A nano water-absorbing disinfectant and its preparation method

Abstract

The present invention discloses a nano water-absorbing disinfectant and a preparation method thereof. The nano water-absorbing disinfectant comprises, by mass percentage, 85-95% of a composite material of a water-absorbing resin / inorganic nanomaterial and 5-15% of functionalized sodium dichloroisocyanurate. The nano water-absorbing disinfectant of the present invention includes nanoscale materials. Due to its unique properties such as small particle size and large specific surface area, the water-absorbing disinfectant of the present invention has significantly improved water absorption rate, water absorption rate, and bactericidal efficacy. The maximum water absorption rate of distilled water is 556.5g / g, and the maximum water absorption rate in 0.9% saline is 90g / g. The water absorption rate of 50 times is no more than 10s, and the KL value of killing efficacy for various body fluid pollutants is greater than 5; and there is no obvious damage to aviation metal materials and cabin interior materials, and it meets international aviation chemical product safety standards.

Description

Technical Field

[0001] The present invention belongs to the technical field of disinfectants for aviation hygiene and public health, and relates to a disinfectant and a preparation method thereof, and in particular to a nano water-absorbing disinfectant and a preparation method thereof. Background Art

[0002] The threat of traditional infectious diseases persists. Class A infectious diseases occur from time to time, while 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 on the rise year by year. Emerging infectious diseases are also on the rise. Therefore, developing efficient disinfection technologies, effectively and promptly disposing of infectious contamination sources, and cutting off transmission routes are important technical measures to curb the spread of infectious diseases.

[0003] Biofluid contaminants (human and animal), including blood, excreta, secretions, and vomitus, are defined by the WHO as contaminants posing a significant epidemiological risk and should be treated as sources of contamination through efficient disinfection. There are two key elements to the harmless disposal of biofluids (human and animal), including blood, excreta, secretions, and vomitus: first, rapid solidification / gelation of the biofluids to prevent leakage, splashing, and flow, thus preventing the spread of contamination; and second, a kill effect on the microorganisms that cause the contamination.

[0004] Patent document CN101961010B discloses a water-absorbing disinfectant dry powder composed of 90-99% polyacrylic acid-based polymer water-absorbing resin and 1-10% trichloroisocyanuric acid. This water-absorbing disinfectant dry powder only has an antibacterial effect on pathogens and lacks disinfection efficacy, and its water absorption rate needs to be improved. Furthermore, existing methods for treating biological fluid contaminants suffer from poor water absorption, uneven disinfection, and incomplete disinfection. Furthermore, due to the leakage, sputtering, and flow characteristics of body fluids, contamination can easily expand, adversely affecting the environment and human health. Summary of the Invention

[0005] In response to the above technical problems, the present invention provides a nano water-absorbing disinfectant and a preparation method thereof. The nano water-absorbing disinfectant of the present invention has a higher liquid absorption capacity and liquid absorption rate for biological fluid (human and animal) pollutants (including blood, excrement, secretions, vomitus), as well as acid resistance, salt resistance, and resistance to organic interference. It has a rapid gelation effect on biological fluid pollutants and achieves a high level of disinfection effect. It is safe and environmentally friendly, has no obvious damage to aviation metal materials and cabin interior materials, and meets international aviation chemical product safety standards.

[0006] In order to achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows:

[0007] A nano water-absorbing disinfectant comprises, by mass percentage, 85-95% of a composite material of a water-absorbing resin / inorganic nanomaterial and 5-15% of functionalized sodium dichloroisocyanurate.

[0008] According to an embodiment of the present invention, in the composite material of water-absorbent resin / inorganic nanomaterial, the water-absorbent 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.

[0009] According to an embodiment of the present invention, in the water-absorbent resin / inorganic nanomaterial composite material, the inorganic nanomaterial refers to a nanoscale (having at least one dimension less than 100 nm) oxide or inorganic salt. Specifically, it can be selected from montmorillonite (specifically, organic montmorillonite, abbreviated as OMMT), silicon dioxide, titanium dioxide, etc.

