A microgel type cleaning agent and its preparation method and application

Abstract

This invention discloses a microgel-type cleaning agent, its preparation method, and its application. The microgel-type cleaning agent comprises the following components by mass percentage: 1-10 wt% poly(N-isopropylacrylamide), 1-10 wt% polyacrylic acid, 1-15 wt% surfactant, 1-10 wt% metal-organic framework material, 0.5-5 wt% bactericide and disinfectant, with the remainder being a solvent. The microgel-type cleaning agent provided by this invention simultaneously achieves cleaning of items and chemical removal of stains, fundamentally solving the harm of pollutants to human health and the ecological environment. Furthermore, this microgel-type cleaning agent has a wide range of applications and multiple uses; it can be used for daily cleaning in high-oil and heavily soiled environments such as homes, restaurant and hotel kitchens, and auto repair shops, and can also be made into portable cleaning wipes for outdoor use.

Description

Technical Field

[0001] This invention belongs to the field of cleaning technology, specifically relating to a microgel-type cleaning agent, its preparation method, and its application. Background Technology

[0002] Cleaning agents are liquids primarily composed of surfactants and bactericides, used to wash clothes, clean utensils, or clean furniture. When applied to the surface of an object, they combine with or dissolve dirt, but they require rinsing with water to remove residues. Ultimately, pollutants are discharged into rivers, lakes, and oceans, rather than being eliminated at their source. These pollutants may have complex structures and stable chemical properties, making them difficult to decompose naturally in the environment. They often possess various toxicities and carcinogenicities, interfering with biological growth processes and human functions even at low concentrations, posing direct or potential harm to the ecological environment and human health. Therefore, the rational design of cleaning agent components to simultaneously achieve cleaning and chemical removal of stains is of great significance. Existing traditional cleaning agents can generally clean items, but they cannot chemically remove some stains, have unsatisfactory antibacterial effects, and require low concentrations and large quantities. Therefore, developing a microgel-type cleaning agent with dual functions of cleaning and stain degradation is imperative. Summary of the Invention

[0003] The main objective of this invention is to provide a microgel-type cleaning agent, its preparation method, and its application, in order to overcome the shortcomings of the prior art.

[0004] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0005] This invention provides a microgel-type cleaning agent comprising the following components by weight percentage: 1-10 wt% poly(N-isopropylacrylamide), 1-10 wt% polyacrylic acid, 1-15 wt% surfactant, 1-10 wt% metal-organic framework material, 0.5-5 wt% bactericide and disinfectant, with the remainder being a solvent.

[0006] Furthermore, the bactericidal disinfectant includes graphene-loaded metal single-atom materials, which include any one or a combination of two or more of graphene-loaded silver single atoms, graphene-loaded iron single atoms, graphene-loaded gold single atoms, and graphene-loaded cobalt single atoms.

[0007] This invention also provides a method for preparing the aforementioned microgel-type cleaning agent, which includes: ultrasonically mixing a metal-organic framework material, a bactericide and disinfectant with a solvent, then adding a surfactant and mixing evenly, and then adding poly(N-isopropylacrylamide) and polyacrylic acid and mixing and reacting thoroughly to obtain a microgel-type cleaning agent.

[0008] The embodiments of the present invention also provide the use of the aforementioned microgel-type cleaning agents in the cleaning field.

[0009] This invention also provides a portable cleaning wipe, which includes the aforementioned microgel-type cleaning agent.

[0010] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0011] (1) Compared with the cleaning agents in the prior art, the microgel-type cleaning agent of the present invention can simultaneously clean the items and chemically remove stains, fundamentally solving the harm of pollutants to human health and the ecological environment.

[0012] (2) The present invention promotes the dispersion of metal-organic framework materials and bactericides by synergistic generation of binary microgels of polyisopropylacrylamide and polyacrylic acid, which significantly improves the detergency, antibacterial and catalytic effects of microgel-type cleaners;

[0013] (3) Compared with the bactericidal and disinfectant agents such as silver nanoparticles in the prior art, the graphene-supported metal single-atom material in this invention has a larger specific surface area and higher efficiency;

[0014] (4) The microgel-type cleaner prepared by the present invention has a wide range of applications and uses. It can be used for daily cleaning in places with high oil and heavy dirt, such as kitchens in homes / restaurants / hotels and car repair shops. It can also be made into portable cleaning wipes for outdoor use. Detailed Implementation

[0015] In view of the deficiencies of the prior art, the inventors of this invention, through long-term research and extensive practice, have come up with the technical solution of this invention.

