CN112661899A - Slow-release carrier, chlorine dioxide gel composition containing same and application thereof - Google Patents
Slow-release carrier, chlorine dioxide gel composition containing same and application thereof Download PDFInfo
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- CN112661899A CN112661899A CN202011397480.1A CN202011397480A CN112661899A CN 112661899 A CN112661899 A CN 112661899A CN 202011397480 A CN202011397480 A CN 202011397480A CN 112661899 A CN112661899 A CN 112661899A
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Abstract
The invention discloses a slow release carrier, a chlorine dioxide gel composition containing the slow release carrier and application thereof. The slow release carrier is prepared by adding a vinyl monomer solution containing a cross-linking agent and an initiator into a dispersion medium containing a separant and adopting a reversed-phase suspension method. The slow release carrier has a three-dimensional network structure and a cross-linking gradient, has super-strong water absorption and water retention performance, and can be used as an excellent reaction site of various slow release preparations. Moreover, after the chlorine dioxide precursor is loaded on the slow-release carrier, the controllable slow release of the chlorine dioxide can be realized, and the slow-release carrier has the application prospects in various aspects such as sterilization, disinfection, air purification, deodorization, fresh keeping and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a slow release carrier, a gel composition containing the slow release carrier and application of the gel composition.
Background
Chlorine dioxide (ClO)2) Has high-efficiency broad-spectrum bactericidal power, is a strong oxidant, and can quickly decompose bacteria, viruses and proteins by its strong oxidizing propertyThe amino acid in the product can react with other reducing substances, various inorganic ions and organic matters. Compared with chlorine, when the chlorine dioxide is used for disinfection, only oxidation reaction, no chlorination reaction and carcinogens such as chlorohydrocarbon and the like are generated, and the oxidation capacity is 2.6 times of that of the chlorine.
However, chlorine dioxide gas is very active and unstable, is difficult to prepare into compressed gas or concentrated solution, needs to be prepared on site when in use, and cannot be stored and transported because the chlorine dioxide gas belongs to explosive gas, so that the application range of the chlorine dioxide is greatly limited.
Some studies have attempted to prepare a stable chlorine dioxide solution or a solid preparation of chlorine dioxide, but the stable chlorine dioxide solution needs an activation treatment before use and still has inconvenience during use and transportation. The existing chlorine dioxide solid preparation is mainly prepared by absorbing stable chlorine dioxide solution by a specific adsorption carrier and mixing the solution with solid acid, stabilizer and the like, and the release speed of chlorine dioxide gas is controlled by controlling the amount of added solid acid or the strength of acid.
Therefore, a novel slow release carrier is urgently needed to be developed to effectively carry chlorine dioxide, break through the application limit of chlorine dioxide in the prior art and widen the application prospect of chlorine dioxide.
Disclosure of Invention
The invention aims to provide a slow-release carrier;
another object of the present invention is to provide a method for preparing the above sustained-release carrier;
it is another object of the present invention to provide a composition;
another object of the present invention is to provide a process for preparing the above composition;
the invention also aims to provide the application of the slow-release carrier or the composition in sterilization and purification.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
a slow release carrier, which is a polymer with a cross-linking gradient and a three-dimensional network structure;
wherein, the crosslinking gradient is increased from the inside of the sustained-release carrier to the outside in a gradient manner;
the slow release carrier contains hydrophilic group sodium carboxylate.
The slow release carrier in the embodiment of the invention is composed of an inner layer and an outer layer of high molecular polymers with different crosslinking degrees, which are prepared by two crosslinking reactions, wherein the high molecular polymers contain a large amount of hydrophilic group sodium carboxylate, and the molecular structure of the high molecular polymers presents a three-dimensional network structure, so that the slow release carrier has super water absorption and water retention capacities. The inner layer and the outer layer of the slow release carrier are high molecular polymers with different crosslinking degrees, so that the whole slow release carrier has a certain crosslinking gradient.
