Bubble-free electrochemical laundry detergent and preparation method thereof

Abstract

The invention relates to a bubble-free electrochemical laundry detergent and a preparation method thereof, and relates to the technical field of cleaning. The laundry detergent disclosed by the invention is prepared from various raw materials such as zirconium oxychloride and terephthalic acid according to specific parts by weight through unique process steps such as preparation and mixing of metal-organic framework catalytic particles with special structures, biodegradable ionic liquid electrolyte and a multifunctional composite additive. The prepared laundry detergent has the advantages of being efficient, clean, environmentally friendly, safe, multifunctional and the like, convenient rinsing is achieved by means of bubble-free design, all the components cooperate to guarantee stability, the preparation process is scientific and rigorous, it is guaranteed that the product performance is excellent, stable and reliable, and the requirement of the market for novel laundry detergents is met.

Description

Technical Field

[0001] This invention relates to the field of cleaning technology, specifically to a non-foaming electrochemical laundry detergent and its preparation method. Background Technology

[0002] In today's society, as people pursue a higher quality of life, their expectations for laundry detergent performance are increasing. While traditional laundry detergents can meet basic cleaning needs, they are gradually revealing many shortcomings when faced with complex and diverse stains, as well as environmental protection and health requirements.

[0003] The core cleaning agent in traditional laundry detergents is primarily surfactant. However, surfactants prove inadequate when dealing with industrial oil stains containing silicone, food stains rich in polysaccharides and proteins, and mixed stains formed over long periods of wear. Furthermore, traditional laundry detergents may contain optical brighteners and phosphorus-based additives, which are not only difficult to biodegrade and cause persistent environmental pollution, but may also remain on clothing, posing a threat to human health. Moreover, traditional laundry detergents have relatively limited functionality and cannot meet consumers' diverse needs for antibacterial, mite-removing, and anti-static properties in clothing.

[0004] With increasing environmental awareness and technological development, the market urgently needs a new type of laundry detergent that can effectively clean all kinds of stubborn stains, is environmentally friendly and healthy, and has a variety of functions. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a non-foaming electrochemical laundry detergent and its preparation method. The laundry detergent of the present invention is composed of multiple raw materials such as zirconium oxychloride and terephthalic acid in specific weight proportions. It is produced through unique process steps including the preparation and mixing of specially structured metal-organic framework catalytic particles, biodegradable ionic liquid electrolytes, and multifunctional composite additives. The laundry detergent prepared by the present invention possesses advantages such as high-efficiency cleaning, environmental safety, and multifunctional integration. Furthermore, its non-foaming design enables convenient rinsing, and the synergistic effect of each component ensures stability. Its scientific and rigorous preparation process ensures excellent and stable product performance, meeting the market demand for novel laundry detergents.

[0006] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: The first objective of this invention is to provide a method for preparing a non-foaming electrochemical laundry detergent, comprising the following steps: (1) Zirconium oxychloride, terephthalic acid and N,N-dimethylformamide are mixed and reacted to obtain Zr-MOFs crystals; the Zr-MOFs crystals are placed in nitrogen gas for high-temperature carbonization, and acid etching is performed after carbonization to obtain metal-organic framework catalytic particles with special structure. (2) Mix 1-methylimidazolium with 2-bromopropionic acid to obtain mixture A, and reflux mixture A in acetonitrile solution to obtain an intermediate; mix the intermediate with sodium L-lactic acid to obtain mixture B, and react mixture B in ethanol solution, followed by rotary evaporation and recrystallization to obtain 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid; (3) Weigh carboxymethyl-β-cyclodextrin and nano zinc oxide, grind and sieve to obtain a mixture; add intelligent pH-responsive polymer to the mixture and perform ultrasonic dispersion to obtain a multifunctional composite additive; (4) The special structure metal-organic framework catalyst particles, the 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid, and the multifunctional composite additive are added sequentially to water, and the mixture is continuously stirred and heated to carry out the reaction, so as to obtain a non-foaming electrochemical laundry detergent.

