing effects, and is synergistic with chlorine dioxide, high-efficiency sterilization and disinfection, and is loaded by using a modified immobilization carrier rich in epoxy groups and isocyanate groups, and further embedded and immobilized by using dialdehyde chitosan gel, wherein the dialdehyde chitosan is-NH 2 Ring-opening addition reaction with modified immobilized carrier and epoxy group in epoxy sodium succinate/epoxy succinic acid, dialdehyde chitosan, sodium sulfanilate/NH in sulfanilate 2 Nucleophilic addition reaction with-N=C=O on the surface of the modified immobilized carrier, and-CHO in dialdehyde chitosan and-NH in sodium sulfanilate/sulfanilate 2 The Schiff base reaction occurs, intermolecular self-assembly is carried out through chemical crosslinking reaction, a three-dimensional interpenetrating network structure is formed, multiple stable immobilization of the disinfectant active ingredients is further realized, and the loading capacity and embedding efficiency of the chlorine dioxide disinfectant are remarkably improved.
According to the invention, the modified immobilization carrier is used for carrying out pressurized impregnation adsorption on sodium chlorite, and the dialdehyde chitosan is further embedded and immobilized by combining a gel method and a chemical crosslinking effect, so that the slow-release solid chlorine dioxide disinfectant is prepared, the chlorine dioxide component can be released stably and slowly, the disinfection and antibacterial effects can be effectively exerted for a long time, and the storage time and the service time are long.
Compared with the traditional hydrochloric acid activator, the invention has the advantages of burst release inhibition, low corrosiveness, non-volatilization and the like, and the prepared chlorine dioxide has excellent sterilization effect.
Drawings
FIG. 1 is a flow chart of the method for producing the efficient chlorine dioxide disinfectant.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
The invention provides a high-efficiency chlorine dioxide disinfectant, which comprises the following raw materials in parts by mass:
35-40 parts of sodium chlorite
25-35 parts of epoxy succinic acid
10-15 parts of sulfanilic acid
4-6 parts of thickening agent
1 to 1.5 parts of dispersant
0.8-1.2 parts of sodium hydroxide
40-50 parts of modified immobilization carrier
Boron trifluoride diethyl etherate 1-2 parts
2.5-5 parts of dialdehyde chitosan
100 parts of deionized water;
the preparation method of the modified immobilization carrier comprises the following steps: adding octaepoxy cage-type silsesquioxane and isocyanate propyl triethoxysilane into tetrahydrofuran, stirring and dissolving, adding tertiary amine catalyst and immobilized carrier with average particle size of 150-500nm, performing ultrasonic dispersion, stirring and reacting in water bath at 55-65deg.C for 1-3h, filtering, and rotary evaporating to remove tetrahydrofuran to obtain modified immobilized carrier; the dosage proportion of the octaepoxy cage type silsesquioxane, the isocyanate propyltriethoxysilane, the tetrahydrofuran, the tertiary amine catalyst and the immobilized carrier is (0.1-0.15) g (0.05-0.1) g (5-8) mL (0.01-0.02) g (1 g); the tertiary amine catalyst is one or more of bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, triethylenediamine and triethylamine;
the thickener is one or two of lithium magnesium silicate and sodium magnesium silicate; the dispersing agent is one or more of sodium metasilicate pentahydrate, lithium metasilicate pentahydrate and potassium metasilicate pentahydrate; the immobilization carrier is one or more of oxide aerogel, zeolite molecular sieve and MOFs material; the oxide aerogel is one or more of zirconia aerogel, alumina aerogel and silica aerogel; the zeolite molecular sieve is one or more of ZSM-5 type zeolite molecular sieve, beta-25 type zeolite molecular sieve, beta-60 type zeolite molecular sieve and SAPO-11 type zeolite molecular sieve; the MOFs material is one or more of UIO-66 material, ZIF-8 material and MIL-125 material.