Wherein, the inner layer has small degree of crosslinking and strong water absorption capacity; the crosslinking degree of the outer layer is high, the pressure resistance is good, the water retention capacity is strong, and the water absorption capacity is weak. When the sustained-release carrier prepared by the preparation method is contacted with water, firstly, a certain amount of water is absorbed by the sustained-release carrier through a capillary effect and a hydration effect of hydrophilic groups, so that the hydrophilic groups of sodium carboxylate are ionized, sodium ions with positive charges become movable ions, and carboxylate ions with negative charges are still fixed on a molecular chain of the sustained-release carrier. Along with the lapse of time, will produce the electrostatic repulsion gradually with the leaving of positive charge sodium ion (positive charge sodium ion will be along with the absorption of water and constantly move to the inlayer) between the carboxylate radical ion with negative charge, make the molecular chain of the slow release carrier begin to extend gradually, the three-dimensional network begins to expand; meanwhile, the concentration of positively charged sodium ions in the inner layer of the slow release carrier is continuously increased, so that the concentration of the aqueous solution in the inner layer is smaller than that in the outer layer, osmotic pressure is generated, and the water in the outer layer is further diffused to the inner layer. Along with the gradual increase of water molecules in the inner layer of the slow release carrier, the concentration difference of sodium ions between the inner layer and the outer layer is gradually reduced, so that the osmotic pressure is reduced, and the moisture content of the inner layer gradually tends to be stable. And when the three-dimensional network of the inner layer and the outer layer of the slow release carrier expands, the elastic contraction force of the slow release carrier is continuously increased, and when the electrostatic repulsion force and the elastic contraction force can be mutually offset, the water absorption of the slow release carrier reaches balance, the slow release carrier does not absorb water any more, and the water retention stage begins. However, once the water in the sustained-release carrier is consumed by an external force (such as a chemical reaction) at this time, the sustained-release carrier enters a water absorption stage again until the water absorption equilibrium is reached again.
Further, the sustained-release carrier comprises the following components in parts by mass:
120-130 parts of vinyl monomer, 0.01-0.05 part of cross-linking agent, 0.1-0.5 part of isolating agent, 580-620 parts of dispersing medium and 0.3-0.5 part of initiator.
Further, the sustained-release carrier is prepared from the following components in parts by mass:
125 parts of vinyl monomer, 0.03 part of cross-linking agent, 0.3 part of separant, 600 parts of dispersion medium and 0.3 part of initiator;
wherein the mass ratio of the oxidation initiator to the reduction initiator is 4: 1.
in a second aspect of the present invention, there is provided:
the preparation method of the sustained-release carrier comprises the following steps:
(1) adding a vinyl monomer solution containing a cross-linking agent and an initiator into a dispersion medium containing a release agent to form a reversed-phase suspension system, and forming a primary product through a polymerization reaction and a cross-linking reaction;
(2) reducing the water content in the reaction system, and adding the cross-linking agent again for cross-linking reaction to obtain the product.
Wherein the addition amount of the cross-linking agent in the step (2) is larger than that in the step (1).
Further, the above-mentioned reducing the moisture content in the system includes reducing the moisture content in the system to 0.
In the preparation method of the sustained-release carrier in the embodiment of the invention, the cross-linking agent is introduced twice in sequence for cross-linking reaction during preparation. In a reversed phase suspension system, after a high molecular polymer (the primary product in the step (1)) is obtained through a first crosslinking reaction, the moisture content in the system is reduced, then a crosslinking agent is added again for a second crosslinking reaction, and after water is removed, the primary product is coated with a layer of high molecular polymer.
Further, the step (2) of reducing the moisture content in the reaction system comprises the following specific steps: and (2) performing high-temperature reflux treatment after the step (1). Wherein the reaction temperature is 40-100 ℃.
Of course, other methods for adjusting the degree of crosslinking that are conventional in the art can be adopted by those skilled in the art to achieve the high molecular polymers with different degrees of crosslinking in the inner and outer layers obtained by the preparation method of the present invention.
Further, the preparation method further comprises cooling, filtering, removing impurities with absolute ethyl alcohol and drying after the crosslinking reaction in the step (2).
Further, the drying is vacuum drying, and the drying temperature is 70-75 ℃, preferably 75 ℃.
Further, the reaction time of the preparation method is 2-6 hours.