[0007] The beneficial effects of this invention are as follows: This invention ensures the high efficiency of the non-foaming electrochemical laundry detergent by precisely preparing each key component in a step-by-step manner. The special metal-organic framework catalytic particle preparation process yields highly active catalytic particles, guaranteeing efficient cleaning; the synthesis of biodegradable ionic liquid electrolytes ensures their biodegradability and stability; the preparation process of multifunctional composite additives allows for thorough mixing of all components, maximizing their synergistic effect; and the mixing and preparation steps, under precise temperature control and stirring, achieve uniform dispersion of all components, improving the overall stability and comprehensive performance of the laundry detergent.

[0008] Based on the above technical solution, the present invention can be further improved as follows.

[0009] Furthermore, the weight ratio of zirconium oxychloride, terephthalic acid, and N,N-dimethylformamide in step (1) is 3~7:7~14:8~21.

[0010] The beneficial effects of adopting the above-mentioned further scheme are as follows: Using zirconium perchlorate, terephthalic acid, and N,N-dimethylformamide as raw materials to prepare specially structured metal-organic framework catalytic particles, and precisely controlling the mass ratio of the raw materials during the preparation process, ensures the reaction proceeds fully, which is conducive to the formation of an ideal crystal structure and lays the foundation for obtaining highly efficient catalytic performance. Furthermore, it generates highly efficient active oxygen species under electrochemical action, achieving a significantly higher removal rate for stubborn stains containing organosilicon oil, polysaccharides, and proteins than traditional laundry detergents, thus achieving highly efficient cleaning.

[0011] Furthermore, the N,N-dimethylformamide has a purity ≥99.5% and a water content <0.05%; the carboxymethyl-β-cyclodextrin has a carboxymethyl substitution degree of 1.5~2.5, a purity ≥98%, and an average particle size of 5μm~20μm.

[0012] The beneficial effects of adopting the above-mentioned further scheme are as follows: limiting the parameters of N,N-dimethylformamide and carboxymethyl-β-cyclodextrin can significantly optimize the performance of non-foaming electrochemical laundry detergent. The purity of N,N-dimethylformamide ≥99.5% greatly reduces the interference of impurities on the synthesis of special structured metal-organic framework catalytic particles, ensuring the reaction proceeds fully and enhancing catalytic activity. Meanwhile, the water content <0.05% prevents water from damaging the structure, improving product stability and cleaning effect. The degree of substitution of carboxymethyl-β-cyclodextrin is 1.5~2.5, ensuring optimal odor encapsulation ability, while a purity ≥98% improves functional stability. The average particle size of 5μm~20μm facilitates rapid dissolution and uniform dispersion, comprehensively improving the cleaning power and overall performance of the laundry detergent.

[0013] Furthermore, the pressure of the mixing reaction in step (1) is 5 MPa to 10 MPa, the temperature is 120°C to 150°C, and the time is 12h to 20h; The heating rate for high-temperature carbonization is 5℃ / min~10℃ / min, the carbonization temperature is 800℃~1000℃, and the holding time is 2h~4h. The acid etching solution used is dilute hydrochloric acid with a concentration of 0.1 mol / L, a temperature of 60℃~80℃, and an etching time of 4h~6h.

[0014] The beneficial effects of adopting the above-mentioned further scheme are as follows: setting specific reaction conditions for the mixed reaction can promote more regular growth of Zr-MOFs crystals and a more stable structure; during the carbonization process, setting the heating rate, temperature increase, and holding time helps to optimize the physicochemical properties of the material and enhance its catalytic activity and stability; the acid etching used in this invention can effectively remove impurities, precisely control the pore structure and surface properties of the material, and ultimately improve the performance of special structure metal-organic framework catalytic particles, thereby enhancing the cleaning ability and stability of laundry detergent.

[0015] Furthermore, in step (2), the weight ratio of 1-methylimidazole and 2-bromopropionic acid in mixture A is 3.2~5.8:2.8~6.3; and the weight ratio of intermediate and sodium L-lactic acid in mixture B is 5:0.6~2.6.