[0016] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Specifically, as one aspect of the technical solution of the present invention, the microgel-type cleaning agent involved includes the following components calculated by mass percentage: 1-10 wt% poly(N-isopropylacrylamide), 1-10 wt% polyacrylic acid, 1-15 wt% surfactant, 1-10 wt% metal-organic framework material, 0.5-5 wt% bactericide and disinfectant, and the remainder includes solvent.

[0018] In some more specific embodiments, the surfactant includes any one or a combination of two or more of sodium dodecylbenzenesulfonate, alkoxyethylene hydroxyethanol, stearic acid, oleic acid, lauric acid, and sodium lauryl sulfate, and is not limited thereto.

[0019] In some more specific embodiments, the metal-organic framework material includes any one or a combination of two or more of Fe-MIL-53, Fe-MIL-88A, and Fe-MIL-101, but is not limited thereto.

[0020] In some more specific implementations, the bactericidal disinfectant includes, but is not limited to, graphene-supported metal single-atom materials.

[0021] As a preferred embodiment, the content of metal single atoms in the graphene-supported metal single-atom material is 0.01–1 wt%, and the specific surface area of ​​the graphene-supported metal single-atom material is 200–2000 m². 2 / g.

[0022] As a preferred embodiment, the graphene-loaded metal single-atom material includes any one or a combination of two or more of graphene-loaded silver single-atom material, graphene-loaded iron single-atom material, graphene-loaded gold single-atom material, and graphene-loaded cobalt single-atom material, and is not limited thereto.

[0023] In some more specific embodiments, the solvent includes, but is not limited to, aqueous solutions of alcohols.

[0024] As a preferred embodiment, the aqueous alcohol solution includes aqueous ethanol solution and / or aqueous isopropanol solution, but is not limited thereto.

[0025] As a preferred embodiment, the water content in the aqueous alcohol solution is greater than or equal to 50 wt%.

[0026] As another aspect of the technical solution of the present invention, the preparation method of the aforementioned microgel-type cleaning agent includes: ultrasonically mixing metal-organic framework material, bactericide and disinfectant with solvent, then adding surfactant and mixing evenly, and then adding poly(N-isopropylacrylamide) and polyacrylic acid and mixing and reacting thoroughly to obtain microgel-type cleaning agent.

[0027] In some more specific embodiments, the method for preparing the microgel-type detergent includes:

[0028] (1) Add metal-organic framework material, bactericide and solvent to the container, disperse by ultrasonication, and stir thoroughly; (the dispersion of metal-organic framework material and bactericide is promoted by the stabilizing effect of charge) (2) Add surfactant and stir thoroughly;

[0029] (3) Add poly(N-isopropylacrylamide) and polyacrylic acid, stir thoroughly to obtain the finished product.

[0030] In this invention, poly(N-isopropylacrylamide) is a weakly positively charged polymer, and polyacrylic acid is a weakly negatively charged polymer. The two react with electrostatic interactions and hydrogen bonds to form a binary microgel (i.e., the aforementioned "microgel-type detergent"). The binary microgel has strong water-locking ability, which is beneficial for cleaning and removing dirt. The graphene-supported metal single atoms have both catalytic and bactericidal effects.

[0031] Another aspect of the present invention provides the use of the aforementioned microgel-type cleaning agent in the cleaning field.

[0032] Another aspect of the present invention provides a portable cleaning wipe comprising the aforementioned microgel-type cleaning agent.