Further, the vinyl monomer comprises one or the combination of acrylic acid, methacrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid; further, the vinyl monomer is preferably acrylic acid.
Further, the acidic vinyl monomer such as acrylic acid may be neutralized to 60 to 80 mol% with an alkali.
Still further, the above base includes sodium hydroxide solution; furthermore, the mass percent of the sodium hydroxide solution is 20-25%.
Still further, the sodium hydroxide solution was 25% by mass.
Further, the neutralization of the acidic vinyl monomer such as acrylic acid is required to be performed in a low temperature environment (0 to 5 ℃), and the low temperature environment is preferably an ice water bath environment (about 0 ℃).
Further, the crosslinking agent comprises one or a combination of N, N' -methylene bisacrylamide, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol diglycidyl ether, divinylbenzene and diisocyanate.
Further, the crosslinking agent is N, N' -methylenebisacrylamide.
Further, the release agent comprises one or a combination of sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether phosphate, polyoxyethylene fatty acid ester and polyoxyethylene ether sorbitan fatty acid ester.
Further, the release agent is polyoxyethylene alkyl ether phosphate.
Further, the dispersion medium includes an alkane and a cycloalkane.
Still further, the above-mentioned alkane includes one or a combination of n-hexane, n-heptane, n-octane, 3-ethylpentane, 2-methylhexane and 3-methylhexane; still further, the cycloalkane includes one or a combination of cyclohexane, cyclopentane, methylcyclopentane, and methylcyclohexane.
Further, the dispersion medium is cyclohexane.
Further, the initiator comprises an oxidation initiator and a reduction initiator, wherein the mass ratio of the oxidation initiator to the reduction initiator is (2-6) to 1.
Wherein, the oxidation initiator comprises one or the combination of potassium persulfate, ammonium persulfate and hydrogen peroxide; the reduction initiator comprises one or the combination of sodium sulfite, sodium bisulfite, potassium sulfite and potassium bisulfite.
Further, the above oxidation initiator is potassium persulfate; the reduction initiator is sodium bisulfite.
In a third aspect of the present invention, there is provided:
a composition comprising the sustained release carrier and a water-soluble compound.
The water-soluble compound is mixed with the slow release carrier, so that the slow release carrier loads the water-soluble compound to form the slow release gel. Based on the water retention property of the sustained-release carrier, the sustained-release gel can play a sustained-release effect on the loaded water-soluble compound.
The existing inorganic or organic carriers, such as silica gel, active carbon, carboxymethyl cellulose, water-absorbing resin, gelatin, starch or cyclodextrin and the like, can not be used together with a chlorine dioxide solid preparation, and can not realize the generation, diffusion and transfer mechanism of chlorine dioxide, and the molecular structure of the slow-release carrier meets the design requirement of chlorine dioxide slow release, so that the situation that the prepared chlorine dioxide disinfection product has unstable release of chlorine dioxide or the release time can not reach the expected purpose in use can not be caused.
Wherein the compound contains 2-32.65% of slow release carrier by mass ratio.
Further, the water-soluble compound comprises a chlorine dioxide precursor, and further, the chlorine dioxide precursor comprises one or a combination of sodium chlorite, potassium chlorite, calcium chlorite and magnesium chlorite.
Further, the chlorine dioxide precursor is sodium chlorite.
The chlorine dioxide precursor can be used as a supply source of chlorine dioxide, and reacts with an acidic substance to generate chlorine dioxide gas, and the reaction chemical equation is as follows:
5ClO2-+4H+→4ClO2+2H2O+Cl-
further, the composition also comprises a stabilizer, a solid acidifier and a passivator.
Still further, the above stabilizer includes one or a combination of magnesium sulfate, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, sodium phosphate, disodium hydrogen phosphate and dipotassium hydrogen phosphate.
Further, the stabilizer is calcium chloride.
The addition of the stabilizer can make the chlorine dioxide precursor in the composition more stable.
Still further, the solid acidulant comprises one or a combination of citric acid, tartaric acid, oxalic acid, malic acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate and aluminum sulfate.