[0016] The beneficial effects of adopting the above-mentioned further scheme are: using a biodegradable ionic liquid electrolyte prepared from 1-methylimidazole, 2-bromopropionic acid and sodium L-lactic acid, the biodegradability rate reaches more than 95%, which greatly reduces environmental pollution, and has good biocompatibility with human skin, significantly reducing the skin allergy rate, and ensuring environmental protection and safety.

[0017] Furthermore, the reflux reaction in step (2) is carried out at a temperature of 35℃~45℃ for 12h~24h; the rotary evaporation reaction time is 8h~12h.

[0018] Furthermore, in step (2), the concentration of the acetonitrile solution is 0.2 mol / L, and the mass ratio of the acetonitrile solution to the mixture A is 1:2~4; the concentration of the ethanol solution is 0.1 mol / L, and the mass ratio of the ethanol solution to the mixture B is 1:8~12.

[0019] The beneficial effects of adopting the above-mentioned further scheme are as follows: In the reflux reaction, the temperature, reflux time, acetonitrile, and acetonitrile specified in this invention can jointly create a suitable reaction environment, which is conducive to the full reaction of 1-methylimidazole and 2-bromopropionic acid, and improves the yield and purity of the intermediate 1-methyl-3-(2-bromopropyl)imidazole bromide; in the subsequent rotary evaporation process, the reaction conditions and raw material ratio specified in this invention can effectively remove impurity solvents, and at the same time, through recrystallization purification, the purity of the 1-methyl-3-(2-amino-3-carboxypropyl)imidazole lactate ionic liquid can be increased to 1.5 to 2 times. The high-purity ionic liquid electrolyte can ensure its performance stability in the laundry detergent system, better provide an excellent conductive environment for the electrochemical cleaning reaction, enhance the overall performance of the laundry detergent, and ensure that its biodegradability, environmental friendliness, and cleaning effect reach a better level.

[0020] Furthermore, in step (3), the weight ratio of carboxymethyl-β-cyclodextrin, nano zinc oxide, and smart pH-responsive polymer is 6~9:4~12:0.01~0.09.

[0021] The beneficial effects of adopting the above-mentioned further solutions are as follows: Carboxymethyl-β-cyclodextrin in the multifunctional composite additive can fully utilize its structural characteristics to encapsulate odor molecules; nano-zinc oxide exerts antibacterial, anti-mite, and antistatic functions with an appropriate ratio; and the intelligent pH-responsive polymer effectively adjusts the pH value of the laundry detergent with precise dosage, optimizing cleaning performance to meet diverse user needs. The foam-free design not only makes rinsing convenient and efficient, reducing the risk of secondary contamination of clothes, but also saves water resources, fossil energy, and rinsing time. The synergistic effect of all raw materials ensures the stable performance of the foam-free electrochemical laundry detergent during storage and use.

[0022] Furthermore, the particle size of the mixture of carboxymethyl-β-cyclodextrin and nano zinc oxide after grinding is 30nm~50nm; the ultrasonic dispersion power is 200W~300W, and the time is 10min~15min.

[0023] The beneficial effects of adopting the above-mentioned further scheme are as follows: controlling the particle size of the mixture of ground carboxymethyl-β-cyclodextrin and nano zinc oxide to 30nm~50nm is beneficial to their uniform dispersion in the system, increasing the specific surface area, increasing the probability of contact with odor molecules, bacteria, etc., and enhancing cleaning, antibacterial and other functions; during ultrasonic dispersion, the power setting of 200W~300W and the ultrasonic time of 10min~15min can make the intelligent pH-responsive polymer uniformly dispersed in the mixture of carboxymethyl-β-cyclodextrin and nano zinc oxide, further strengthening the interaction between the components, improving the stability and overall performance of the multifunctional composite additive, thereby making the laundry detergent perform better in terms of cleaning, antibacterial, mite removal, antistatic and pH adjustment.

[0024] Furthermore, the intelligent pH-responsive polymer is a Danming-polyethylene glycol copolymer.