In the embodiment, sodium chlorite is used as a chlorine dioxide matrix, epoxy succinic acid and sulfanilic acid are used as acid activators, and the three are reacted together to prepare chlorine dioxide, and the reaction equation is as follows:
Figure SMS_2
the sodium epoxy succinate and the sodium sulfanilate produced by the reaction have complexation, can chelate heavy metal ions to form a stable metal complex, further achieve the effects of removing heavy metal ions and inhibiting scale and releasing slowly, and meanwhile, the sodium sulfanilate/the sulfanilate also have antibacterial and sterilizing effects, are synergistic with chlorine dioxide, high-efficiency in sterilization and disinfection, are loaded by utilizing a modified immobilization carrier rich in epoxy groups and isocyanate groups, and are further embedded and immobilized by adopting dialdehyde chitosan gel, so that the-NH in the dialdehyde chitosan is obtained 2 Ring-opening addition reaction with modified immobilized carrier and epoxy group in epoxy sodium succinate/epoxy succinic acid, dialdehyde chitosan, sodium sulfanilate/NH in sulfanilate 2 Nucleophilic addition reaction with-N=C=O on the surface of the modified immobilized carrier, and-CHO in dialdehyde chitosan and-NH in sodium sulfanilate/sulfanilate 2 The Schiff base reaction occurs, and a three-dimensional interpenetrating network structure is formed through chemical crosslinking reaction, so that the multiple stable immobilization of the active ingredients of the disinfectant is realized, and the loading capacity and the embedding efficiency of the disinfectant are obviously improved.
The method for producing the efficient chlorine dioxide disinfectant comprises the following steps:
s1: adding sodium chlorite into deionized water, stirring and dissolving, adding a thickening agent, a dispersing agent and a modified immobilized carrier, performing ultrasonic dispersion, and performing pressurized impregnation and adsorption for 15-30min under the pressure of 0.4-0.5MPa to obtain a mixed suspension;
s2: adding epoxy succinic acid, sulfanilic acid and sodium hydroxide into the mixed suspension, stirring and mixing, adding boron trifluoride diethyl etherate and dialdehyde chitosan, and stirring and reacting for 1h at 20-30 ℃ to obtain gel suspension;
s3: and (3) drying the gel suspension in vacuum at 30-50 ℃ to obtain the high-efficiency chlorine dioxide disinfectant.
Example 1
The production method of the efficient chlorine dioxide disinfectant comprises the following steps:
s1: preparing a modified immobilization carrier: adding octaepoxy cage-type silsesquioxane and isocyanate propyl triethoxysilane into tetrahydrofuran, stirring and dissolving, adding bis (2-dimethylaminoethyl) ether and zirconia aerogel with the average particle size of 150nm, performing ultrasonic dispersion, stirring and reacting for 1h in a water bath at 55 ℃, filtering, and removing tetrahydrofuran by rotary evaporation to obtain a modified immobilization carrier; the dosage proportion of the octaepoxy cage type silsesquioxane, the isocyanate propyltriethoxysilane, the tetrahydrofuran, the bis (2-dimethylaminoethyl) ether and the zirconia aerogel is 0.1g:0.05 g:5mL:0.01g:1 g;
s2: weighing the following raw materials in parts by mass for standby: 35 parts of sodium chlorite, 25 parts of epoxy succinic acid, 10 parts of sulfanilic acid, 4 parts of lithium magnesium silicate, 1 part of sodium metasilicate pentahydrate, 0.8 part of sodium hydroxide, 40 parts of modified immobilization carrier, 1 part of boron trifluoride diethyl ether, 2.5 parts of dialdehyde chitosan and 100 parts of deionized water;
s3: adding sodium chlorite into deionized water, stirring and dissolving, adding magnesium lithium silicate, sodium metasilicate pentahydrate and modified immobilization carrier, performing ultrasonic dispersion, and performing pressurized impregnation and adsorption for 20min under the pressure of 0.4MPa to obtain mixed suspension;
s4: adding epoxy succinic acid, sulfanilic acid and sodium hydroxide into the mixed suspension, stirring and mixing, adding boron trifluoride diethyl etherate and dialdehyde chitosan, and stirring and reacting for 1h at 20 ℃ to obtain gel suspension;
s5: and (3) drying the gel suspension in vacuum at 30 ℃ to obtain the high-efficiency chlorine dioxide disinfectant.