[0033] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments. These embodiments are implemented on the premise of the technical solution of the invention, and detailed implementation methods and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0034] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0035] Example 1

[0036] (1) Add 1wt% Fe-MIL-53, 0.5wt% graphene-supported silver single atoms, 46.5wt% water and 40wt% ethanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0037] (2) Add 1 wt% sodium dodecylbenzenesulfonate and stir thoroughly;

[0038] (3) Add 1 wt% polyisopropylacrylamide and 10 wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0039] Example 2

[0040] (1) Add 10wt% Fe-MIL-88A, 5wt% graphene-supported iron single atoms, 39wt% water and 20wt% isopropanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0041] (2) Add 15wt% alkoxypolyethylene hydrooxyethanol and stir thoroughly;

[0042] (3) Add 10wt% polyisopropylacrylamide and 1wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0043] Example 3

[0044] (1) Add 2wt% Fe-MIL-101, 2wt% graphene-loaded gold single atoms, 50wt% water and 31wt% ethanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0045] (2) Add 5 wt% stearic acid and stir thoroughly;

[0046] (3) Add 5wt% polyisopropylacrylamide and 5wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0047] Example 4

[0048] (1) Add 3wt% Fe-MIL-101, 3wt% graphene-supported cobalt single atoms and 54wt% water and 30wt% ethanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0049] (2) Add 3wt% surfactant oleic acid and stir thoroughly;

[0050] (3) Add 3wt% polyisopropylacrylamide and 4wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0051] Example 5

[0052] (1) Add 4wt% Fe-MIL-101, 3wt% graphene-supported cobalt single atoms, and 47wt% water and 30wt% ethanol as solvents to a container, disperse by ultrasonication, and stir thoroughly;

[0053] (2) Add 6wt% lauric acid and stir thoroughly;

[0054] (3) Add 6wt% polyisopropylacrylamide and 4wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0055] Example 6

[0056] (1) Add 2wt% Fe-MIL-101, 2wt% graphene-supported cobalt single atoms and 45wt% water and 31wt% ethanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0057] (2) Add 10wt% sodium lauryl sulfate and stir thoroughly;

[0058] (3) Add 5.5wt% polyisopropylacrylamide and 4.5wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0059] Example 7

[0060] (1) Add 2wt% Fe-MIL-101, 2wt% graphene-supported cobalt single atoms and 45wt% water and 31wt% ethanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0061] (2) Add 10wt% sodium lauryl sulfate and stir thoroughly;

[0062] (3) Add 5.5 wt% polyisopropylacrylamide and 4.5 wt% polyacrylic acid, and stir thoroughly;

[0063] (4) Add dry paper towels, soak them thoroughly, remove them, squeeze out the liquid, and ensure that the liquid residue is 2 to 5 times the initial weight of the dry paper towels to obtain wet paper towels.

[0064] Comparative Example 1

[0065] Add 2wt% Fe-MIL-101, 2wt% graphene-supported cobalt single atoms, and 45wt% water and 31wt% ethanol as solvents to a container, disperse by ultrasonication, and stir thoroughly.

[0066] (2) Add 10wt% sodium lauryl sulfate and stir thoroughly;

[0067] (3) Add 10wt% polyacrylic acid and stir thoroughly to obtain the finished product.

[0068] Comparative Example 2

[0069] Add 2wt% Fe-MIL-101, 2wt% graphene-supported cobalt single atoms, and 45wt% water and 31wt% ethanol as solvents to a container, disperse by ultrasonication, and stir thoroughly.

[0070] (2) Add 10wt% sodium lauryl sulfate and stir thoroughly;

[0071] (3) Add 10wt% poly(N-isopropylacrylamide), stir thoroughly, and obtain the finished product.

[0072] Comparative Example 3

[0073] (1) Add 2wt% Fe-MIL-101, 2wt% graphene-supported cobalt single atoms and 55wt% water and 31wt% ethanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0074] (2) Add 5.5wt% polyisopropylacrylamide and 4.5wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0075] Comparative Example 4

[0076] (1) Add 2wt% graphene-loaded cobalt single atoms and 47wt% water and 31wt% ethanol as solvents to a container, disperse by ultrasonication, and stir thoroughly;

[0077] (2) Add 10wt% sodium lauryl sulfate and stir thoroughly;

[0078] (3) Add 5.5wt% polyisopropylacrylamide and 4.5wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0079] Comparative Example 5

[0080] (1) Add 2wt% graphene-loaded cobalt single atoms and 47wt% water and 31wt% ethanol as solvents to a container, disperse by ultrasonication, and stir thoroughly;

[0081] (2) Add 10wt% sodium lauryl sulfate and stir thoroughly;

[0082] (3) Add 5.5wt% polyisopropylacrylamide and 4.5wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0083] Comparative Example 6

[0084] (1) Add 2wt% Fe-MIL-101, 2wt% graphene-supported cobalt single atoms and 54wt% water and 31wt% ethanol as solvent to a container, disperse by ultrasonication and stir thoroughly;

[0085] (2) Add 10wt% sodium lauryl sulfate and stir thoroughly;

[0086] (3) Add 0.5wt% polyisopropylacrylamide and 0.5wt% polyacrylic acid, stir thoroughly to obtain the finished product.