Further, the solid acidulant is citric acid.
The solid acidifying agent is used in the above composition as a reaction activator, the purpose of which is to provide H for the chlorine dioxide precursor+. The solid acidulant must first be sufficiently combined with a quantity of water to release H+And reacting with chlorine dioxide precursor. In the composition in the embodiment of the invention, the water needed by the solid acidifier is provided by the slow release carrier with water absorption and retention functions, and the reaction rate is regulated and controlled by regulating the molecular structure and the internal and external crosslinking gradient of the slow release carrier and changing the addition amount of the slow release carrier.
Further, the passivating agent comprises inorganic clay; the inorganic clay comprises one or more of montmorillonite, kaolin, diatomite, attapulgite and perlite.
Further, the passivating agent is montmorillonite.
In the composition of the embodiment of the invention, the passivating agent is coated on the outer layer of the solid acidifying agent, so that the solid acidifying agent can be prevented from directly contacting with the chlorine dioxide precursor in the sustained-release gel before the product takes effect, and meanwhile, due to the existence of the passivating agent, the solid acidifying agent can not immediately react with the chlorine dioxide precursor to rapidly generate chlorine dioxide even if accidents such as collision occur in the product transportation process.
Furthermore, the compound comprises 2-32.65% of slow release carrier, 2-10.21% of chlorine dioxide precursor, 0.4-8.16% of stabilizer, 2-16.33% of solid acidifier and 2-32.65% of deactivator in mass ratio.
The addition amount of the solid acidifying agent can be adjusted according to the type and the reaction degree of the chlorine dioxide precursor, so that the solid acidifying agent can be fully reacted with the chlorine dioxide precursor in the composition to achieve the optimal reaction.
In a fourth aspect of the present invention, there is provided:
the preparation method of the composition comprises the following steps:
(1) mixing the chlorine dioxide precursor solution, the slow release carrier and the stabilizer to prepare a component A; coating a solid acidifier in a passivator to prepare a component B;
(2) mixing the component A and the component B to obtain the composition.
Furthermore, the preparation method also comprises the step of adding a slow-release carrier into the component B.
Further, the preparation method also comprises the step of packaging after the component A and the component B are mixed.
Still further, the packaging includes vacuum hybrid packaging.
Of course, it is also possible to package the component A and the component B separately before mixing them, depending on the actual use, until the component A and the component B are mixed at the time of use.
Furthermore, the preparation method also comprises the step of adding different auxiliary materials, so that the prepared composition has different formulations including paste, gel, powder and the like, and meets the actual use requirements.
In a fifth aspect of the present invention, there is provided:
the slow release carrier or the composition is applied to sterilization and purification.
Further, the sterilization and purification includes purification of harmful substances (such as formaldehyde in the air), air or surface sterilization, deodorization and freshness preservation.
When the composition is used for sterilization and purification, the composition can be used in a special release container or directly vacuum-sealed in the release container. The packaging device, the release container and the special release device for the composition are made of plastic materials, such as polypropylene, polyethylene, polyester, and the like.
The invention has the beneficial effects that:
1. the slow release carrier provided by the invention is a high molecular polymer with a proper three-dimensional network structure and a certain crosslinking degree, the molecular structure of the carrier contains a large number of hydrophilic groups, and the inner layer and the outer layer have a certain crosslinking gradient, so that the carrier has super-strong water absorption and water retention performances, and provides an excellent reaction site for carrying various slow release preparations.
2. The composition provided by the invention can effectively load chlorine dioxide precursors, overcomes the use defects of the existing chlorine dioxide solid preparation, realizes the controllable slow release of chlorine dioxide, can be prepared into paste, gel and powder, can be placed in a proper place, and has the functions of sterilization, disinfection, air purification, deodorization, fresh keeping and the like.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention will be described in further detail with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental materials and reagents used are, unless otherwise specified, all consumables and reagents which are conventionally available from commercial sources.
In the present specification, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise specified.