[0025] Furthermore, in step (4), the mass ratio of the special structure metal-organic framework catalytic particles, the 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid, and the multifunctional composite additive is 1:0.2~0.5:0.3~0.8. The amount of water added is 4.5 to 8.5 times the total mass of the special structure metal-organic framework catalytic particles, the 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid, and the multifunctional composite additive.

[0026] The beneficial effects of adopting the above-mentioned further solution are: the special structured metal-organic framework catalytic particles, the biodegradable ionic liquid electrolyte, and the multifunctional composite additive work together in the laundry detergent system to achieve optimal performance balance. This ensures that the special structured metal-organic framework catalytic particles effectively catalyze the generation of sufficient active oxygen species for efficient stain removal, while the biodegradable ionic liquid electrolyte provides a good conductive environment to support the electrochemical cleaning reaction. Simultaneously, the multifunctional composite additive fully utilizes its multiple functions, including cleaning, antibacterial, and antistatic properties.

[0027] Furthermore, the temperature after heating in step (4) is 80℃~120℃; the pressure of the reaction is 8MPa~15MPa, and the time is 8h~12h.

[0028] The beneficial effects of adopting the above-mentioned further approach are that the specific reaction pressure, reaction temperature, and reaction time create suitable conditions for the interaction between the components. Under this environment, the components can more fully integrate to form a stable and homogeneous system, thereby improving the stability of the laundry detergent.

[0029] The second objective of this invention is to provide a non-foaming electrochemical laundry detergent.

[0030] The beneficial effects of this invention are as follows: The laundry detergent of this invention is composed of a variety of raw materials such as zirconium oxychloride and terephthalic acid in specific weight proportions. It is made through unique process steps such as the preparation and mixing of special structured metal-organic framework catalytic particles, biodegradable ionic liquid electrolytes, and multifunctional composite additives. The laundry detergent prepared by this invention has advantages such as high-efficiency cleaning, environmental protection and safety, and multifunctional integration. It also achieves convenient rinsing with its foam-free design. The components work together to ensure stability. Its preparation process is scientific and rigorous, ensuring that the product has excellent performance and is stable and reliable, meeting the market demand for new types of laundry detergent. Attached Figure Description

[0031] Figure 1 This is a flowchart of the preparation process in Example 1 of the present invention. Detailed Implementation

[0032] The principles and features of this invention are described below. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they should be performed according to the techniques or conditions described in the literature in this field, or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0033] The reagents used in the examples were purchased from the following sources: Zirconium oxychloride (Maclean's reagent), terephthalic acid (Maclean's reagent), N,N-dimethylformamide (Aladdin's reagent), 1-methylimidazole (Aladdin's reagent), 2-bromopropionic acid (Aladdin's reagent), sodium L-lactic acid (Aladdin's reagent), carboxymethyl-β-cyclodextrin (Maclean's reagent), nano zinc oxide (Maclean's reagent), rhodamine-polyethylene glycol (PEG) copolymer (Shanghai Jixiang Biotechnology Co., Ltd.).

[0034] The N,N-dimethylformamide has a purity ≥99.5% and a water content <0.05%; the carboxymethyl-β-cyclodextrin has a carboxymethyl substitution degree of 1.5~2.5, a purity ≥98%, and an average particle size of 5μm~20μm.