Example 2
The production method of the efficient chlorine dioxide disinfectant comprises the following steps:
s1: preparing a modified immobilization carrier: adding octaepoxy cage-type silsesquioxane and isocyanate propyl triethoxysilane into tetrahydrofuran, stirring and dissolving, adding pentamethyl diethylenetriamine and ZSM-5 zeolite molecular sieve with the average particle size of 300nm, performing ultrasonic dispersion, stirring and reacting for 2 hours in a water bath at 60 ℃, filtering, and removing tetrahydrofuran by rotary evaporation to obtain a modified immobilization carrier; the dosage ratio of the octaepoxy group cage type silsesquioxane to the isocyanate propyl triethoxysilane to the tetrahydrofuran to the pentamethyl diethylenetriamine to the ZSM-5 zeolite molecular sieve is 0.13g to 0.08g to 6.5mL to 0.02g to 1g;
s2: weighing the following raw materials in parts by mass for standby: 37.5 parts of sodium chlorite, 30 parts of epoxy succinic acid, 12.5 parts of sulfanilic acid, 5 parts of magnesium lithium silicate, 1.5 parts of lithium metasilicate pentahydrate, 1 part of sodium hydroxide, 45 parts of modified immobilization carrier, 1.5 parts of boron trifluoride diethyl ether, 4 parts of dialdehyde chitosan and 100 parts of deionized water;
s3: adding sodium chlorite into deionized water, stirring and dissolving, adding magnesium lithium silicate, lithium metasilicate pentahydrate and modified immobilization carrier, performing ultrasonic dispersion, and performing pressurized impregnation and adsorption under the pressure of 0.5MPa for 25min to obtain mixed suspension;
s4: adding epoxy succinic acid, sulfanilic acid and sodium hydroxide into the mixed suspension, stirring and mixing, adding boron trifluoride diethyl etherate and dialdehyde chitosan, and stirring and reacting at 25 ℃ for 1h to obtain gel suspension;
s5: and (3) drying the gel suspension in vacuum at 40 ℃ to obtain the high-efficiency chlorine dioxide disinfectant.
Example 3
The production method of the efficient chlorine dioxide disinfectant comprises the following steps:
s1: preparing a modified immobilization carrier: adding octaepoxy cage-type silsesquioxane and isocyanate propyl triethoxysilane into tetrahydrofuran, stirring and dissolving, adding triethylene diamine and UIO-66 material with the average particle diameter of 500nm, performing ultrasonic dispersion, stirring and reacting for 3 hours in a water bath at 65 ℃, filtering, and performing rotary evaporation to remove tetrahydrofuran to obtain a modified immobilization carrier; the dosage proportion of the octaepoxy cage type silsesquioxane, the isocyanate propyl triethoxysilane, the tetrahydrofuran, the triethylene diamine and the UIO-66 material is 0.15g:0.1g:8mL:0.02g:1g;
s2: weighing the following raw materials in parts by mass for standby: 40 parts of sodium chlorite, 35 parts of epoxy succinic acid, 15 parts of sulfanilic acid, 6 parts of magnesium sodium silicate, 1.5 parts of pentahydrate potassium metasilicate, 1.2 parts of sodium hydroxide, 50 parts of modified immobilization carrier, 2 parts of boron trifluoride diethyl ether, 5 parts of dialdehyde chitosan and 100 parts of deionized water;
s3: adding sodium chlorite into deionized water, stirring and dissolving, adding magnesium sodium silicate, potassium metasilicate pentahydrate and modified immobilization carrier, performing ultrasonic dispersion, and performing pressurized impregnation and adsorption for 30min under the pressure of 0.5MPa to obtain mixed suspension;
s4: adding epoxy succinic acid, sulfanilic acid and sodium hydroxide into the mixed suspension, stirring and mixing, adding boron trifluoride diethyl etherate and dialdehyde chitosan, and stirring and reacting for 1h at 30 ℃ to obtain gel suspension;
s5: and (3) drying the gel suspension in vacuum at 45 ℃ to obtain the high-efficiency chlorine dioxide disinfectant.
Comparative example 1 is the same as example 1, except that: the modified immobilization support in example 1 was replaced with a zirconia aerogel having an average particle diameter of 150 nm.
Comparative example 2 is the same as example 1, except that: in the S1 process of preparing the modified immobilization carrier, no octaepoxy group cage-type silsesquioxane is added, specifically: adding isocyanate propyl triethoxysilane into tetrahydrofuran, stirring and dissolving, adding bis (2-dimethylaminoethyl) ether and zirconia aerogel with the average particle size of 150nm, performing ultrasonic dispersion, stirring and reacting in a water bath at 55 ℃ for 1h, filtering, and removing tetrahydrofuran by rotary evaporation to obtain a modified immobilization carrier; the dosage ratio of the isocyanate propyl triethoxysilane, the tetrahydrofuran, the bis (2-dimethylaminoethyl) ether and the immobilized carrier is 0.15g to 5mL to 0.01g to 1g.
Comparative example 3 is the same as example 1, except that: in the preparation process of S4, no sulfanilic acid is added, and the mass part of the epoxy succinic acid is 35 parts.
Comparative example 4 is the same as example 1, except that: in the S4 preparation process, dialdehyde chitosan is not added.
Comparative example 5 is the same as example 1, except that: the modified immobilization carrier in example 1 was replaced with zirconia aerogel having an average particle diameter of 150nm, and dialdehyde chitosan was not added in the preparation process of S4.
