CN112335651B

CN112335651B - Preparation method of chlorine dioxide disinfection slow-release gel

Info

Publication number: CN112335651B
Application number: CN202011226533.3A
Authority: CN
Inventors: 赵东育
Original assignee: Liaoning Blue Water Chemical Manufacturing Co ltd
Current assignee: Liaoning Blue Water Chemical Manufacturing Co ltd
Priority date: 2020-11-05
Filing date: 2020-11-05
Publication date: 2022-09-06
Anticipated expiration: 2040-11-05
Also published as: CN112335651A

Abstract

The invention discloses a method for preparing chlorine dioxide disinfection slow-release gel, belonging to the field of disinfection and sterilization and air purification. The preparation process of slow released chlorine dioxide gel includes the following steps: preparing a gel prepolymer, adding gamma-glycidyl ether oxypropyl trimethoxy silane, tetraethoxy silane and sodium dodecyl diphenyl ether disulfonate into a reaction kettle, stirring, adding a sulfuric acid solution into the reaction kettle, continuously stirring until hydrolysis, adding water, uniformly stirring, carrying out reduced pressure distillation, and cooling to room temperature to prepare the gel prepolymer; preparing an aqueous sodium chlorite solution; mixing the gel prepolymer with sodium chlorite aqueous solution according to the weight ratio of 1: 1, canning, sealing and standing to obtain the chlorine dioxide disinfection slow-release gel. The gel prepared by the method is not liquefied and diluted permanently, can keep a good gel state, can be preserved for more than 1 year under the sealed and light-proof room temperature condition, and the loss of chlorine dioxide storage is less than 10 percent.

Description

Preparation method of chlorine dioxide disinfection slow-release gel

Technical Field

The invention relates to a method for preparing chlorine dioxide disinfection slow-release gel, which belongs to the field of disinfection and sterilization and air purification.

Background

Chlorine dioxide is a broad-spectrum biocide, has the advantages of good biocidal effect, wide applicable pH, low toxicity, less generation of potential carcinogen halohydrocarbon and the like, and is widely applied to the fields of drinking water treatment, industrial cooling water treatment, wastewater treatment, air deodorization and sterilization, food preservation, fresh keeping and the like.

Chlorine dioxide is a yellow green or orange red gas at normal temperature, and chlorine dioxide vapor is exactly like chlorine and nitric acid in appearance and taste and has suffocation odor. When cooled and above-40 deg.C, it is dark red or red brown liquid, and when the temperature is below-59 deg.C, it is orange yellow solid. Chlorine dioxide is unstable and readily decomposes into oxygen and chlorine upon heating or exposure to light, causing an explosion. Explosion can also occur when encountering substances that promote oxidation, such as organic matter. The chlorine dioxide gas is safer when diluted to the concentration below 10 percent by air. Concentrations of chlorine dioxide water solutions below about 8-10 g/L will not produce high vapor pressures sufficient to cause explosion hazards. In the practice of water treatment, the concentration of chlorine dioxide rarely exceeds 4g/L, and the treatment level is generally in the range of 0.1-0.5 mg/L.

Chlorine dioxide gas is readily soluble in water, has a solubility about 5 times that of chlorine gas, forms a greenish-yellow solution during dissolution, and has a pungent odor similar to that of chlorine gas and nitric acid. The concentration of chlorine dioxide in the liquid phase at equilibrium at 25 ℃ is 23 times that in the gas phase. In contrast to the hydrolysis of chlorine in water, chlorine dioxide cannot be hydrolyzed to any significant amount in water, but instead remains in solution as a dissolved gas. The chlorine dioxide is dissolved in glacial acetic acid and carbon tetrachloride, and paramagnetism exists in the carbon tetrachloride. Is easily absorbed by sulfuric acid, but does not react with sulfuric acid.

The concentrated chlorine dioxide vapor exploded above atmospheric pressure 41Kpa, i.e., exploded at 40 Kpa. When the chlorine dioxide concentration in the solution is higher than 10% (Wt/V) or more than 10% (V/V) in the air, a low level of explosion is liable to occur, and such explosion may become intense in the presence of organic vapors. All attempts to compress or store chlorine dioxide, either alone or in combination with other gases, have not been commercially successful. Because of its explosive hazard, chlorine dioxide must be produced at the point of use.

The characteristics make it unsuitable for small-sized occasions, such as small-sized industrial water treatment and wastewater treatment, small-sized or household water storage tank disinfection and sterilization, indoor and other small-sized space air disinfection and deodorization, refreshing and purification, refrigerator or refrigeration house sterilization and food preservation, household mildew prevention, fabric bleaching and the like.

In recent years, a plurality of slow-release solid chlorine dioxide products appear at home and abroad, and the chlorine dioxide slow-release gel disinfectant becomes a new hot spot in the disinfection field. At present, organic gels such as super absorbent resin, gelatin, fish gelatin and the like are mostly used for the products, and are mixed with chlorine dioxide solution to prepare gel products. The problem exists in that the liquefaction is inverse dilution, when the gel is liquefied and disintegrated, the release speed of the chlorine dioxide is greatly accelerated, and the product loses efficacy within a few days.

