Nano water-absorbing disinfectant and preparation method thereof

Abstract

The invention discloses a nano water-absorbing disinfectant and a preparation method thereof, and the nano water-absorbing disinfectant comprises the following components in percentage by mass: 85-95% of a water-absorbing resin / inorganic nano material composite material and 5-15% of functionalized sodium dichloroisocyanurate. The nano water-absorbing disinfectant comprises nano-scale materials, due to the unique properties of small particle size, large specific surface area and the like, the water-absorbing rate, the water-absorbing rate and the bacterium killing effect of the water-absorbing disinfectant are remarkably improved, the maximum water-absorbing rate of distilled water is 556.5 g / g, the maximum water-absorbing rate of 0.9% saline water is 90 g / g, and the water-absorbing disinfectant has the advantages that the water-absorbing rate is high, the water-absorbing rate is high and the bacterium killing effect is good. The water absorption rate reaches 50 times and does not exceed 10S, and the KL value of the killing effect on various body fluid pollutants is greater than 5; and the paint has no obvious damage effect on aviation metal materials and passenger cabin interior materials, and meets the international aviation chemical product safety standard.

Description

[0001] This application is a divisional application filed by the applicant with the China National Intellectual Property Administration on May 6, 2024, with patent application number 202410549972X and title "A Nano-Absorbent Disinfectant and Its Preparation Method". Technical Field

[0002] This invention belongs to the field of disinfectant technology for aviation and public health, and relates to a disinfectant and its preparation method, specifically to a nano-water-absorbing disinfectant and its preparation method. Background Technology

[0003] The global infectious disease epidemic is becoming increasingly severe. The threat of traditional infectious diseases persists, and Class A infectious diseases occur frequently. Class B infectious diseases, such as viral hepatitis, tuberculosis, syphilis, dysentery, and hemorrhagic fever, as well as Class C infectious diseases, such as mumps, influenza, and hand-foot-and-mouth disease, are showing an upward trend year by year, especially with the emergence of novel coronavirus infection. New infectious diseases are constantly emerging. Recently, the WHO issued a risk warning of a global pandemic of "Infectious Disease X," calling for a comprehensive improvement in global public health risk prevention capabilities. Therefore, developing efficient disinfection technologies to promptly and effectively treat infectious sources and cut off transmission routes are crucial technical measures to curb the spread of infectious diseases.

[0004] Biological bodily fluids (human and animal) contaminants, including blood, excrement, secretions, and vomit, are defined by the WHO as contaminants posing a significant epidemiological risk and should be treated as sources of infectious disease with highly efficient disinfection. Two key elements for the harmless disposal of biological bodily fluids (human and animal), including blood, excrement, secretions, and vomit, are: first, the ability to rapidly solidify / gel the bodily fluids to prevent leakage, splashing, and flow of contaminated liquids, thus preventing the spread of contamination; and second, the ability to kill the contaminating microorganisms.

[0005] Patent document CN101961010B discloses a water-absorbing disinfectant dry powder, which is composed of 90-99% polyacrylic acid-based superabsorbent polymer and 1-10% trichloroisocyanuric acid. This water-absorbing disinfectant dry powder only inhibits the growth of pathogenic bacteria and does not have disinfection effects; furthermore, its water absorption capacity needs improvement. In addition, existing methods for treating biological bodily fluid contaminants suffer from problems such as poor water absorption, uneven disinfection, and incomplete disinfection. Moreover, due to the leakage, splashing, and flow characteristics of bodily fluids, the contamination area can easily expand, adversely affecting the environment and human health. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a nano-absorbent disinfectant and its preparation method. The nano-absorbent disinfectant of this invention exhibits higher absorption capacity and rate for biological bodily fluid (human and animal) contaminants (including blood, excrement, secretions, and vomit), as well as resistance to acids, salts, and organic interferences. It also demonstrates rapid gelation of biological bodily fluid contaminants, achieving a high level of disinfection. Furthermore, it is safe and environmentally friendly, causing no significant damage to aerospace metal materials or cabin interior materials, and complies with international safety standards for aerospace chemical products.

[0007] To achieve the above-mentioned objectives, the technical solution of the present invention is as follows:

[0008] A nano-absorbent disinfectant, by weight percentage, comprises 85-95% a composite material of absorbent resin / inorganic nanomaterials and 5-15% functionalized sodium dichloroisocyanurate.

[0009] According to an embodiment of the present invention, in the composite material of the water-absorbing resin / inorganic nanomaterial, the water-absorbing resin is selected from acrylic polymer resins, such as maleic anhydride grafted modified polyacrylic acid resin, acrylic acid-maleic anhydride copolymer resin, maleic anhydride grafted modified acrylic acid-acrylamide copolymer resin, acrylic acid-acrylamide-maleic anhydride copolymer resin, etc.