Example 1A sustained Release Carrier and a sustained Release chlorine dioxide gel composition thereof
(1) Preparation of the sustained-release carrier:
preparation of aqueous phase solution:
under the condition of an ice-water bath, 125 parts of an acrylic acid aqueous solution (concentration: 80%) was titrated with a 25% sodium hydroxide solution to make the neutralization degree of the solution 65%, and then 0.01 part of N, N' -methylenebisacrylamide, 0.24 part of potassium persulfate, and 0.06 part of sodium bisulfite were added in this order to prepare an aqueous solution.
Preparing an oil phase solution:
0.3 part of polyoxyethylene alkyl ether phosphate is added to 600 parts of cyclohexane and dissolved to prepare an oil phase solution.
Preparation of the sustained-release carrier:
slowly heating the oil phase solution to 70 ℃, dropwise adding the water phase solution into the oil phase solution under the protection of nitrogen, and continuously reacting for 3 hours to obtain a primary product (primary polymer) with a certain crosslinking degree; removing water in the system by high-temperature reflux, adding 0.02 part of N, N' -methylene bisacrylamide for secondary crosslinking, cooling and filtering to obtain a high molecular polymer with crosslinking gradient, soaking and washing the high molecular polymer with absolute ethyl alcohol twice to remove impurities, and drying at 75 ℃ in vacuum to constant weight to obtain the slow-release carrier.
(2) Preparation of sustained-release chlorine dioxide gel composition:
preparing 5g of 80% sodium chlorite into 10% chlorine dioxide precursor water solution, and adding 9g of the slow release carrier prepared in the step (1) and 2.5g of calcium chloride to prepare gel solid A (component A).
2.26g of citric acid and 3.74g of montmorillonite were mixed uniformly to prepare a solid B (component B).
And uniformly mixing the gel solid A and the solid B to prepare the slow-release chlorine dioxide gel composition.
Example 2A sustained Release Carrier and a sustained Release chlorine dioxide gel composition thereof
(1) Preparation of the sustained-release carrier:
preparation of aqueous phase solution:
under the condition of an ice-water bath, 125 parts of an acrylic acid aqueous solution (concentration: 80%) was titrated with a 25% sodium hydroxide solution to make the neutralization degree of the solution 75%, and then 0.01 part of N, N' -methylenebisacrylamide, 0.24 part of potassium persulfate, and 0.06 part of sodium bisulfite were added in this order to prepare an aqueous solution.
Preparing an oil phase solution:
0.3 part of polyoxyethylene alkyl ether phosphate is added to 600 parts of cyclohexane and dissolved to prepare an oil phase solution.
Preparation of the sustained-release carrier:
slowly heating the oil phase solution to 70 ℃, dropwise adding the water phase solution into the oil phase solution under the protection of nitrogen, and continuously reacting for 3 hours to obtain a primary product (primary polymer) with a certain crosslinking degree; removing water in the system by high-temperature reflux, adding 0.02 part of N, N' -methylene bisacrylamide for secondary crosslinking, cooling and filtering to obtain a high molecular polymer with crosslinking gradient, soaking and washing the high molecular polymer with absolute ethyl alcohol twice to remove impurities, and drying at 75 ℃ in vacuum to constant weight to obtain the slow-release carrier.
(2) Preparation of sustained-release chlorine dioxide gel composition:
preparing 5g of 80% sodium chlorite into 10% chlorine dioxide precursor water solution, and adding 9g of the slow release carrier prepared in the step (1) and 2.5g of calcium chloride to prepare gel solid A (component A).
2.26g of citric acid and 3.74g of montmorillonite were mixed uniformly to prepare a solid B (component B).
And uniformly mixing the gel solid A and the solid B to prepare the slow-release chlorine dioxide gel composition.
In this example, the neutralization degree in example 1 was changed to 75% only, as compared with example 1.
Example 3A sustained Release Carrier and a sustained Release chlorine dioxide gel composition thereof
(1) Preparation of the sustained-release carrier:
preparation of aqueous phase solution:
under the condition of an ice-water bath, 125 parts of an acrylic acid aqueous solution (concentration: 80%) was titrated with a 25% sodium hydroxide solution to make the neutralization degree of the solution 75%, and then 0.01 part of N, N' -methylenebisacrylamide, 0.24 part of potassium persulfate, and 0.06 part of sodium bisulfite were added in this order to prepare an aqueous solution.