The reason for liquefaction and reverse dilution is caused by multiple factors such as pH value, salinity, inorganic salt types and the like in different gel preparation systems, but the most important reason is that the organic high molecular polymers are oxidized by chlorine dioxide solution, molecular chains are broken and degraded, and gel is disintegrated.

Experiment research shows that the product is sealed and protected from light under the conditions of 6000-7000mg/L chlorine dioxide concentration, pH of 3-5 and room temperature of 25 ℃. The chlorine dioxide gel prepared by using 4% of super absorbent resin obviously generates fluidity after 3 days, and is completely liquefied into liquid after 2 weeks. The amount of the super absorbent resin is increased to 10%, the gel starts to generate obvious fluidity after 7 days, becomes viscous in 14 days, and becomes a solution in about 30 days.

When the gel is disintegrated, the release speed of the chlorine dioxide is greatly accelerated, the chlorine dioxide in the porous bottle is completely released within 2 days, and the product is ineffective. The rapid release of chlorine dioxide also results in excessive space concentration and secondary pollution.

Disclosure of Invention

The invention aims to solve the technical problems, and provides a preparation method of chlorine dioxide disinfection slow-release gel, which is characterized in that the gel prepared by the method is not liquefied and not diluted permanently, can keep a good gel state, can be preserved for more than 1 year under the sealed and light-proof room temperature condition, and the loss of chlorine dioxide storage is less than 10%.

In order to solve the technical problems, the invention is realized by the following technical scheme:

a method for preparing chlorine dioxide disinfection slow-release gel comprises the following steps:

the first step is as follows: preparing a gel prepolymer; 1.23-1.27 parts by mass of concentrated sulfuric acid with the mass percentage of 98% is taken and stirred and is dripped into 12-13 parts by mass of water to prepare dilute sulfuric acid solution for standby; adding 0.72-0.77 parts by mass of gamma-glycidoxypropyltrimethoxysilane, 52-53.5 parts by mass of tetraethoxysilane and 0.51-0.53 parts by mass of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding the prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 73-78 parts by mass of water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 55-65 ℃, then continuously stirring for 35-45 minutes, carrying out reduced pressure distillation, cooling the materials in the reaction kettle to room temperature, and preparing a gel prepolymer for later use;

the second step is that: preparing an aqueous sodium chlorite solution; taking 3.0-3.4 parts by mass of sodium chlorite with the mass percentage of 80%, adding the sodium chlorite into a proportioning tank, and adding 96.6-97 parts by mass of water to obtain a sodium chlorite aqueous solution for later use;

the third step: canning; mixing the gel prepolymer prepared in the first step with the sodium chlorite aqueous solution prepared in the second step according to the mass ratio of 1: 1, respectively filling the materials into the same packaging bottle, covering and sealing the bottle, and standing the bottle until the materials in the bottle form yellow gel to prepare the chlorine dioxide disinfection slow-release gel.

The preparation method of the chlorine dioxide disinfection slow-release gel preferably comprises the following steps:

the first step is as follows: preparing a gel prepolymer; 1.25 parts by mass of concentrated sulfuric acid with the mass percentage of 98% is taken and stirred and is dripped into 12.5 parts by mass of water to prepare dilute sulfuric acid solution for standby; adding 0.75 mass part of gamma-glycidoxypropyltrimethoxysilane, 52.8 mass parts of tetraethoxysilane and 0.52 mass part of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 75 mass parts of water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 60 ℃, then continuously stirring for 40 minutes, introducing circulating water into a condenser of the reaction kettle, starting a vacuum pump for decompression to 0.08MPA for distillation, stopping distillation of the distillate, opening the vacuum pump, recovering the pressure in the reaction kettle to normal pressure, introducing cooling water into a reaction coil kettle, and cooling the materials in the reaction kettle to room temperature to prepare a gel prepolymer for later use;

the second step is that: preparing an aqueous sodium chlorite solution; taking 3.2 parts by mass of sodium chlorite with the mass percentage of 80%, adding the sodium chlorite into a proportioning tank, and adding 96.8 parts by mass of water to obtain a sodium chlorite aqueous solution for later use;

the third step: canning; mixing the gel prepolymer prepared in the first step with the sodium chlorite aqueous solution prepared in the second step according to the mass ratio of 1: 1, respectively filling the components into the same packaging bottle, capping and sealing the bottle, and standing the bottle until the substances in the bottle form yellow gel to prepare the chlorine dioxide disinfection slow-release gel.

Preferably, the water added in the preparation of the dilute sulfuric acid solution in the first step is purified water.

Preferably, 73 to 78 parts by mass of water is added to the reaction kettle in the first step as purified water.