1. Stability test:
the stability (the reduction rate of the content of the effective components is less than or equal to 10%) of the chlorine dioxide disinfectant prepared in examples 1-3 and comparative examples 1-5 is measured according to GB/T26366-2021 "hygienic requirement for chlorine dioxide disinfectant", and the test results are shown in Table 1:
TABLE 1
Stability/month
Example 1 24
Example 2 27
Example 3 25
Comparative example 1 15
Comparative example 2 17
Comparative example 3 23
Comparative example 4 13
Comparative example 5 10
As can be seen from Table 1, compared with comparative examples 1-5, the stability of the chlorine dioxide disinfectant prepared in examples 1-3 is improved to different degrees, and the chlorine dioxide disinfectant prepared in examples 1-3 has excellent controlled release and slow release properties, and can be used for long-acting disinfection and antibiosis.
2. Disinfectant kill microbiology test:
after the chlorine dioxide disinfectants prepared in examples 1-3 and comparative example 3 are diluted with water according to a solid-to-liquid ratio of 1g/3mL, the microbial killing performance is further measured according to GB/T26366-2021 hygienic requirement for chlorine dioxide disinfectants, and the test results are shown in Table 2:
TABLE 2
Figure SMS_3
As can be seen from Table 2, compared with comparative example 3 without adding sulfanilic acid, the microbial killing performance of the chlorine dioxide disinfectant prepared in examples 1-3 is obviously improved, and especially the sterilizing effect on Aspergillus niger is improved, and the synergistic effect of sulfanilic acid/sodium sulfanilic acid and chlorine dioxide is proved.
Examples 1-3 firstly use epoxy succinic acid and sulfanilic acid as acid activators and sodium chlorite as chlorine dioxide precursors, and the three react together to produce chlorine dioxide, and the epoxy succinic acid sodium and the sulfanilic acid sodium produced by the reaction have complexation, can chelate heavy metal ions to form stable metal complexes, further achieve the effects of removing heavy metal ions and inhibiting scale and slow release, and simultaneously, have the effects of reducing the scale and the corrosion resistance of the heavy metal ionsThe sodium aminobenzenesulfonate/sulfanilic acid also has antibacterial and sterilizing effects, and is synergistic with chlorine dioxide, and has high-efficiency sterilization and disinfection, and uses modified immobilization carrier rich in epoxy groups and isocyanate groups for carrying out loading, and then adopts dialdehyde chitosan gel for further embedding immobilization, and the-NH in dialdehyde chitosan 2 Ring-opening addition reaction with modified immobilized carrier and epoxy group in epoxy sodium succinate/epoxy succinic acid, dialdehyde chitosan, sodium sulfanilate/NH in sulfanilate 2 Nucleophilic addition reaction with-N=C=O on the surface of the modified immobilized carrier, and-CHO in dialdehyde chitosan and-NH in sodium sulfanilate/sulfanilate 2 The Schiff base reaction occurs, intermolecular self-assembly is carried out through chemical crosslinking reaction, a three-dimensional interpenetrating network structure is formed, multiple stable immobilization of the disinfectant active ingredients is further realized, and the loading capacity and embedding efficiency of the chlorine dioxide disinfectant are remarkably improved.
In the embodiment 1-3, sodium chlorite is subjected to pressurized impregnation adsorption through a modified immobilized carrier, and is further embedded and immobilized by utilizing a dialdehyde chitosan combined gel method and a chemical crosslinking effect, so that the slow-release solid chlorine dioxide disinfectant is prepared, the chlorine dioxide component can be released smoothly and slowly, the disinfection and antibacterial effects can be exerted permanently and efficiently, and the storage time and the service time are long.
The examples 1-3 use epoxy succinic acid and sulfanilic acid as acid activators for the first time, and compared with the traditional hydrochloric acid activators, the chlorine dioxide sterilizing effect is excellent, wherein the chlorine dioxide sterilizing effect is excellent.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.

Claims (10)

1. The efficient chlorine dioxide disinfectant is characterized by comprising the following raw materials in parts by mass:
35-40 parts of sodium chlorite
25-35 parts of epoxy succinic acid
10-15 parts of sulfanilic acid
4-6 parts of thickening agent
1 to 1.5 parts of dispersant
0.8-1.2 parts of sodium hydroxide
40-50 parts of modified immobilization carrier
Boron trifluoride diethyl etherate 1-2 parts
2.5-5 parts of dialdehyde chitosan
100 parts of deionized water;
the preparation method of the modified immobilization carrier comprises the following steps: adding octaepoxy cage-type silsesquioxane and isocyanate propyl triethoxysilane into tetrahydrofuran, stirring for dissolving, adding tertiary amine catalyst and immobilized carrier with average particle size of 150-500nm, performing ultrasonic dispersion, stirring in water bath at 55-65deg.C for reaction for 1-3 hr, filtering, and rotary evaporating to remove tetrahydrofuran to obtain modified immobilized carrier.