[0010] According to an embodiment of the present invention, in the composite material of the absorbent resin / inorganic nanomaterial, the inorganic nanomaterial refers to nanoscale (at least one dimension smaller than 100 nm) oxides or inorganic salts. Specifically, it can be selected from montmorillonite (specifically, organomontmorillonite, abbreviated as OMMT), silica, titanium dioxide, etc.

[0011] According to an embodiment of the present invention, in the nano-water-absorbing disinfectant, the content of the composite material, by mass percentage, is any specific point value within the range of 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, or any combination of the above point values.

[0012] According to an embodiment of the present invention, in the nano-water-absorbing disinfectant, the content of the functionalized sodium dichloroisocyanurate, by mass percentage, is any specific point value within the range of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or any combination of the above point values.

[0013] For example, the composite material has a mass percentage of 90% and the functionalized sodium dichloroisocyanurate has a mass percentage of 10%; another example is that the composite material has a mass percentage of 89% and the functionalized sodium dichloroisocyanurate has a mass percentage of 11%; yet another example is that the composite material has a mass percentage of 88% and the functionalized sodium dichloroisocyanurate has a mass percentage of 12%.

[0014] According to an embodiment of the present invention, the composite material of the water-absorbing resin / inorganic nanomaterial is a copolymer of acrylic acid (AA), acrylamide (AM), maleic anhydride (MA) and organomontmorillonite (OMMT); or, it is a copolymer of acrylic resin, polyacrylamide, maleic anhydride and organomontmorillonite, which can be denoted as P(AA-AM / OMMT) nanocomposite material.

[0015] According to an embodiment of the present invention, the functionalized sodium dichloroisocyanurate has the following structural formula, which can also be written as DCCNa:

[0016]

[0017] The sodium dichloroisocyanurate (DCCNa) of this invention has the following advantages: 1) Strong microbial killing effect: DCCNa has strong oxidizing properties and a strong bactericidal effect on various pathogenic microorganisms such as viruses, bacterial spores, and fungi. It is a widely applicable and highly efficient bactericide. The effective chlorine content of pure DCCNa is 64.5%, and the effective chlorine content of high-quality products is greater than 60%, which has a strong disinfection and bactericidal effect. At 20 ppm, the bactericidal rate reaches 99%. It has a strong killing effect on various bacteria, algae, fungi, and pathogens; 2) Low toxicity: The median lethal dose (LD50) is as high as 1.67 g / kg (the median lethal dose of trichloroisocyanuric acid is only 0.72-0.78 g / kg). The use of DCCNa in the disinfection and sterilization of food and drinking water has long been approved both domestically and internationally; 3) High effective chlorine utilization rate: DCCNa has a high solubility in water. At 25°C, 30 g of DCCNa can dissolve in 100 mL of water. Even in aqueous solutions at temperatures as low as 4°C, DCCNa can rapidly release all of its available chlorine, maximizing its disinfection and sterilization effects. Other solid chlorine-containing products have lower solubility or slower chlorine release rates, resulting in significantly lower chlorine values ​​than DCCNa. 4) Good stability: Due to the high stability of the triazine ring in the chloroisocyanuric acid molecule, DCCNa is very stable. Measurements show that after one year of storage in a warehouse, dried DCCNa experiences less than 1% loss of available chlorine.

[0018] According to an embodiment of the present invention, the functionalized sodium dichloroisocyanurate is a complex of sodium dichloroisocyanurate and inorganic oxides. Specifically, the inorganic oxides have a particle size in the nanometer range, for example, selected from nano-silica or nano-titanium dioxide. More specifically, the inorganic oxides in the functionalized sodium dichloroisocyanurate have a mass percentage content of 0.10-8%. For example, the nano-titanium dioxide in the functionalized sodium dichloroisocyanurate has a mass percentage content of 5%; and for another example, the nano-silica in the functionalized sodium dichloroisocyanurate has a mass percentage content of 0.10%.

[0019] According to an embodiment of the present invention, the particle size of the nano-water-absorbing disinfectant is 80-100 nm.

[0020] The present invention also provides a method for preparing the above-mentioned nano-water-absorbing disinfectant, the method comprising the following steps:

[0021] Step 1: Prepare or manufacture functionalized sodium dichloroisocyanurate;

[0022] Step 2: Prepare or fabricate a composite material of water-absorbing resin / inorganic nanomaterials;

[0023] Step 3: Mix the functionalized sodium dichloroisocyanurate from Step 1 and the composite material of water-absorbing resin / inorganic nanomaterial from Step 2 to prepare the nano-water-absorbing disinfectant.