[0035] Example 1: Preparation of non-foaming electrochemical laundry detergent The preparation steps in this embodiment are as follows: Figure 1 As shown, the details are as follows: (1) Preparation of special structure metal-organic framework catalytic particles: 3 kg zirconium oxychloride, 11.4 kg terephthalic acid and 8.1 kg N,N-dimethylformamide were placed in a reactor for reaction at a pressure of 8 MPa, a temperature of 125 °C and a time of 18 h to obtain Zr-MOFs crystals; Zr-MOFs crystals were carbonized at high temperature in nitrogen atmosphere at a heating rate of 7 °C / min, a temperature of 850 °C and a holding time of 2.5 h; the carbonized Zr-MOFs crystals were acid etched with 0.1 mol / L dilute hydrochloric acid solution at a temperature of 60 °C and a stirring etching time of 5 h, and then centrifuged, washed and dried under normal pressure convection (temperature of 70 °C and drying time of 3 h) to obtain special structure metal-organic framework catalytic particles; (2) Preparation of biodegradable ionic liquid electrolyte: 4.3 kg of 1-methylimidazolium and 3.6 kg of 2-bromopropionic acid were refluxed in 2.7 kg of 0.2 mol / L acetonitrile solution at 40 °C for 15 h to obtain the intermediate 1-methyl-3-(2-bromopropyl)imidazolium bromide; the intermediate 1-methyl-3-(2-bromopropyl)imidazolium bromide was reacted with 2.8 kg of L-lactic acid sodium in 1.2 kg of 0.1 mol / L ethanol solution, the solvent was removed by rotary evaporation for 10 h, and then purified by recrystallization to obtain 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid with a purity 1.5 times that of the solvent removed before recrystallization purification; (3) Preparation of multifunctional composite additive: 7 kg of carboxymethyl-β-cyclodextrin and 7 kg of nano zinc oxide were ground and sieved to obtain a mixture with a particle size of 35~40 nm; 0.047 kg of rhodamine-polyethylene glycol copolymer was added to the mixture and ultrasonically dispersed at a power of 200 W for 10 min to obtain the multifunctional composite additive. (4) Mixing preparation: In a reaction vessel (Anhui Kemi Instruments) equipped with a stirring device and a temperature control system, 195.5 kg of deionized water was added, followed by 23 kg of special structure metal-organic framework catalyst particles, 6.9 kg of biodegradable ionic liquid electrolyte, and 9.2 kg of multifunctional composite additive. The reaction pressure was set to 10 MPa, the reaction temperature to 90 °C, and the reaction time to 8 h. The mixture was continuously stirred to ensure that the components were evenly dispersed, thus obtaining a non-foaming electrochemical laundry detergent.

[0036] Examples 2-5: Preparation of non-foaming electrochemical laundry detergent Examples 2-5 are prepared using the same method as Example 1, except for the amount of each raw material added. All other steps and conditions are the same as in Example 1. The amounts of each raw material component are shown in Table 1. Table 1 (Unit: kg) Comparative Example 1: Preparation of Non-Fogging Electrochemical Laundry Detergent Comparative Example 1 was prepared using the same method as Example 1, except that the amount of N,N-dimethylformamide added in step (1) was different. All other raw materials, steps, and conditions were the same as in Example 1. Step (1) is as follows: (1) Preparation of special structure metal-organic framework catalytic particles: 3 kg zirconium oxychloride, 11.4 kg terephthalic acid and 1.5 kg N,N-dimethylformamide were placed in a reactor for reaction at a pressure of 8 MPa, a temperature of 125 °C and a time of 18 h to obtain Zr-MOFs crystals; Zr-MOFs crystals were placed in nitrogen for high-temperature carbonization at a heating rate of 7 °C / min, a temperature of 850 °C and a holding time of 2.5 h; the carbonized Zr-MOFs crystals were acid etched with 0.1 mol / L dilute hydrochloric acid solution at a temperature of 60 °C and a stirring etching time of 5 h, and then centrifuged, washed and dried under normal pressure (temperature of 70 °C and drying time of 3 h) to obtain special structure metal-organic framework catalytic particles.

[0037] Comparative Example 2: Preparation of Non-foaming Electrochemical Laundry Detergent Comparative Example 2 was prepared using the same method as Example 1, except that the carbonization temperature was different in step (1). All other raw materials, steps, and conditions were the same as in Example 1. Step (1) is as follows: (1) Preparation of special structure metal-organic framework catalytic particles: 3 kg zirconium oxychloride, 11.4 kg terephthalic acid and 8.1 kg N,N-dimethylformamide were placed in a reactor for reaction at a pressure of 8 MPa, a temperature of 125 °C and a time of 18 h to obtain Zr-MOFs crystals; Zr-MOFs crystals were placed in nitrogen for high-temperature carbonization at a heating rate of 7 °C / min, a temperature of 250 °C and a holding time of 2.5 h; the carbonized Zr-MOFs crystals were acid etched with 0.1 mol / L dilute hydrochloric acid solution at a temperature of 60 °C and a stirring etching time of 5 h, and then centrifuged, washed and dried under normal pressure (temperature of 70 °C and drying time of 3 h) to obtain special structure metal-organic framework catalytic particles.