2. The efficient chlorine dioxide disinfectant according to claim 1, wherein the dosage ratio of the octaepoxycage silsesquioxane, the isocyanate propyltriethoxysilane, the tetrahydrofuran, the tertiary amine catalyst and the immobilization carrier is (0.1-0.15) g (0.05-0.1) g (5-8) mL (0.01-0.02) g/1 g.
3. The efficient chlorine dioxide disinfectant according to claim 1 or 2, wherein the tertiary amine catalyst is one or more of bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, triethylenediamine, triethylamine.
4. The high-efficiency chlorine dioxide disinfectant according to claim 1, wherein the thickener is one or both of lithium magnesium silicate and sodium magnesium silicate.
5. The high-efficiency chlorine dioxide disinfectant according to claim 1, wherein the dispersant is one or more of sodium metasilicate pentahydrate, lithium metasilicate pentahydrate, and potassium metasilicate pentahydrate.
6. The efficient chlorine dioxide disinfectant according to claim 1 or 2, wherein the immobilization carrier is one or more of an oxide aerogel, a zeolite molecular sieve, MOFs materials.
7. The efficient chlorine dioxide disinfectant according to claim 6, wherein the oxide aerogel is one or more of zirconia aerogel, alumina aerogel, silica aerogel.
8. The efficient chlorine dioxide disinfectant according to claim 6, wherein the zeolite molecular sieve is one or more of ZSM-5 type zeolite molecular sieve, beta-25 type zeolite molecular sieve, beta-60 type zeolite molecular sieve, SAPO-11 type zeolite molecular sieve.
9. The high-efficiency chlorine dioxide disinfectant according to claim 6, wherein the MOFs material is one or more of UIO-66 material, ZIF-8 material, MIL-125 material.
10. The method for producing high-efficiency chlorine dioxide disinfectant according to any of claims 1, 2, 4 to 9, comprising the steps of:
s1: adding sodium chlorite into deionized water, stirring and dissolving, adding a thickening agent, a dispersing agent and a modified immobilized carrier, performing ultrasonic dispersion, and performing pressurized impregnation and adsorption for 15-30min under the pressure of 0.4-0.5MPa to obtain a mixed suspension;
s2: adding epoxy succinic acid, sulfanilic acid and sodium hydroxide into the mixed suspension, stirring and mixing, adding boron trifluoride diethyl etherate and dialdehyde chitosan, and stirring and reacting for 1h at 20-30 ℃ to obtain gel suspension;
s3: and (3) drying the gel suspension in vacuum at 30-50 ℃ to obtain the high-efficiency chlorine dioxide disinfectant.
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CN116548467B (en) * 2023-07-11 2023-09-19 山东华实药业有限公司 Chlorine dioxide disinfectant and its production process and application
CN116649362B (en) * 2023-07-31 2023-09-26 山东华实药业有限公司 Chlorine dioxide disinfection tablet and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110250199A (en) * 2019-05-20 2019-09-20 天津大学 A kind of disinfection agent of chlorine dioxide containing load-type solid acid and preparation method and application
CN111493087A (en) * 2020-04-22 2020-08-07 浙江施维康生物医学材料有限公司 Slow-release chlorine dioxide disinfectant and preparation method thereof
CN111567552A (en) * 2020-05-22 2020-08-25 中节能(唐山)环保装备有限公司 Slow-release chlorine dioxide air purification gel and preparation method thereof
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
CN114403157A (en) * 2022-02-11 2022-04-29 山东大学 Double-component gel slow-release chlorine dioxide disinfectant and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10660339B2 (en) * 2018-06-04 2020-05-26 Spectrum Doxyicide, Llc Chlorine dioxide based formulation with improved stability
CN111771907A (en) * 2020-08-03 2020-10-16 中山大学 Antivirus nano material for slowly releasing chlorine dioxide and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110250199A (en) * 2019-05-20 2019-09-20 天津大学 A kind of disinfection agent of chlorine dioxide containing load-type solid acid and preparation method and application
CN111493087A (en) * 2020-04-22 2020-08-07 浙江施维康生物医学材料有限公司 Slow-release chlorine dioxide disinfectant and preparation method thereof
CN111567552A (en) * 2020-05-22 2020-08-25 中节能(唐山)环保装备有限公司 Slow-release chlorine dioxide air purification gel and preparation method thereof
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
CN114403157A (en) * 2022-02-11 2022-04-29 山东大学 Double-component gel slow-release chlorine dioxide disinfectant and preparation method and application thereof

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