[0010] According to an embodiment of the present invention, in the nano water-absorbing disinfectant, the content of the composite material is 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95 or any specific point value within the range of any combination of any two of the above point values, calculated as a percentage by mass.

[0011] According to an embodiment of the present invention, in the nano water-absorbing disinfectant, the content of the functionalized sodium dichloroisocyanurate is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or any specific point value within the range of any combination of any two of the above point values, measured in mass percentage.

[0012] For example, the mass percentage of the composite material is 90%, and the mass percentage of the functionalized sodium dichloroisocyanurate is 10%; for another example, the mass percentage of the composite material is 89%, and the mass percentage of the functionalized sodium dichloroisocyanurate is 11%; for another example, the mass percentage of the composite material is 88%, and the mass percentage of the functionalized sodium dichloroisocyanurate is 12%.

[0013] According to an embodiment of the present invention, the water-absorbent resin / inorganic nanomaterial composite material is a copolymer of acrylic acid (AA), acrylamide (AM), maleic anhydride (MA) and organic montmorillonite (OMMT); or, it is a copolymer of acrylic resin, polyacrylamide, maleic anhydride and organic montmorillonite, which can be recorded as P(AA-AM / OMMT) nanocomposite material.

[0014] According to an embodiment of the present invention, the structural formula of sodium dichloroisocyanurate in the functionalized sodium dichloroisocyanurate is as follows, which can also be expressed as DCCNa:

[0015]

[0016] The sodium dichloroisocyanurate (DCCNa) of the present invention has the following advantages: 1) Strong microbial killing efficacy: DCCNa has strong oxidizing properties and has a strong killing effect on various pathogenic microorganisms such as viruses, bacterial spores, and fungi, making it a highly effective bactericide with a wide range of applications. Pure DCCNa has an available chlorine content of 64.5%, and high-quality products have an available chlorine content of greater than 60%, demonstrating a strong disinfecting and sterilizing effect, with a sterilization rate of 99% at 20 ppm. 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 (compared to the median lethal dose of trichloroisocyanuric acid, which is only 0.72 to 0.78 g / kg). DCCNa has long been approved for use in food and drinking water disinfection and sterilization processes both domestically and internationally. 3) High available chlorine utilization: DCCNa has a high solubility in water, with 30 g of DCCNa dissolving per 100 mL of water at 25°C. Even in aqueous solutions as cold as 4°C, DCCNa rapidly releases all of its available chlorine, fully maximizing its disinfection and sterilization effectiveness. Other solid chlorine-containing products have much lower chlorine values ​​than DCCNa due to their lower solubility or slow chlorine release rates. 4) Excellent stability: Due to the high stability of the triazine ring in the molecules of chloroisocyanuric acid products, DCCNa is very stable. According to tests, after one year of storage, the available chlorine loss of dried DCCNa in a warehouse is less than 1%.

[0017] According to an embodiment of the present invention, the functionalized sodium dichloroisocyanurate is a complex of sodium dichloroisocyanurate and an inorganic oxide. Specifically, the inorganic oxide has a nanometer-scale particle size, for example, selected from nano-silicon dioxide and nano-titanium dioxide. Furthermore, the weight percentage of the inorganic oxide in the functionalized sodium dichloroisocyanurate is 0.10-8%. For example, the weight percentage of nano-titanium dioxide in the functionalized sodium dichloroisocyanurate is 5%. Furthermore, for example, the weight percentage of nano-silicon dioxide in the functionalized sodium dichloroisocyanurate is 0.10%.

[0018] According to an embodiment of the present invention, the particle size of the nano water-absorbing disinfectant is 80-100 nm.

[0019] The present invention also provides a method for preparing the above-mentioned nano water-absorbing disinfectant, which comprises the following steps:

[0020] Step 1: preparing or preparing functionalized sodium dichloroisocyanurate;

[0021] Step 2: preparing or preparing a composite material of water-absorbent resin / inorganic nanomaterial;

[0022] Step 3: Mix the functionalized sodium dichloroisocyanurate in the above step 1 and the water-absorbing resin / inorganic nanomaterial composite material in step 2 to prepare the nano water-absorbing disinfectant.