[0038] Comparative Example 3: Preparation of Non-foaming Electrochemical Laundry Detergent Comparative Example 3 was prepared using the same method as Example 1, except that recrystallization was not performed in step (2). All other raw materials, steps, and conditions were the same as in Example 1. Step (2) is as follows: (2) Preparation of biodegradable ionic liquid electrolyte: 4.3 kg of 1-methylimidazolium and 3.6 kg of 2-bromopropionic acid were refluxed in 2.7 kg of 0.2 mol / L acetonitrile solution at 40 °C for 15 h to obtain the intermediate 1-methyl-3-(2-bromopropyl)imidazolium bromide; the intermediate 1-methyl-3-(2-bromopropyl)imidazolium bromide was reacted with 2.8 kg of L-lactic acid sodium in 1.2 kg of 0.1 mol / L ethanol solution, and the solvent was removed by rotary evaporation for 10 h to obtain 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid.

[0039] Comparative Example 4: Preparation of Non-Fogging Electrochemical Laundry Detergent Comparative Example 4 was prepared using the same method as Example 1, except that nano zinc oxide was not added in step (3). All other raw materials, steps, and conditions were the same as in Example 1. Step (3) is as follows: (3) Preparation of multifunctional composite additive: 7 kg of carboxymethyl-β-cyclodextrin was ground and sieved to a particle size of 35~40 nm. 0.047 kg of rhodamine-polyethylene glycol copolymer was added to the ground carboxymethyl-β-cyclodextrin and ultrasonically dispersed at a power of 200 W for 10 min to obtain the multifunctional composite additive.

[0040] Comparative Example 5: Preparation of Non-Fogging Electrochemical Laundry Detergent The only difference between this comparative example and Example 1 is that in step (4), the special structure metal-organic framework catalytic particles, biodegradable ionic liquid electrolyte, and multifunctional composite additives were not added in the corresponding proportions. All other raw materials and steps are the same as in Example 1. Step (4) is as follows: (4) Mixing preparation: In a reaction vessel equipped with a stirring device and a temperature control system, add 167.4 kg of deionized water, then add 17.3 kg of special structure metal-organic framework catalyst particles, 10.7 kg of biodegradable ionic liquid electrolyte and 4.2 kg of multifunctional composite additive in sequence. Set the reaction pressure to 10 MPa, the reaction temperature to 90 °C and the reaction time to 8 h. Stir continuously to ensure that the components are evenly dispersed to obtain non-foaming electrochemical laundry detergent.