Preferably, after the temperature of the materials in the reaction kettle is reduced to room temperature in the first step, dry air or nitrogen after filtering and dedusting is introduced into the solution in the reaction kettle, and the residual organic volatile matters are removed by explosion until no odor exists, so that the gel prepolymer is prepared.

Preferably, the reduced pressure distillation in the first step is as follows: circulating water is introduced into a condenser of the reaction kettle, a vacuum pump is started to reduce the pressure to 0.07-0.09MPA for distillation, the vacuum pump is stopped when the distillation of distillate is stopped, a vent valve is opened to restore the pressure in the reaction kettle to normal pressure, and cooling water is introduced into a coil pipe of the reaction kettle.

Due to the adoption of the technical scheme, the invention has the following advantages and effects:

1. the invention is a single-component chlorine dioxide slow-release gel, which is not required to be prepared again when in use, can be used after being opened and is convenient to use.

2. And (3) stabilizing a gel system: the gel system of the organic silicon has the anti-oxidation characteristic and cannot be oxidized and degraded by chlorine dioxide. The gel system remained intact until the end of the release.

This stability is a key property of the product, and once the gel disintegrates, the rate of chlorine dioxide release increases uncontrollably. On one hand, the concentration of the rapidly released chlorine dioxide is too high, which can lead the environment to exceed the standard and bring potential harm, on the other hand, the product itself can be rapidly failed, and the initial purpose of using the gel slow-release body by a user can not be met. Thirdly, the gel is degraded by oxidation, and is consumed in the process of chlorine dioxide.

4. The validity period of the product is ensured: the effective period of the common chlorine dioxide gel products is at least more than 3 months, otherwise, the stock loss rate is greatly improved. The unsold goods go bad or go bad when being stored, which causes troubles for both manufacturers and consumers, and brings many disputes. The quality guarantee period of the chlorine dioxide gel prepared by the method is more than 1 year.

7. The technical innovation is as follows: the traditional chlorine dioxide sustained-release gel appeared in the first generation is mostly produced by using super absorbent resin, namely, macromolecular absorbent resin is swelled in chlorine dioxide solution. Along with the use, the problem of liquefaction and delignification is found, the dosage of the resin is continuously increased from 2% to more than 10%, but the liquefaction and delignification time is only prolonged from 7 days to 30 days, the liquidity is gradually increased, the content of chlorine dioxide is gradually reduced, and the essential problem is not solved. Meanwhile, the macromolecular water-absorbing resin which is not oxidation-resistant consumes the chlorine dioxide in the solution, and the loss rate of the chlorine dioxide is increased along with the increase of the adding amount of the resin. The traditional second generation product adopts split package, solid raw materials are packaged by plastic bags, and consumers return to prepare gel. Thus solving the quality guarantee period of the product. But by the time the consumer is in hand, the problem of the inverse lean liquefaction is resumed from the consumer's hand. The problems are transferred and not solved, the internal consumption of CLO2 is occurring, the liquefaction and back dilution are occurring, and the odor of CLO2 is getting bigger and bigger. In the traditional third generation products, manufacturers in the industry begin to change the composition of gel substances, and mostly utilize the characteristic of selective oxidation of chlorine dioxide, and hope to obtain a stable gel system. Gels such as gelatin, fish gelatin, etc. were tested sequentially. The stable organosilicon chlorine dioxide slow-release gel prepared by adopting the organosilicon hydrogel system thoroughly solves the problems of liquefaction, back dilution and chlorine dioxide internal consumption in the processes of storage and use of the chlorine dioxide gel, and the organosilicon hydrogel system has sufficient oxidation resistance.

The gel prepared by the method is not liquefied and not diluted permanently, can keep a good gel state, can be preserved for more than 1 year under the sealed and light-proof room temperature condition, and the loss of chlorine dioxide storage is less than 10 percent.

Detailed Description

The methods in the following examples are conventional methods unless otherwise specified.

The percentages in the following examples are by mass unless otherwise specified. In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and experimental data, it being understood that the specific examples described herein are only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention.

Example 1

The preparation process of slow released chlorine dioxide gel includes the following steps:

the first step is as follows: preparing a gel prepolymer; 1.23 parts by mass of concentrated sulfuric acid with the mass percentage of 98% is taken and stirred and is dripped into 12 parts by mass of purified water to prepare dilute sulfuric acid solution for later use; adding 0.72 mass part of gamma-glycidoxypropyltrimethoxysilane, 52 mass parts of tetraethoxysilane and 0.51 mass part of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 73 mass parts of purified water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 55 ℃, continuing stirring for 35 minutes, introducing circulating water into a condenser of the reaction kettle, starting a vacuum pump for decompression to 0.07MPA for distillation, stopping distilling the distillate, opening a vent valve to restore the pressure in the reaction kettle to normal pressure, introducing cooling water into a coil pipe of the reaction kettle, cooling the materials in the reaction kettle to room temperature, introducing filtered and dedusted dry air or nitrogen into the solution in the reaction kettle, exploding gas to remove residual organic volatile matters until the volatile matters are odorless, preparing a gel prepolymer for later use;

the second step is that: preparing an aqueous sodium chlorite solution; taking 3.0 parts by mass of sodium chlorite with the mass percentage of 80%, adding the sodium chlorite into a proportioning tank, and adding 97 parts by mass of water to obtain a sodium chlorite aqueous solution for later use;