[0023] According to an embodiment of the present invention, step 1 specifically includes: mixing sodium dichloroisocyanurate (DCCNa) and an inorganic oxide to prepare the functionalized sodium dichloroisocyanurate.

[0024] 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.

[0025] According to an embodiment of the present invention, in step 1, the definition of the inorganic oxide is the same as the definition of the inorganic oxide in the functionalized sodium dichloroisocyanurate.

[0026] Specifically, step 1 may be: mixing sodium dichloroisocyanurate (DCCNa) and nano-titanium dioxide to prepare the functionalized sodium dichloroisocyanurate, which may be referred to as a DCCNa / TiO2 composite material.

[0027] 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 water-absorbent resin / inorganic nanomaterial composite material.

[0028] According to an embodiment of the present invention, the inorganic nanomaterial in step 2 is defined as above.

[0029] According to an embodiment of the present invention, in step 2, the mass ratio of acrylic resin, polyacrylamide, maleic anhydride, and inorganic nanomaterial is 7-6:2-3:0.1-0.2:0.2-0.8.

[0030] 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.

[0031] According to an embodiment of the present invention, in step 2, the content of the cross-linking agent is 0.01-0.08‰ of the total mass of the four monomers.

[0032] 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.

[0033] According to an embodiment of the present invention, in step 2, the cross-linking agent is selected from at least one of N,N-methylenebisacrylamide (MBA), N-hydroxymethyl acrylamide (N-MAM), and the like.

[0034] 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.

[0035] According to an embodiment of the present invention, in step 2, the neutralization degree of the acrylic resin is 65-72%, for example, 70%.

[0036] According to an embodiment of the present invention, in step 2, the degree of amination of maleic anhydride is 70-78%, for example 75%.

[0037] According to an embodiment of the present invention, in step 3, the mass ratio of the functionalized sodium dichloroisocyanurate and the water-absorbing resin / inorganic nanomaterial composite material is 5-15:85-95.

[0038] According to an embodiment of the present invention, step 3 further comprises post-processing of the product such as grinding and screening.

[0039] Beneficial effects of the present invention:

[0040] The nano-water-absorbing disinfectant of the present invention comprises a composite material of a water-absorbing resin / inorganic nanomaterial and functionalized sodium dichloroisocyanurate, including nanoscale materials. Due to its unique properties, such as small particle size and large specific surface area, the nano-water-absorbing disinfectant of the present invention significantly improves water absorption rate, water absorption rate, and bactericidal efficacy. The maximum water absorption rate is 556.5 g / g in distilled water and 90 g / g in 0.9% saline, reaching a 50-fold absorption rate in less than 10 seconds. Its KL value for killing microorganisms in various body fluid contaminants is greater than 5. It also has no significant damage to aviation metal materials and cabin interior materials, meeting international aviation chemical product safety standards. Therefore, the nano-water-absorbing disinfectant of the present invention can be used in various emergency situations to dispose of biological fluid contaminants (human and animal), such as blood, excretions, secretions, and vomitus, effectively controlling the spread of harmful substances or pathogens in biological fluids. It has broad application value in the fields of aviation cabin hygiene, hospital, and public health and epidemic prevention.

[0041] The method of the present invention first utilizes the polymerization technology of multiple hydrophilic monomers to effectively improve the organization of various chemical groups within the chemical structure of a superabsorbent resin, fully utilizing the hydrophilic sites of hydrophilic functional groups such as carboxyl (-COOH) and amide (-CONH2) to enhance the resin's water absorption and salt and acid resistance. Maleic anhydride (MA) with a certain degree of amination and an inorganic nanomaterial (such as organic montmorillonite OMMT) are then added. Free radical polymerization is then carried out under the action of a crosslinking agent and an initiator to produce a superabsorbent resin P(AA-AM / OMMT) nanocomposite. DETAILED DESCRIPTION

[0042] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations 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 encompassed within the scope of protection that the present invention is intended to protect.