[0087] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0088] Performance characterization: Decontamination and antibacterial tests were conducted on the samples from Examples 1-7 and Comparative Examples 1-6;

[0089] 1. Decontamination test:

[0090] The whiteness of the white cotton knitted fabric was tested and the whiteness retention rate was calculated, according to the method in "Application Research of Anti-redeposition Agent in Laundry Detergent", Daily Chemical Science, 2011, 34(10):21. The results are shown in Table 1.

[0091] 2. Antibacterial test:

[0092] The tests were conducted in accordance with Appendix C of the "Hygienic Standard for Disposable Sanitary Products GB 15979 2002", and the results are shown in Table 1.

[0093] Table 1 Comparison of detergency and antibacterial effects between Examples 1-7 and Comparative Examples 1-6

[0094] Whiteness retention rate (%) Staphylococcus aureus inhibition rate (%) Escherichia coli inhibition rate (%) Example 1 95.4±2.1 99.8±0.1 97.8±0.3 Example 2 96.7±1.9 98.7±0.3 97.4±0.5 Example 3 95.1±1.3 97.6±0.4 98.3±0.2 Example 4 97.4±1.7 97.2±0.7 98.5±0.2 Example 5 95.1±2.4 98.6±0.4 97.6±0.4 Example 6 93.8±0.9 97.9±0.1 99.1±0.6 Example 7 94.6±1.2 98.2±1.3 98.7±0.6 Comparative Example 1 82.3±1.3 88.6±2.1 76.8±1.4 Comparative Example 2 79.6±2.7 79.3±1.7 79.3±2.1 Comparative Example 3 73.1±1.7 81.1±0.5 80.5±0.9 Comparative Example 4 77.5±2.8 70.6±0.3 83.2±3.9 Comparative Example 5 66.7±1.5 88.2±0.6 79.4±1.8 Comparative Example 6 71.2±1.3 80.5±1.9 75.3±0.7

[0095] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. A microgel-type cleaning agent, characterized in that... It includes the following components by mass percentage: 1-10 wt% poly(N-isopropylacrylamide), 1-10 wt% polyacrylic acid, 1-15 wt% surfactant, 1-10 wt% metal-organic framework material, 0.5-5 wt% bactericide and disinfectant, with the remainder including solvent; The surfactant comprises any one or a combination of two of alkoxylated polyethylene glycol and sodium lauryl sulfate; the bactericide comprises graphene-supported metal single-atom materials, which comprises any one or a combination of two or more of graphene-supported iron single-atom materials, graphene-supported gold single-atom materials, and graphene-supported cobalt single-atom materials; the metal-organic framework material comprises any one or a combination of two or more of Fe-MIL-53, Fe-MIL-88A, and Fe-MIL-101.

2. The microgel-type cleaning agent according to claim 1, characterized in that: The content of metal single atoms in the graphene-supported metal single-atom material is 0.01–1 wt%, and the specific surface area of ​​the graphene-supported metal single-atom material is 200–2000 m². 2 / g.

3. The microgel-type cleaning agent according to claim 1, characterized in that: The solvent includes an aqueous solution of an alcohol; the aqueous solution of an alcohol includes an aqueous solution of ethanol; and the water content in the aqueous solution of the alcohol is greater than or equal to 50 wt%.

4. The method for preparing the microgel-type detergent according to any one of claims 1-3, characterized in that... include: The metal-organic framework material, bactericide and disinfectant are ultrasonically mixed with solvent, then a surfactant is added and mixed evenly. Finally, poly(N-isopropylacrylamide) and polyacrylic acid are added and mixed thoroughly to prepare a microgel-type cleaning agent.

5. A portable cleaning wipe, characterized in that... Includes the microgel-type cleaner according to any one of claims 1-3.