[0041] Performance testing: The detergency of the non-foaming electrochemical laundry detergents prepared in Examples 1-5 and Comparative Examples 1-5 was tested, and the test methods and steps are as follows: (1) The experiment was divided into 10 groups, namely Examples 1-5 and Comparative Examples 1-5. The protein-stained cloth was cut into 6cm*6cm sizes. The number of pieces tested in each group was 3. The whiteness value before the test was recorded using a benchtop whiteness meter (Shanghai Xinrui WSB-3) (based on the center position of the soiled cloth). The average value was taken. The soiled cloth was immersed in 500ml of the solution of non-foaming electrochemical laundry detergent of Examples 1-5 diluted with water at a volume ratio of 1:100. The cloth was stirred with an electric mixer for 20min at a speed of about 200r / min. After stirring, the cloth was rinsed with 1.5L of tap water for 30s, repeated twice, and then manually dehydrated and air-dried. (2) After the protein-soaked cloth is dried, the whiteness value after testing is recorded using a benchtop whiteness meter (Shanghai Xinrui WSB-3) (based on the center position of the cloth), and the average value is taken. The difference between the average whiteness values ​​of the protein-soaked cloth before and after the test can be used to obtain the stain removal value, which is used to evaluate the stain removal power. The results are shown in Tables 2 and 3: Table 2 Table 3 From Tables 2 and 3, we can obtain: (1) The non-foaming electrochemical laundry detergents prepared in Examples 1-5 all had a detergency value of over 3.90 for protein-stained cloths. In contrast, only Comparative Examples 3 and 5 had a detergency value of over 2.00, while the rest were less than 2.00. Comparing Comparative Example 1 with Example 1, it can be seen that N,N-dimethylformamide plays an important role in the formation of special structure metal-organic framework catalytic particles. It is crucial to ensure the performance of the catalytic particles and thus improve the detergency of the non-foaming electrochemical laundry detergent. It directly affects the degree of reaction between zirconium oxychloride and terephthalic acid and the quality of Zr-MOF crystal formation. When the amount is insufficient, catalytic particles with ideal structure and performance cannot be formed, resulting in a reduction or decrease in the activity of active oxygen species generated under electrochemical action, ultimately leading to a decrease in the ability to decompose stubborn stains. (2) Comparison of Comparative Example 2 and Example 1 of the present invention shows that, in the process of preparing non-foaming electrochemical laundry detergent, changing the carbonization temperature of Zr-MOFs crystals is a key factor affecting the performance of special structure metal-organic framework catalytic particles. A suitable carbonization temperature helps to optimize the physicochemical properties of the material and enhance catalytic activity, thereby enabling the special structure metal-organic framework catalytic particles to efficiently generate active oxygen species under electrochemical action, thus improving the detergency of the laundry detergent. When the carbonization temperature is too low, the structure and properties of the material cannot be sufficiently changed, resulting in insufficient activity of the catalytic particles and poor stain removal effect; (3) Compared with Example 1, it can be seen that in Comparative Example 3, the ionic liquid is not recrystallized and purified, which will result in residual impurities in the ionic liquid, affecting the performance of its electrolyte in the laundry detergent system, failing to provide a good conductive environment for the electrochemical cleaning reaction, and ultimately causing the detergent's cleaning ability to decrease.

[0042] (4) In the non-foaming electrochemical laundry detergent prepared in Comparative Example 4, the absence of nano zinc oxide disrupted the synergistic effect between the components of the multifunctional composite additive, affecting the overall cleaning effect of the detergent and reducing its ability to decompose and remove stains. Furthermore, the lack of nano zinc oxide also weakened the detergent's antibacterial, mite-removing, and antistatic properties, failing to meet consumers' diverse needs for clothing cleaning.

[0043] (5) Comparison of Example 5 and Example 1 shows that the appropriate ratio between the special structure metal-organic framework catalytic particles, the biodegradable ionic liquid electrolyte, and the multifunctional composite additive is crucial for the performance of the laundry detergent. A suitable ratio ensures that the key components work together in the laundry detergent system to achieve the best performance balance. The special structure metal-organic framework catalytic particles can effectively catalyze the generation of sufficient active oxygen species to achieve efficient stain removal, the biodegradable ionic liquid electrolyte provides a good conductive environment to support the electrochemical cleaning reaction, and the multifunctional composite additive plays multiple functions such as cleaning, antibacterial, and antistatic. Once the ratio is unbalanced, the synergistic effect between the components is weakened, and they cannot fully perform their respective functions, thereby reducing the cleaning ability of the laundry detergent.

[0044] In summary, this invention provides a non-foaming electrochemical laundry detergent and its preparation method, aiming to address the shortcomings of traditional laundry detergents in terms of cleaning, environmental protection, and functionality. This laundry detergent is composed of various raw materials such as zirconium oxychloride and terephthalic acid in specific weight proportions. It is produced through unique process steps including the preparation and mixing of specially structured metal-organic framework catalytic particles, biodegradable ionic liquid electrolytes, and multifunctional composite additives. Comparative examples and comparative figures demonstrate that this laundry detergent possesses advantages such as high-efficiency cleaning, environmental safety, multifunctional integration, non-foaming and easy rinsing, and good stability. The preparation method ensures excellent and stable product performance, meeting market demand for novel laundry detergents.