[0043] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0044] Example 1

[0045] Preparation of Nano Water-Absorbing Disinfectant

[0046] Step 1: Using sodium dichloroisocyanurate (DCCNa) as the matrix, DCCNa and titanium dioxide nanoparticles (TiO2, particle size 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.

[0047] After testing, the concentration of DCCNa / TiO2 composite material was 500μg / ml, and the action time was 5 minutes, and the killing rate against Escherichia coli (8099), Staphylococcus aureus (TACC 6538), and Candida albicans (ATCC 10231) reached 99.99%; the concentration of DCCNa / TiO2 composite material was 1000μg / ml and the action time was 30 minutes, and the killing rate against Mycobacterium abscessus subspecies (CMCC 93326) and Bacillus subtilis var. niger spores (ATCC 9372) reached 99.99%.

[0048] Step 2: A free radical solution polymerization method is used to copolymerize acrylic resin (AA), polyacrylamide (AM), maleic anhydride (MA), and organic montmorillonite (OMMT) as comonomers, with inorganic hydrogen peroxide as an initiator and N,N methylenebisacrylamide (MBA) as a crosslinker. The reactants are washed, filtered, and vacuum-dried to prepare acrylamide and acrylic acid / montmorillonite nanocomposite water-absorbing material P (AA-AM / OMMT) (denoted as component B).

[0049] Among them: the neutralization degree of AA is 70%, the amination degree of MA is 75%, the mass ratio of AA, AM, MA, and OMMT is 6:2:0.1:0.3, the amounts of initiator and cross-linker are 0.2‰ and 0.04‰ of the total mass of the four monomers, respectively, the polymerization temperature is 65°C, and the polymerization reaction time is 50 min.

[0050] Step 3: Place the above-mentioned component A and component B in a customized mixing and grinding machine at a mass ratio of 1:9 for mixing and multi-stage grinding (special grinding media and specific grinding aids), and pass through a 160-mesh sieve to prepare a nano-scale water-absorbing disinfectant. According to the requirements of the aircraft cabin use environment, the packaging specification is 100g.

[0051] According to the GB / T1034-2008 test method, ISO 19699-1 2017, and ISO 19699-2 2017, the various properties of the water-absorbing disinfectant of Example 1 were tested. The test results are shown in Table 1 below.

[0052] Table 1 Example 1 Water-absorbing disinfectant performance test results

[0053]

[0054] As can be seen from Table 1, the water absorption rate of the water-absorbing disinfectant is 556 g / g for distilled water, 90.8 g / g for 0.9% sodium chloride solution, a centrifugal retention capacity of >45 g / g, a pH value of 6-7, a particle size of 80-100 nm, and a 140-mesh sieve pass rate of ≥85%. In addition, the water-absorbing disinfectant of the present invention takes less than 10 seconds to semi-solidify / gel 5 ml of blood, less than 30 seconds to fully gel 50 ml of urine and 30 ml of serum, and less than 30 seconds to semi-solidify / gel 100 ml of vomitus.

[0055] Example 2 On-site use effect evaluation

[0056] The nano water-absorbing disinfectant provided in Example 1 of the present invention was used to treat various pollutants (human urine, serum, blood, and vomitus) (wherein the water-absorbing disinfectant and the pollutant ratio are shown in Table 1 below). After 10 minutes of action, it was observed that the target object quickly turned into a gel solid state within 10 to 20 seconds, which can effectively prevent the spread of body fluids and is easy to remove.

[0057] The target body fluids were sampled before and 3 minutes after treatment, and the microbial killing efficacy of the nano water-absorbing disinfectant provided in Example 1 was tested with reference to the 2002 edition of the National Technical Specifications for Disinfection. The test results are shown in Table 2 below.