Example 2

the first step is as follows: preparing a gel prepolymer; 1.27 parts by mass of concentrated sulfuric acid with the mass percentage of 98% is taken and stirred and is dripped into 13 parts by mass of purified water to prepare dilute sulfuric acid solution for later use; adding 0.77 parts by mass of gamma-glycidoxypropyltrimethoxysilane, 53.5 parts by mass of tetraethoxysilane and 0.53 parts by mass of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 78 parts by mass of purified water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 65 ℃, then continuously stirring for 35-45 minutes, introducing circulating water into a condenser of the reaction kettle, starting a vacuum pump for decompression to 0.09MPA for distillation, stopping the distillation of distillate, opening a vent valve to restore the pressure in the reaction kettle to normal pressure, introducing cooling water into a coil pipe of the reaction kettle, cooling the materials in the reaction kettle to room temperature, introducing filtered and dedusted dry air or nitrogen into the solution in the reaction kettle, and removing residual organic volatile matters by explosion, until no smell, preparing gel prepolymer for standby;

the second step is that: preparing an aqueous sodium chlorite solution; taking 3.4 parts by mass of 80% sodium chlorite, adding the sodium chlorite into a dosing tank, and adding 96.6 parts by mass of water to obtain a sodium chlorite aqueous solution for later use;

Example 3

the first step is as follows: preparing a gel prepolymer; 1.25 parts by mass of concentrated sulfuric acid with the mass percentage of 98% is taken and stirred and is dripped into 12.5 parts by mass of purified water to prepare dilute sulfuric acid solution for standby; adding 0.75 mass part of gamma-glycidoxypropyltrimethoxysilane, 52.8 mass parts of tetraethoxysilane and 0.52 mass part of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 75 mass parts of purified water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 60 ℃, then continuously stirring for 40 minutes, introducing circulating water into a condenser of the reaction kettle, starting a vacuum pump for decompression to 0.08MPA for distillation, stopping distillation of the distillate, opening the vacuum pump, returning the pressure in the reaction kettle to normal pressure, introducing cooling water into a coil pipe kettle, cooling the materials in the reaction kettle to room temperature, introducing filtered and dedusted dry air or nitrogen into the solution in the reaction kettle, removing residual organic volatile matters by explosion gas until the odor is no more, preparing a gel prepolymer for later use;

the second step: preparing an aqueous sodium chlorite solution; taking 3.2 parts by mass of 80% sodium chlorite, adding the sodium chlorite into a dosing tank, and adding 96.8 parts by mass of water to obtain a sodium chlorite aqueous solution for later use;

Example 4

the first step is as follows: preparing a gel prepolymer; 1.24 parts by mass of 98% concentrated sulfuric acid is taken and added dropwise into 12.8 parts by mass of purified water under stirring to prepare dilute sulfuric acid solution for later use; adding 0.73 mass part of gamma-glycidoxypropyltrimethoxysilane, 53.1 mass parts of tetraethoxysilane and 0.51 mass part of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until transparent and uniform hydrolysate is obtained, adding 74 mass parts of purified water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 63 ℃, continuing stirring for 37 minutes, introducing circulating water into a condenser of the reaction kettle, starting a vacuum pump for decompression to 0.07MPA for distillation, stopping distilling the distillate, opening a vent valve, recovering the pressure in the reaction kettle to normal pressure, introducing cooling water into a coil of the reaction kettle, cooling the materials in the reaction kettle to room temperature, introducing filtered and dedusted dry air or nitrogen into the solution in the reaction kettle, removing residual organic volatile matters by explosion until the smell is no more, preparing a gel prepolymer for later use;

the second step is that: preparing an aqueous sodium chlorite solution; taking 3.1 parts by mass of sodium chlorite with the mass percentage of 80%, adding the sodium chlorite into a proportioning tank, and adding 96.9 parts by mass of water to obtain a sodium chlorite aqueous solution for later use;