[0045] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing a non-foaming electrochemical laundry detergent, characterized in that, Includes the following steps: (1) Zirconium oxychloride, terephthalic acid and N,N-dimethylformamide are mixed and reacted to obtain Zr-MOFs crystals; the Zr-MOFs crystals are placed in nitrogen gas for high-temperature carbonization, and acid etching is performed after carbonization to obtain metal-organic framework catalytic particles with special structure. (2) Mix 1-methylimidazolium with 2-bromopropionic acid to obtain mixture A, and reflux mixture A in acetonitrile solution to obtain an intermediate; mix the intermediate with sodium L-lactic acid to obtain mixture B, and react mixture B in ethanol solution, followed by rotary evaporation and recrystallization to obtain 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid; (3) Weigh carboxymethyl-β-cyclodextrin and nano zinc oxide, grind and sieve to obtain a mixture; add intelligent pH-responsive polymer to the mixture and perform ultrasonic dispersion to obtain a multifunctional composite additive; (4) The special structure metal-organic framework catalyst particles, the 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid, and the multifunctional composite additive are added sequentially to water, and the mixture is continuously stirred and heated to carry out the reaction, so as to obtain a non-foaming electrochemical laundry detergent.

2. The method for preparing a non-foaming electrochemical laundry detergent according to claim 1, characterized in that, The weight ratio of zirconium oxychloride, terephthalic acid, and N,N-dimethylformamide in step (1) is 3~7:7~14:8~21.

3. The method for preparing a non-foaming electrochemical laundry detergent according to claim 1, characterized in that, The pressure of the mixing reaction in step (1) is 5 MPa to 10 MPa, the temperature is 120℃ to 150℃, and the time is 12h to 20h. The heating rate for high-temperature carbonization is 5℃ / min~10℃ / min, the carbonization temperature is 800℃~1000℃, and the holding time is 2h~4h. The acid etching solution used is dilute hydrochloric acid with a concentration of 0.1 mol / L, a temperature of 60℃~80℃, and an etching time of 4h~6h.

4. The method for preparing a non-foaming electrochemical laundry detergent according to claim 1, characterized in that, In step (2), the weight ratio of 1-methylimidazole and 2-bromopropionic acid in mixture A is 3.2~5.8:2.8~6.3; and the weight ratio of intermediate and sodium L-lactic acid in mixture B is 5:0.6~2.

6.

5. The method for preparing a non-foaming electrochemical laundry detergent according to claim 1, characterized in that, The reflux reaction in step (2) is carried out at a temperature of 35℃~45℃ for 12h~24h; the rotary evaporation reaction time is 8h~12h.

6. The method for preparing a non-foaming electrochemical laundry detergent according to claim 5, characterized in that, In step (2), the concentration of the acetonitrile solution is 0.2 mol / L, and the mass ratio of the acetonitrile solution to the mixture A is 1:2~4; the concentration of the ethanol solution is 0.1 mol / L, and the mass ratio of the ethanol solution to the mixture B is 1:8~12.

7. The method for preparing a non-foaming electrochemical laundry detergent according to claim 1, characterized in that, The weight ratio of carboxymethyl-β-cyclodextrin, nano zinc oxide, and smart pH-responsive polymer in step (3) is 6~9:4~12:0.01~0.

09.

8. The method for preparing a non-foaming electrochemical laundry detergent according to claim 1, characterized in that, The mass ratio of the special structure metal-organic framework catalytic particles, the 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid, and the multifunctional composite additive in step (4) is 1:0.2~0.5:0.3~0.8; The amount of water added is 4.5 to 8.5 times the total mass of the special structure metal-organic framework catalytic particles, the 1-methyl-3-(2-amino-3-carboxypropyl)imidazolium lactate ionic liquid, and the multifunctional composite additive.

9. The method for preparing a non-foaming electrochemical laundry detergent according to claim 1, characterized in that, The temperature after heating in step (4) is 80℃~120℃; the pressure of the reaction is 8MPa~15MPa, and the time is 8h~12h.

10. A non-foaming electrochemical laundry detergent, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 9.

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