[0024] According to an embodiment of the present invention, step 1 specifically includes: mixing sodium dichloroisocyanurate (DCCNa) and inorganic oxides to prepare the functionalized sodium dichloroisocyanurate.

[0025] According to an embodiment of the present invention, in step 1, the mass percentage of the inorganic oxide is 0.1% to 8% of DCCNa.

[0026] According to an embodiment of the present invention, in step 1, the definition of inorganic oxide is the same as that of inorganic oxide in the previously functionalized sodium dichloroisocyanurate.

[0027] Specifically, step 1 can be: mixing sodium dichloroisocyanurate (DCCNa) and nano-titanium dioxide to prepare the functionalized sodium dichloroisocyanurate, which can be referred to as DCCNa / TiO2 composite material.

[0028] According to an embodiment of the present invention, step 2 specifically includes: copolymerizing acrylic resin, polyacrylamide, maleic anhydride and inorganic nanomaterials under the action of an initiator and / or a crosslinking agent to prepare a composite material of water-absorbing resin / inorganic nanomaterials.

[0029] According to an embodiment of the present invention, the definition of inorganic nanomaterials in step 2 is the same as before.

[0030] According to an embodiment of the present invention, in step 2, the mass ratio of acrylic resin, polyacrylamide, maleic anhydride, and inorganic nanomaterials is 7-6:2-3:0.1-0.2:0.2-0.8.

[0031] According to an embodiment of the present invention, in step 2, the content of the initiator is 0.05-0.2‰ of the total mass of the four monomers.

[0032] According to an embodiment of the present invention, in step 2, the content of the crosslinking agent is 0.01-0.08‰ of the total mass of the four monomers.

[0033] According to an embodiment of the present invention, in step 2, the initiator is selected from at least one of hydrogen peroxide, ammonium persulfate, or potassium persulfate.

[0034] According to an embodiment of the present invention, in step 2, the crosslinking agent is selected from at least one of N,N-methylenebisacrylamide (MBA), N-hydroxymethylacrylamide (N-MAM), etc.

[0035] According to an embodiment of the present invention, in step 2, the copolymerization temperature is 50-80°C and the copolymerization time is 10-70 min.

[0036] According to an embodiment of the present invention, in step 2, the degree of neutralization of the acrylic resin is 65-72%, for example 70%.

[0037] According to an embodiment of the present invention, in step 2, the degree of amination of maleic anhydride is 70-78%, for example 75%.

[0038] According to an embodiment of the present invention, in step 3, the mass ratio of functionalized sodium dichloroisocyanurate and the composite material of water-absorbing resin / inorganic nanomaterial is 5-15:85-95.

[0039] According to an embodiment of the present invention, step 3 further includes post-processing of the product such as grinding and sieving.

[0040] The beneficial effects of this invention are:

[0041] The nano-absorbent disinfectant of this invention comprises a composite material of absorbent resin / inorganic nanomaterials and functionalized sodium dichloroisocyanurate. The nanomaterials, due to their small particle size and large specific surface area, significantly enhance the absorbent disinfectant's absorption rate, absorption capacity, and bactericidal efficacy. The maximum absorption capacity is 556.5 g / g in distilled water and 90 g / g in 0.9% saline solution, reaching a 50-fold absorption capacity in less than 10 seconds. It exhibits a KL value >5 for microbial killing efficacy against various bodily fluid contaminants and shows no significant damage to aerospace metal materials or cabin interior materials, meeting international aviation chemical product safety standards. Therefore, the nano-absorbent disinfectant of this invention can be used for emergency treatment of biological bodily fluid contaminants (human and animal), such as blood, excrement, secretions, and vomit, in various locations, effectively controlling the spread of harmful substances or pathogens in bodily fluids. It has particularly wide application value in aviation cabin hygiene, hospitals, and public health and epidemic prevention.

[0042] This invention first employs a polymerization technique using multiple hydrophilic monomers to effectively improve the structure of various chemical groups within the superabsorbent resin, fully utilizing the hydrophilic sites of hydrophilic functional groups such as carboxyl groups (-COOH) and amide groups (-CONH2) to enhance the resin's water absorption, salt and acid resistance. Simultaneously, maleic anhydride (MA) with a certain degree of amination and inorganic nanomaterials (such as organo-montmorillonite OMMT) are added, and free radical polymerization is carried out under the action of a crosslinking agent and initiator to prepare the superabsorbent resin P(AA-AM / OMMT) nanocomposite material. Detailed Implementation

[0043] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0044] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0045] Example 1

[0046] Preparation of nano-water-absorbing disinfectant

[0047] Step 1: Using sodium dichloroisocyanurate (DCCNa) as the matrix, DCCNa and titanium dioxide nanoparticles (TiO2, particle size of 50nm) are mixed by a blending method. The mass ratio of DCCNa to titanium dioxide nanoparticles is 1:0.05 to prepare DCCNa / TiO2 composite disinfection material, namely functionalized sodium dichloroisocyanurate.