Preparing an oil phase solution:
0.3 part of polyoxyethylene alkyl ether phosphate is added to 600 parts of cyclohexane and dissolved to prepare an oil phase solution.
Preparation of the sustained-release carrier:
slowly heating the oil phase solution to 70 ℃, dropwise adding the water phase solution into the oil phase solution under the protection of nitrogen, and continuously reacting for 3 hours to obtain a primary product (primary polymer) with a certain crosslinking degree; removing water in the system by high-temperature reflux, adding 0.04 part of N, N' -methylene bisacrylamide for secondary crosslinking, cooling and filtering to obtain a high molecular polymer with crosslinking gradient, soaking and washing the high molecular polymer with absolute ethyl alcohol twice to remove impurities, and drying at 75 ℃ in vacuum to constant weight to obtain the slow-release carrier.
(2) Preparation of sustained-release chlorine dioxide gel composition:
preparing 5g of 80% sodium chlorite into 10% chlorine dioxide precursor water solution, and adding 9g of the slow release carrier prepared in the step (1) and 2.5g of calcium chloride to prepare gel solid A (component A).
2.26g of citric acid and 3.74g of montmorillonite were mixed uniformly to prepare a solid B (component B).
And uniformly mixing the gel solid A and the solid B to prepare the slow-release chlorine dioxide gel composition.
In this example, the amount of N, N' -methylenebisacrylamide added for the second crosslinking in example 2 was increased to 0.04 parts as compared with example 2.
Example 4A sustained Release Carrier and a sustained Release chlorine dioxide gel composition thereof
(1) Preparation of the sustained-release carrier:
preparation of aqueous phase solution:
under the condition of an ice-water bath, 125 parts of an acrylic acid aqueous solution (concentration: 80%) was titrated with a 25% sodium hydroxide solution to make the neutralization degree of the solution 75%, and then 0.01 part of N, N' -methylenebisacrylamide, 0.24 part of potassium persulfate, and 0.06 part of sodium bisulfite were added in this order to prepare an aqueous solution.
Preparing an oil phase solution:
0.3 part of polyoxyethylene alkyl ether phosphate is added to 600 parts of cyclohexane and dissolved to prepare an oil phase solution.
Preparation of the sustained-release carrier:
slowly heating the oil phase solution to 70 ℃, dropwise adding the water phase solution into the oil phase solution under the protection of nitrogen, and continuously reacting for 3 hours to obtain a primary product (primary polymer) with a certain crosslinking degree; removing water in the system by high-temperature reflux, adding 0.02 part of N, N' -methylene bisacrylamide for secondary crosslinking, cooling and filtering to obtain a high molecular polymer with crosslinking gradient, soaking and washing the high molecular polymer with absolute ethyl alcohol twice to remove impurities, and drying at 75 ℃ in vacuum to constant weight to obtain the slow-release carrier.
(2) Preparation of sustained-release chlorine dioxide gel composition:
preparing 5g of 80% sodium chlorite into 10% chlorine dioxide precursor aqueous solution, and adding 7g of the slow release carrier prepared in the step (1) and 2.5g of calcium chloride to prepare gel solid A (component A).
2.26g of citric acid and 3.74g of montmorillonite were mixed uniformly to prepare a solid B (component B).
And uniformly mixing the gel solid A and the solid B to prepare the slow-release chlorine dioxide gel composition.
In this example, the amount of the sustained-release carrier added in example 2 was reduced to 7g only, as compared with example 2.
Example 5A sustained Release Carrier and a sustained Release chlorine dioxide gel composition thereof
(1) Preparation of the sustained-release carrier:
preparation of aqueous phase solution:
under the condition of an ice-water bath, 125 parts of an acrylic acid aqueous solution (concentration: 80%) was titrated with a 25% sodium hydroxide solution to make the neutralization degree of the solution 75%, and then 0.01 part of N, N' -methylenebisacrylamide, 0.24 part of potassium persulfate, and 0.06 part of sodium bisulfite were added in this order to prepare an aqueous solution.