[0058] Table 2 Evaluation results of the killing efficacy of nano water-absorbing disinfectants on various body fluid pollutants

[0059]

[0060] Note: E C Escherichia coli (8099), Sa Staphylococcus aureus (TACC 6538), Ca Candida albicans (ATCC10231)

[0061] As can be seen from Table 2, the action time is 3 minutes, and the killing logarithm value (KL value) of Escherichia coli (8099), Staphylococcus aureus (TACC6538), and Candida albicans (ATCC 10231) is greater than 5, meeting the requirements of national disinfection technical specifications.

[0062] In accordance with the provisions and management requirements of the Civil Aviation Administration of China's Aviation Chemical Products Airworthiness Management Regulations (CCAR Part 53), the nano water-absorbing disinfectant of Example 1 was subjected to an airworthiness evaluation test. The testing methods and evaluation criteria were implemented in accordance with SAE SMS1450C. The evaluation criteria included: flash point test, full immersion corrosion test, interlayer corrosion test, polyacrylate stress crazing test, polycarbonate stress crazing test, painted surface, rubber impact test, vinyl plastic impact test, and Tadllar impact test. The test results are shown in Table 3 below. Under the condition of 30 water absorption rate and 8 hours of action, there was no significant damage to aviation metal materials and cabin interior materials, meeting international aviation chemical product safety standards.

[0063] Table 3 Airworthiness test results of nano water-absorbing disinfectants

[0064]

[0065] The above is an exemplary description of the embodiments of the present invention. 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 shall be included in the scope of protection of the present invention.

Claims

1. A nano water-absorbing disinfectant, characterized in that: Calculated by mass percentage, it comprises 85-95% of a composite material of a water-absorbent resin / inorganic nanomaterial and 5-15% of functionalized sodium dichloroisocyanurate; The inorganic nanomaterial is selected from montmorillonite; The water-absorbing resin is acrylic acid-acrylamide-maleic anhydride copolymer resin; The functionalized sodium dichloroisocyanurate is a composite of sodium dichloroisocyanurate and nano-titanium dioxide.

2. The nano water-absorbing disinfectant according to claim 1, characterized in that In the functionalized sodium dichloroisocyanurate, the particle size of the nano titanium dioxide is nanometer scale.

3. The nano water-absorbing disinfectant according to claim 1, characterized in that The mass percentage of nano-titanium dioxide in the functionalized sodium dichloroisocyanurate is 0.10-8%.

4. The nano water-absorbing disinfectant according to claim 1, characterized in that The particle size of the nano water-absorbing disinfectant is 80-100 nm.

5. The method for preparing the nano water-absorbing disinfectant according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: Step 1: preparing or preparing functionalized sodium dichloroisocyanurate, comprising: mixing sodium dichloroisocyanurate and nano-titanium dioxide to prepare the functionalized sodium dichloroisocyanurate; Step 2: preparing or preparing a composite material of water-absorbent resin / inorganic nanomaterial; Step 3: Mix the functionalized sodium dichloroisocyanurate in the above step 1 and the water-absorbing resin / inorganic nanomaterial composite material in step 2 to prepare the nano water-absorbing disinfectant.

6. The method according to claim 5, characterized in that 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 water-absorbent resin / inorganic nanomaterial composite material.

7. The method according to claim 6, characterized in that In step 2, the mass ratio of acrylic resin, polyacrylamide, maleic anhydride and inorganic nanomaterial is 7-6:2-3:0.1-0.2:0.2-0.

8.

8. The method according to claim 6, characterized in that In step 2, the cross-linking agent is selected from N,N methylene bisacrylamide.

9. The method according to claim 6, characterized in that In step 2, the neutralization degree of the acrylic resin is 65-72%.

10. The method according to claim 6, characterized in that In step 2, the degree of amination of maleic anhydride is 70-78%.

11. The method according to claim 5, wherein In step 3, the mass ratio of the functionalized sodium dichloroisocyanurate to the water-absorbent resin / inorganic nanomaterial composite material is 5-15: 85-95.

Images