[0048] Testing showed that the DCCNa / TiO2 composite material at a concentration of 500 μg / ml, after 5 min of action, achieved a 99.99% kill rate against Escherichia coli (8099), Staphylococcus aureus (TACC 6538), and Candida albicans (ATCC 10231); and at a concentration of 1000 μg / ml, after 30 min of action, achieved a 99.99% kill rate against Mycobacterium tumefaciens subsp. abscessus (CMCC 93326) and Bacillus subtilis var. niger spores (ATCC 9372).

[0049] Step 2: Using free radical solution polymerization, acrylic resin (AA), polyacrylamide (AM), maleic anhydride (MA), and organomontmorillonite (OMMT) were used as comonomers. The reaction was carried out with inorganic hydrogen peroxide as an initiator and N,N-methylenebisacrylamide (MBA) as a crosslinking agent. The reactants were washed, filtered, and vacuum dried to prepare acrylamide and acrylic / montmorillonite nanocomposite water-absorbing material P(AA-AM / OMMT) (denoted as component B).

[0050] The degree of neutralization of AA is 70%, the degree of amination of MA is 75%, the mass ratio of AA, AM, MA and OMMT is 6:2:0.1:0.3, the amount of initiator and crosslinking agent is 0.2‰ and 0.04‰ of the total mass of the four monomers, respectively, the polymerization temperature is 65℃, and the polymerization reaction time is 50min.

[0051] Step 3: Mix and grind components A and B at a mass ratio of 1:9 in a custom-made mixing and grinding machine (using special grinding media and specific grinding aids), and pass through a 160-mesh sieve to prepare a nano-sized water-absorbing disinfectant. Packaging specifications are 100g according to the requirements of the aircraft cabin environment.

[0052] According to the test methods of GB / T1034-2008, ISO 19699-1 2017, and ISO 19699-2 2017, the various properties of the water-absorbing disinfectant in Example 1 were tested, and the test results are shown in Table 1 below.

[0053] Table 1. Performance test results of the water-absorbing disinfectant in Example 1

[0054]

[0055]

[0056] As shown in Table 1, the water absorption ratio of the water-absorbing disinfectant is 556 g / g for distilled water and 90.8 g / g for 0.9% sodium chloride solution. The centrifugal retention is >45 g / g, the pH value is 6-7, the particle size is 80-100 nm, and the passing rate through a 140-mesh sieve is ≥85%. Furthermore, the water-absorbing disinfectant of this invention achieves semi-solidification / gelation in <10 seconds for 5 ml of blood, complete gelation in <30 seconds for 50 ml of urine and 30 ml of serum, and semi-solidification / gelation in <30 seconds for 100 ml of vomit.

[0057] Example 2: On-site evaluation of usage effect

[0058] Using the nano-absorbent disinfectant provided in Example 1 of this invention to treat various contaminants (human urine, serum, blood, vomit) (wherein, the absorbent disinfectant and the contaminants are shown in Table 1 below), after 10 minutes of action, it can be observed that the target object rapidly turns into a gel solid state within 10 to 20 seconds, which can effectively prevent the spread of body fluids and is easy to remove.

[0059] Samples were taken from the target body fluid before and 3 minutes after treatment. The microbial killing efficacy of the nano-water-absorbing disinfectant provided in Example 1 was tested according to the testing methods of the 2002 edition of the National Disinfection Technical Specifications. The test results are shown in Table 2 below.

[0060] Table 2. Evaluation results of the efficacy of nano-water-absorbing disinfectants against various bodily fluid contaminants.

[0061]

[0062] Note: E C Escherichia coli (8099), Staphylococcus aureus (S) (TACC 6538), Candida albicans (Ca) (ATCC10231)

[0063] As shown in Table 2, the action time was 3 minutes, and the log killing value (KL value) against Escherichia coli (8099), Staphylococcus aureus (TACC6538), and Candida albicans (ATCC 10231) was greater than 5, which meets the requirements of the national disinfection technical specifications.