Example 5

the first step is as follows: preparing a gel prepolymer; 1.26 parts by mass of 98% concentrated sulfuric acid is taken and added dropwise into 12.3 parts by mass of purified water under stirring to prepare dilute sulfuric acid solution for later use; adding 0.76 mass part of gamma-glycidoxypropyltrimethoxysilane, 52.3 mass parts of tetraethoxysilane and 0.53 mass part of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 77 mass parts of purified water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 58 ℃, then continuously stirring for 42 minutes, introducing circulating water into a condenser of the reaction kettle, starting a vacuum pump for decompression to 0.08MPA for distillation, stopping distillation of the distillate, starting the vacuum pump, recovering the pressure in the reaction kettle to normal pressure, introducing cooling water into a coil pipe kettle, cooling the materials in the reaction kettle to room temperature, introducing filtered and dedusted dry air or nitrogen into the solution in the reaction kettle, removing residual organic volatile matters by explosion gas until the odor is not smelly, preparing a gel prepolymer for later use;

the second step: preparing an aqueous sodium chlorite solution; taking 3.3 parts by mass of sodium chlorite with the mass percentage of 80%, adding the sodium chlorite into a proportioning tank, and adding 96.7 parts by mass of water to obtain a sodium chlorite aqueous solution for later use;

the third step: can package

Mixing the gel prepolymer prepared in the first step with the sodium chlorite aqueous solution prepared in the second step according to the mass ratio of 1: 1, respectively filling the components into the same packaging bottle, capping and sealing the bottle, and standing the bottle until the substances in the bottle form yellow gel to prepare the chlorine dioxide disinfection slow-release gel.

The reaction kettle used in the preparation method of the embodiment 1-5 is a stainless steel organic synthesis complete equipment, and specifically, a 200L electric heating double-layer conical reaction kettle is adopted, a polytetrafluoroethylene coating is lined, a 3 square meter condenser is connected, a 200L vacuum collection tank and a 0.1Mpa water circulation vacuum pump are connected. This should not be taken as limiting the scope of the invention.

In the canning process of the preparation methods of examples 1-5, air exhaust is carried out at a canning water outlet, and a small amount of overflowed chlorine dioxide is filtered and discharged along with an air exhaust system. The exhaust of the workshop adopts a water spraying system, the reducing agent solution is used for purifying the air and then the air is discharged harmlessly, and other air purifying technologies can also be adopted.

The following simultaneous experimental data further illustrate the organosilicon chlorine dioxide disinfection sustained-release gel prepared by the method of the invention.

Test example 1:

pH of disinfecting gels prepared in examples 1-5, chlorine dioxide (as ClO) ₂ Meter) detection: and (4) detecting items: pH value

Firstly, equipment:

1. test samples: 500mL each of the disinfectant gels prepared in examples 1-5.

2. Thunder magnetic ZDJ-5B automatic titrator (potential); a glass electrode; a reference electrode; and a temperature electrode.

3. Set of pH buffers (72003069) lot number: 20171106, respectively; potassium hydrogen phthalate standard buffer (pH4.00, 20 ℃); phosphate standard buffer (pH6.88, 20 ℃); borax standard buffer (pH9.23, 20 ℃).

Secondly, the method comprises the following steps:

1. the detection is based on the Disinfection technical Specification 2002 edition 2.2.1.4

2. The detection basis does not include or needs special explanation to possibly influence the detection result. Thirdly, obtaining a result:

detecting the index	pH value	Mean value of
			pH	3.47-3.49	3.48

Detecting items: chlorine dioxide (with ClO) ₂ Meter)

First, equipment

1. Test samples: 500mL each of the disinfectant gels prepared in examples 1-5.

2. Acid burette (25mL0.1 graduation).

3. Sodium thiosulfate titration solution (0.1mol/L F ═ 1.000).

Second, method

1. The test was according to Disinfection Specification 2002 edition 2.2.1.2.6.

2. The detection basis does not include or needs special explanation to possibly influence the detection result.

Third, the results

Test example 2:

stability of antiseptic gels prepared in examples 1-5 for 1 year test:

firstly, equipment:

1. test samples: 500mL each of the disinfectant gels prepared in examples 1-5.

2. Acid burette (25ml0.1 divisions).

3. Sodium thiosulfate titration solution (0.1mol/L F ═ 1.000).

4. An incubator at 54 ℃.

Secondly, the method comprises the following steps:

the method is based on the Disinfection technical Specification 2.2.1.2.6 and the Disinfection technical Specification 2.2.3.

The detection basis does not include or need special explanation to possibly influence the detection result.

Third, the results

Fourth, conclusion

The chlorine dioxide stability of the antiseptic gels prepared in examples 1-5 was 1 year compliant with the antiseptic Specification, 2002 edition 2.2.3.

Test example 3:

acute oral toxicity test:

the detection basis is as follows: disinfection technical Specification (2002 edition) 2.3.1

Evaluation basis: disinfection Specification (2002 edition) 2.3.1

And (4) detection conclusion:

the product is tested according to the maximum limit test in 2.3.1 of the technical Specification for disinfection (2002 edition) (for example, the one-time intragastric administration dosage of 20 animals (each half of male and female) is 5000mg/kg of body weight, no death occurs within 14 days, and LD50 can be judged to be more than 5000mg/kg of body weight), the test result is evaluated and judged according to 2.3.1.6 in 2.3.1 of the technical Specification for disinfection (2002 edition), and the test result of the test object on the acute oral toxicity of mice is practically nontoxic.

Materials and animals

1. The test substance: examples 1-5 prepared disinfecting gels. Strain: KM mice, source: liaoning Biotechnology GmbH, 10 male mice, 10 female mice, SPF grade, 15-17g, date of introduction: on 10/07/2020, the production license number of the experimental animal is SCXK (Liao) 2015-0001.