Preparing an oil phase solution:
0.3 part of polyoxyethylene alkyl ether phosphate is added to 600 parts of cyclohexane and dissolved to prepare an oil phase solution.
Preparation of the sustained-release carrier:
slowly heating the oil phase solution to 70 ℃, dropwise adding the water phase solution into the oil phase solution under the protection of nitrogen, and continuously reacting for 3 hours to obtain a primary product (primary polymer) with a certain crosslinking degree; removing water in the system by high-temperature reflux, adding 0.02 part of N, N' -methylene bisacrylamide for secondary crosslinking, cooling and filtering to obtain a high molecular polymer with crosslinking gradient, soaking and washing the high molecular polymer with absolute ethyl alcohol twice to remove impurities, and drying at 75 ℃ in vacuum to constant weight to obtain the slow-release carrier.
(2) Preparation of sustained-release chlorine dioxide gel composition:
preparing 5g of 80% sodium chlorite into 10% chlorine dioxide precursor water solution, and adding 5g of the slow release carrier prepared in the step (1) and 2.5g of calcium chloride to prepare gel solid A (component A).
2.26g of citric acid and 3.74g of montmorillonite were mixed uniformly to prepare a solid B (component B).
And uniformly mixing the gel solid A and the solid B to prepare the slow-release chlorine dioxide gel composition.
In this example, the amount of the sustained-release carrier added in example 2 was reduced to 5g only, as compared with example 2.
Comparative example 1 a chlorine dioxide gel composition
5g of 80% sodium chlorite was prepared into a 10% chlorine dioxide precursor aqueous solution, and 2.5g of calcium chloride was added to prepare a gel solid A (component A).
2.26g of citric acid and 3.74g of montmorillonite were mixed uniformly to prepare a solid B (component B).
And uniformly mixing the gel solid A and the solid B to prepare the chlorine dioxide gel composition.
In this example, compared to example 2, the sustained release carrier of example 2 above was not added.
Chlorine dioxide release effect detection
The sustained-release chlorine dioxide gel compositions prepared in examples 1 to 5 and the control sample prepared in comparative example 1 were tested for the amount of released chlorine dioxide.
The test method is as follows:
placing the test object in a light-proof sealed environment, taking the generated chlorine dioxide out by using constant air flow and dissolving the chlorine dioxide in distilled water, and measuring the concentration of the chlorine dioxide in the distilled water by using an ultraviolet spectrophotometry.
The results are shown in Table 1.
TABLE 1 chlorine dioxide release amounts of examples 1 to 5 and comparative example 1
As can be seen from table 1, the neutralization degree and the crosslinking degree of the sustained-release carrier affect the performance of the sustained-release carrier, and the low neutralization degree and the high crosslinking degree affect the network structure in the molecular structure of the sustained-release carrier, so that the absorption and water retention capacity of the sustained-release carrier is reduced, and the release rate of chlorine dioxide in the chlorine dioxide gel composition is reduced; under the condition of the same neutralization degree and crosslinking degree, the addition amount of the slow release carrier can also influence the release rate of chlorine dioxide, and the addition amount of the slow release carrier is reduced to reduce the release rate of chlorine dioxide under the condition of ensuring the normal release of chlorine dioxide; under the condition of not adding a slow release carrier, the chlorine dioxide can be released in a short time.
According to the above conclusion, it can be further illustrated that the composition in the above embodiments can adjust the release rate of chlorine dioxide by adjusting the molecular structure and the addition amount of the sustained-release carrier, so as to adapt to different usage scenarios.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The slow release carrier is characterized in that the slow release carrier is a polymer with a cross-linking gradient and a three-dimensional network structure;
wherein the crosslinking gradient is increased from the inside of the sustained-release carrier to the outside in a gradient manner;
the polymer contains a hydrophilic group sodium carboxylate.
2. The slow release carrier according to claim 1, which is prepared from 120 to 130 parts by mass of a vinyl monomer, 0.01 to 0.05 part by mass of a cross-linking agent, 0.1 to 0.5 part by mass of a release agent, 580 to 620 parts by mass of a dispersion medium, and 0.3 to 0.5 part by mass of an initiator;
wherein the initiator preferably comprises an oxidation initiator and a reduction initiator; the mass ratio of the oxidation initiator to the reduction initiator is (2-6): 1.