[0064] In accordance with the regulations and management requirements of the Civil Aviation Administration of China (CCAR53), an airworthiness evaluation test was conducted on the nano-water-absorbing disinfectant of Example 1. The testing methods and evaluation standards were performed according to SAE SMS1450C. Evaluation indicators included: flash point test, full immersion corrosion test, intercalation corrosion test, polyacrylate stress silvering test, polycarbonate stress silvering test, influence on painted surfaces and rubber, influence on vinyl plastics, and Tadlar influence test. The test results are shown in Table 3 below. Under a water absorption ratio of 30, after 8 hours of contact, there was no significant damage to aviation metal materials or cabin interior materials, meeting international safety standards for aviation chemical products.

[0065] Table 3. Airworthiness Test Results of Nano-Water Absorbent Disinfectant

[0066]

[0067]

[0068] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A nano-water-absorbing disinfectant, characterized in that, By weight percentage, it comprises 85-95% of a composite material of water-absorbing resin / inorganic nanomaterials and 5-15% of functionalized sodium dichloroisocyanurate. The functionalized sodium dichloroisocyanurate is a complex of sodium dichloroisocyanurate and inorganic oxides, wherein the inorganic oxides have a particle size of nanometers and the mass percentage of the inorganic oxides in the functionalized sodium dichloroisocyanurate is 0.10-8%.

2. The nano-water-absorbing disinfectant according to claim 1, characterized in that, In the composite material of the water-absorbing resin / inorganic nanomaterial, the water-absorbing resin is selected from acrylic polymer resins; Preferably, the water-absorbing resin is at least one of maleic anhydride grafted modified polyacrylic acid resin, acrylic acid-maleic anhydride copolymer resin, maleic anhydride grafted modified acrylic acid-acrylamide copolymer resin, and acrylic acid-acrylamide-maleic anhydride copolymer resin. Preferably, in the composite material of the water-absorbing resin / inorganic nanomaterial, the inorganic nanomaterial refers to nanoscale oxides or inorganic salts; Preferably, the inorganic nanomaterial is selected from at least one of montmorillonite, silicon dioxide, and titanium dioxide.

3. The nano-water-absorbing disinfectant according to claim 1, characterized in that, The composite material of the water-absorbing resin / inorganic nanomaterial is a copolymer of acrylic acid, acrylamide, maleic anhydride and organomontmorillonite; Alternatively, it may be a copolymer of acrylic resin, polyacrylamide, maleic anhydride, and organomontmorillonite.

4. The nano-water-absorbing disinfectant according to any one of claims 1-3, characterized in that, The inorganic oxide is selected from one or both of nano-silica or nano-titanium dioxide; Preferably, the functionalized sodium dichloroisocyanurate contains 5% by mass of nano-titanium dioxide; or, the functionalized sodium dichloroisocyanurate contains 0.10% by mass of nano-silica.

5. The nano-water-absorbing disinfectant according to any one of claims 1-4, characterized in that, The particle size of the nano-absorbent disinfectant is 80-100 nm.

6. The method for preparing the nano-water-absorbing disinfectant according to any one of claims 1-5, characterized in that, The method includes the following steps: Step 1: Prepare or manufacture functionalized sodium dichloroisocyanurate; Step 2: Prepare or fabricate a composite material of water-absorbing resin / inorganic nanomaterials; Step 3: Mix the functionalized sodium dichloroisocyanurate from Step 1 and the composite material of water-absorbing resin / inorganic nanomaterial from Step 2 to prepare the nano-water-absorbing disinfectant.

7. The method according to claim 6, characterized in that, Step 1 specifically includes: mixing sodium dichloroisocyanurate and inorganic oxides to prepare the functionalized sodium dichloroisocyanurate.

8. The method according to claim 6, characterized in that, Step 2 specifically includes: copolymerizing acrylic resin, polyacrylamide, maleic anhydride and inorganic nanomaterials under the action of an initiator and / or crosslinking agent to prepare a composite material of water-absorbing resin / inorganic nanomaterials; Preferably, in step 2, the mass ratio of acrylic resin, polyacrylamide, maleic anhydride, and inorganic nanomaterials is 7-6:2-3:0.1-0.2:0.2-0.8; Preferably, in step 2, the crosslinking agent is selected from at least one of N,N-methylenebisacrylamide and N-hydroxymethylacrylamide.

9. The method according to claim 6, characterized in that, In step 2, the degree of neutralization of the acrylic resin is 65-72%; Preferably, in step 2, the degree of amination of maleic anhydride is 70-78%.

10. The method according to claim 6, characterized in that, In step 3, the mass ratio of functionalized sodium dichloroisocyanurate and the composite material of water-absorbing resin / inorganic nanomaterial is 5-15:85-95.

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