2. The feed source is as follows: SPF-grade rat maintenance feed, available from Liaoning Biotechnology Ltd, lot 20023213.

3. The test conditions are as follows: feeding room number a012, temperature: 20.2-23.7 ℃, relative humidity: 65-67 ℃. The license number of the experimental animal is SYXK (Liao) 2015-0006.

Second, method

1. The detection basis is as follows: disinfection technical Specification (2002 edition) 2.3.1

2. Grouping: animals were divided into 5 groups according to male and female: each group contains 4 animals and is fed in cages. Before the test, the test is generally fasted overnight without limiting the drinking water. Dose setting: one dose group is set according to one maximum test, the dose group is 5000mg/kg, the stomach is irrigated according to the standard for contamination, and the administration volume is 0.2mL/10 g. After the infection, the toxic manifestation, death number and death time of the animals are observed, dead animals and sacrificed animals after the observation are subjected to autopsy, and the dead animals and the sacrificed animals after the observation are observed by naked eyes, so that abnormal tissues or organs are found, and further histopathology examination is needed. The observation time 14 d.

And thirdly, carrying out autopsy on the killed animals at the end of observation according to the test results, wherein the animals are not abnormal.

Fourth, conclusion

The test result is judged according to 2.3.1.6 in disinfection technical Specification (2002 edition) 2.3.1, and the test object is practically nontoxic to the test result of the acute oral toxicity of mice.

Test example 4:

identification test (carrier method) of staphylococcus aureus neutralizer, detection test:

firstly, equipment:

1. sample name: the antiseptic gel prepared in example 3.

2. Test strain name, strain number, supply unit and culture passage number: staphylococcus aureus, ATCC6538, Kyoto-Kay Microbiol technologies, Inc., 6 th generation.

3. Media and others:

1) tryptone soy agar medium (TSA);

2) tryptone Soy Broth (TSB);

3)0.03mol/L Phosphate Buffer (PBS) pH7.2;

4) diluting liquid: physiological saline solution (TPS) containing 0.1% tryptone;

5) neutralizer components and concentrations: 0.8% sodium thiosulfate, 0.5% lecithin and a PBS solution with the volume fraction of 5% Tween 80;

6) pure cotton plain white cloth piece.

4. Instrument name/model/number: a constant temperature incubator/DH 6000BII/L-516, a constant temperature water bath pot/DK-98-IIA/L-515, a vertical steam pressure sterilizer/LDZX-60 KSB/L-484, an electronic balance/SQP/L-326, an electronic microscope/BM 2100/L-511, and a biological safety cabinet/BSC-1500 IIA 2-X/L-499.

Secondly, the method comprises the following steps:

1. the detection basis is as follows: disinfection Specification (2002) 2.1.1.5.6.

2. Neutralizer identification test:

3. the concentration of the sterilizing liquid is as follows: example 3 preparation of a prototype of a sterilising gel;

preparation of staphylococcus aureus bacterial suspension: diluted to the concentration used with a physiological saline solution containing 0.1% tryptone.

4. The test was repeated 3 times at a test temperature of 20 ℃. + -. 1 ℃.

Thirdly, obtaining a result:

the test was repeated 3 times at a test temperature of 20 ℃. + -. 1 ℃ for 1min, and the prototype of the disinfectant gel prepared in example 3 had an average number of growing bacteria of 0cfu/mL in the 1 st group, 0cfu/mL in the 2 nd group, and 4.58X 10 in the 3 rd group ⁶ cfu/mL, mean growth number of 4 th group 4.62X 10 ⁶ cfu/mL, mean growth number of 4.40X 10 of group 5 ⁶ cfu/mL, group 6 aseptically grown. The error rate among the groups 3, 4 and 5 was < 15%.

Identification test result of neutralizer

Note: all negative controls were aseptically grown

Fourth, conclusion

The test is repeated for 3 times, the test temperature is 20 +/-1 ℃, and the result shows that the test temperature is 0.8 percent of sodium thiosulfate, 0.5 percent of lecithin and 5 percent of Tween 80 by volume of PBS solution; the effect of residual disinfection gel on the surfaces of thalli on test bacteria can be effectively neutralized, and the neutralizing agent and a neutralized product thereof have no obvious adverse effect on the test bacteria and a culture medium. The neutralizer is shown to be suitable for the carrier quantitative killing test of the disinfection gel prototype prepared in the example 3 on escherichia coli and staphylococcus aureus.

Test example 5:

identification test (carrier method) of candida albicans neutralizer, detection test:

first, equipment

1. Sample name: the antiseptic gel prepared in example 3.

2. Test strain name, strain number, supply unit and culture passage number: candida albicans, ATCC10231, Kyork Microtechnology, Inc., 6 th generation.