3. a process for preparing an extended release carrier according to claim 2, comprising the steps of:
(1) adding a vinyl monomer solution containing a cross-linking agent and an initiator into a dispersion medium containing a release agent to form a reversed-phase suspension system, and forming a primary product through a polymerization reaction and a cross-linking reaction;
(2) reducing the water content in the reaction system, and adding the cross-linking agent again for cross-linking reaction to obtain the product.
4. The method of claim 3, wherein the vinyl monomer comprises one or a combination of acrylic acid, methacrylic acid, acrylamide and 2-acrylamido-2-methylpropanesulfonic acid;
the cross-linking agent comprises one or the combination of N, N' -methylene bisacrylamide, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol diglycidyl ether, divinylbenzene and diisocyanate;
the separant comprises one or a combination of sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether phosphate, polyoxyethylene fatty acid ester and polyoxyethylene ether sorbitan fatty acid ester;
the dispersion medium comprises alkane and cycloalkane;
wherein the alkane comprises one or the combination of n-hexane, n-heptane, n-octane, 3-ethylpentane, 2-methylhexane and 3-methylhexane;
the cycloalkane comprises one or the combination of cyclohexane, cyclopentane, methyl cyclopentane and methyl cyclohexane.
5. The production method according to claim 3, wherein the initiator includes an oxidation initiator and a reduction initiator;
wherein the mass ratio of the oxidation initiator to the reduction initiator is (2-6): 1;
the oxidation initiator comprises one or the combination of potassium persulfate, ammonium persulfate and hydrogen peroxide;
the reduction initiator comprises one or the combination of sodium sulfite, sodium bisulfite, potassium sulfite and potassium bisulfite.
6. A composition comprising the sustained-release carrier of claim 1 or 2 and a water-soluble compound; wherein the water-soluble compound comprises a chlorine dioxide precursor.
7. The composition according to claim 6, further comprising a stabilizer, a solid acidifier, and a deactivator;
wherein, the stabilizer preferably comprises one or the combination of magnesium sulfate, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, sodium phosphate, disodium hydrogen phosphate and dipotassium hydrogen phosphate;
the solid acidulant preferably comprises one or a combination of citric acid, tartaric acid, oxalic acid, malic acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate and aluminum sulfate;
the passivating agent preferably comprises inorganic clay; the inorganic clay comprises one or the combination of montmorillonite, kaolin, diatomite, attapulgite and perlite.
8. The composition as claimed in claim 7, wherein the components of the composition comprise: the composite material comprises, by mass, 2-32.65% of a slow release carrier, 2-10.21% of a chlorine dioxide precursor, 0.4-8.16% of a stabilizer, 2-16.33% of a solid acidifying agent and 2-32.65% of a passivating agent.
9. A method of preparing the composition of claim 8, comprising the steps of:
(1) mixing a chlorine dioxide precursor, the sustained-release carrier of claim 1 or 2 and a stabilizer to prepare a component A; coating a solid acidifier in a passivator to prepare a component B;
(2) and (2) mixing the component A and the component B in the step (1) to obtain the composition.
10. Use of a slow release carrier according to claim 1 or 2 or a composition according to any one of claims 6 to 8 for bactericidal decontamination.
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| CN113207877A (en) * | 2021-05-18 | 2021-08-06 | 陕西科技大学 | Slow-release solid chlorine dioxide and preparation method thereof |
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| CN111296427A (en) * | 2020-04-08 | 2020-06-19 | 青岛普泰克化工有限公司 | Immobilized chlorine dioxide slow-release gel |
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| CN111296427A (en) * | 2020-04-08 | 2020-06-19 | 青岛普泰克化工有限公司 | Immobilized chlorine dioxide slow-release gel |
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| CN113207877A (en) * | 2021-05-18 | 2021-08-06 | 陕西科技大学 | Slow-release solid chlorine dioxide and preparation method thereof |
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