3. Media and others:

1) a Sabouraud agar medium;

2) liquid saybolt medium;

3)0.03mol/L Phosphate Buffer Solution (PBS) with pH7.2;

5) neutralizer component and concentration: 0.8% sodium thiosulfate, 0.5% lecithin and a PBS solution with the volume fraction of 5% Tween 80;

6) pure cotton plain white cloth piece.

Second, the method

2. Neutralizer identification test:

the concentration of the sterilizing liquid is as follows: example 3 preparation of a prototype sterile gel;

preparation of candida albicans suspension: diluted to the concentration used with a physiological saline solution containing 0.1% tryptone.

3. The test was repeated 3 times at a test temperature of 20 ℃. + -. 1 ℃.

Three, result in

The test was repeated 3 times at a test temperature of 20 ℃. + -. 1 ℃. The prototype of antiseptic gel prepared in example 3 had an action time of 1min, an average number of growing bacteria of 0cfu/mL in group 1, an average number of growing bacteria of 0cfu/mL in group 2, and an average number of growing bacteria of 3.28X 10 in group 3 ⁶ cfu/mL, mean growth number of group 4 of 3.65X 10 ⁶ cfu/mL, mean growth number of group 5 of 3.60X 10 ⁶ cfu/mL, group 6 aseptically grown. The error rate among the groups 3, 4 and 5 is less than 15%.

Identification test result of neutralizer

Note: all negative controls were aseptically grown

Fourth, conclusion

The test is repeated for 3 times, the test temperature is 20 +/-1 ℃, and the result shows that the test temperature is 0.8 percent of sodium thiosulfate, 0.5 percent of lecithin and 5 percent of Tween 80 by volume of PBS solution; the effect of residual disinfection gel on the surfaces of thalli on test bacteria can be effectively neutralized, and the neutralizing agent and a neutralized product thereof have no obvious adverse effect on the test bacteria and a culture medium. The neutralizer is shown to be suitable for the carrier quantitative killing test of the disinfection gel prototype prepared in the example 3 on the candida albicans.

Test example 6:

coli sterilization test (vector method) detection test:

first, equipment

1. Name of test sample: the antiseptic gel prepared in example 3;

2. test strain name, strain number, supply unit and culture passage number: escherichia coli, 8099, Kyoto Loop Microscience, Inc., 6 th generation.

3. Media and others: nutrient agar medium, phosphate buffer solution (0.03mol/L pH7.2); neutralizer components and concentrations: 0.8% sodium thiosulfate, 0.5% lecithin and a PBS solution with the volume fraction of 5% Tween 80; pure cotton plain white cloth piece.

Second, the method

1. The detection basis is as follows: disinfection Specification 2002 edition 2.1.1.7.5.

2. Coli killing test (vector quantification method)

(1) The concentration of the sterilizing liquid is as follows: example 3 preparation of a prototype of a sterilising gel;

(2) preparing an escherichia coli bacterial suspension: diluted to the concentration used with a physiological saline solution containing 0.1% tryptone.

(3) The test was repeated 3 times at a test temperature of 20 ℃. + -. 1 ℃.

Three, result in

After 3 times of repeated tests, the result shows that the action time of the prototype of the disinfection gel prepared in the embodiment 3 is 1min, and the average killing logarithm value of the prototype of the disinfection gel to escherichia coli is more than or equal to 3.00.

Test results of quantitative killing of Escherichia coli by the prototype of the Disinfection gel prepared in example 3

Note: all negative controls were aseptically grown

Fourth, conclusion

After 3 times of repeated tests, the result shows that the action time of the prototype disinfection gel prepared in the embodiment 3 is 1min, the average killing log value of the prototype disinfection gel on escherichia coli is more than or equal to 3.00, and the prototype disinfection gel meets the requirements of disinfection technical specification 2002 edition 2.1.1.7.7.

Test example 7:

staphylococcus aureus sterilization test (vehicle method) detection test:

first, equipment

1. Name of test sample: the antiseptic gel prepared in example 3;

3. Media and others: nutrient agar medium, phosphate buffer solution (0.03mol/L pH7.2); neutralizer component and concentration: 0.8% sodium thiosulfate, 0.5% lecithin and a PBS solution with the volume fraction of 5% Tween 80; pure cotton plain white cloth pieces;

4. instrument name/model/number: constant temperature incubator/DH 6000BII/L-516, constant temperature water bath/DK-98-IIA/L-515, vertical steam pressure sterilizer/LDZX-60 KSB/L-484, electronic balance/SQP/L-326, electronic microscope/BM 2100/L-511, biological safety cabinet/BSC-1500 IIA 2-X/L-499.

Second, the method

2. Staphylococcus aureus killing test (vector quantitation method)

(2) preparation of staphylococcus aureus bacterial suspension: diluted to the concentration used with a physiological saline solution containing 0.1% tryptone.

(3) The test was repeated 3 times at a test temperature of 20 ℃. + -. 1 ℃.

Three, result in

After 3 times of repeated tests, the result shows that the disinfection gel prototype prepared in the example 3 has the action time of 1min and the average killing log value of staphylococcus aureus is more than or equal to 3.00.

Results of the Carrier quantitative kill test for Staphylococcus aureus in the sterilized gel prepared in example 3

Note: all negative controls were aseptically grown

Fourth, conclusion

After 3 repeated tests, the result shows that the disinfection gel prototype prepared in the embodiment 3 has the action time of 1min, the average killing log value of the staphylococcus aureus is more than or equal to 3.00, and the requirements of disinfection technical specification 2002 edition 2.1.1.7.7 are met.

Test example 8:

candida albicans sterilization test (vehicle method) detection test:

first, equipment

1. Name of test sample: the antiseptic gel prepared in example 3;

2. test strain name, strain number, supply unit and culture passage number: candida albicans, ATCC10231, Kyoto Tokyo Microscience, Inc., 6 th generation.

3. Media and others: sabouraud agar medium, phosphate buffer (0.03mol/L pH7.2); neutralizer components and concentrations: 0.8% sodium thiosulfate, 0.5% lecithin and a PBS solution with the volume fraction of 5% Tween 80; pure cotton plain white cloth pieces;

Second, the method

1. The detection basis is as follows: disinfection Specification 2002 edition 2.1.1.9.5.

2. Candida albicans killing test (vector quantification method)

(2) preparation of candida albicans suspension: diluted to the concentration used with a physiological saline solution containing 0.1% tryptone.

(3) The test was repeated 3 times at a test temperature of 20 ℃. + -. 1 ℃.

Third, the results

After 3 times of repeated tests, the result shows that the action time of the prototype disinfection gel prepared in the example 3 is 1min, and the average killing log value of the prototype disinfection gel on the candida albicans is more than or equal to 3.00.

Results of the quantitative killing test of Candida albicans by the disinfectant gel prepared in example 3

Note: all negative controls were aseptically grown

Fourth, conclusion

After 3 repeated tests, the result shows that the action time of the prototype of the disinfection gel prepared in the example 3 is 1min, the average killing log value of the prototype of the disinfection gel to the candida albicans is more than or equal to 3.00, and the requirements of the disinfection technical specification 2002 edition 2.1.1.9.6 are met.

Test example 9:

comparative stability test of antiseptic gels prepared in examples 1-5:

。

Claims

1. the preparation method of the chlorine dioxide disinfection slow-release gel is characterized by comprising the following steps:

the first step is as follows: preparing a gel prepolymer; 1.23-1.27 parts by mass of concentrated sulfuric acid with the mass percentage of 98% is taken and stirred and is dripped into 12-13 parts by mass of water to prepare dilute sulfuric acid solution for standby; adding 0.72-0.77 parts by mass of gamma-glycidoxypropyltrimethoxysilane, 52-53.5 parts by mass of tetraethoxysilane and 0.51-0.53 parts by mass of sodium dodecyl diphenyl ether disulfonate into a reaction kettle, stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle, continuously stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 73-78 parts by mass of water into the reaction kettle, uniformly stirring, heating the materials in the reaction kettle to 55-65 ℃, continuously stirring for 35-45 minutes, carrying out reduced pressure distillation, cooling the materials in the reaction kettle to room temperature, introducing filtered and dedusted dry air or nitrogen into the solution in the reaction kettle, removing residual organic volatile matters by using the gas until the gas is odorless, and preparing a gel prepolymer for later use;

2. The method for preparing chlorine dioxide disinfection slow-release gel according to claim 1, characterized by the following steps:

the first step is as follows: preparing a gel prepolymer; 1.25 parts by mass of 98% concentrated sulfuric acid is taken and added dropwise into 12.5 parts by mass of water under stirring to prepare a dilute sulfuric acid solution for later use; adding 0.75 mass part of gamma-glycidoxypropyltrimethoxysilane, 52.8 mass parts of tetraethoxysilane and 0.52 mass part of sodium dodecyl diphenyl ether disulfonate into a reaction kettle for stirring, adding a prepared dilute sulfuric acid solution into the reaction kettle for continuous stirring until the dilute sulfuric acid solution becomes transparent and uniform hydrolysate, adding 75 mass parts of water into the reaction kettle for uniform stirring, heating the materials in the reaction kettle to 60 ℃, then continuously stirring for 40 minutes, carrying out reduced pressure distillation, cooling the materials in the reaction kettle to room temperature, introducing dry air or nitrogen after filtering and dedusting into the solution in the reaction kettle, exploding gas to remove residual organic volatile matters until the organic volatile matters are odorless, and preparing a gel prepolymer for later use;

3. A method for preparing a slow-release gel for chlorine dioxide disinfection according to claim 1 or 2, characterized in that the water added in the first step for preparing the dilute sulfuric acid solution is purified water.

4. A method for preparing a chlorine dioxide disinfectant sustained-release gel according to claim 1, wherein 73 to 78 parts by mass of water is added to the reaction kettle in the first step as purified water.