Use of highly stable bimetallic complexes in the field of domestic washing, bleaching and disinfection

Abstract

This invention provides an application of a bimetallic complex as an oxidation catalyst in the field of household detergents. It features bimetallic multi-coordination, excellent oxidation catalytic effect, no biotoxicity, and good biodegradability. It also exhibits good storage stability, demonstrating better stability than catalysts used in disclosed detergents, bleaching agents, and disinfectants under a preferred pH environment. It remains stable in detergent, disinfectant, and bleaching products during both storage and the washing process. This invention meets the current market demand for detergent and bleaching catalysts and has promising commercial prospects.

Description

Technical Field

[0001] This invention belongs to the field of detergent technology, specifically relating to the application of a highly efficient and stable bimetallic complex in household washing, bleaching and disinfection, and the washing, disinfecting or bleaching agents made therefrom. Background Technology

[0003] In the history of household cleaning, it was discovered early on that bleaching agents such as hydrogen peroxide could be used to remove stains from clothing and tableware, including those from tea, coffee, wine, fruit, and curry. Because hydrogen peroxide is highly unstable when exposed to heat or other chemicals, Henkel first used sodium perborate in its detergents in 1907. Sodium perborate releases hydrogen peroxide during washing to achieve a bleaching effect, a practice that continued until the 1990s. Later, due to concerns about the ecotoxicity of perborate, sodium percarbonate replaced sodium perborate as a more environmentally friendly source of hydrogen peroxide.

[0004] Peroxyacids are a more potent bleaching agent than hydrogen peroxide, but like hydrogen peroxide, they suffer from instability. A bleaching activator was discovered that possesses a corresponding acylation group, forming peroxyacids with hydrogen peroxide during washing, which proved more effective than using hydrogen peroxide alone. The first bleaching activator was patented in 1927, using fatty acids, such as octanoic acid, to generate organic peracids to aid bleaching. Subsequently, a series of aliphatic carboxylic amides (RCONR'R'') were patented for improving bleaching at temperatures below 100°C. However, bleaching activators must be relatively inexpensive, biodegradable, and compliant with regulations to be successfully commercialized. Currently, only tetraacetylethylenediamine (TAED) and sodium nonanoyloxybenzenesulfonate (SNOBS) are commercially available in Europe and the United States.

[0005]

[0006] Each mole of SNOBS releases one mole of peroxyacid, compared to two moles of TAED, making SNOBS less volumetric efficient. Currently, most formulations sold in the UK and EU use a sodium percarbonate / TAED bleaching combination.

[0007] However, the bleaching performance of the sodium percarbonate / TAED combination decreases significantly at temperatures below 50°C, which conflicts with consumers' desire for low-temperature, high-efficiency bleaching. To address these shortcomings, various bleaching catalysts have been developed and reported, becoming a favorable means to reduce washing temperature and bleach dosage.

[0008] Studies have shown that transition metals such as Mn, Fe, Cu, and Cr all have the ability to improve the bleaching performance of hydrogen peroxide.

[0009] For example, Unilever's patent EP0082563B1 reported the potential of using MnSO4 as a catalyst. It showed that adding manganese salts in the presence of carbonate ions can improve bleaching performance at 40°C. However, standalone transition metal salts still present many problems. They have low thermodynamic stability under alkaline conditions and readily decompose rapidly into high-valence Mn(IV) oxides or Fe(III) oxides. These oxides interact with H2O2 in alkaline solutions, causing them to decompose into oxygen and water molecules or potentially generate hydroxyl radicals and other reactive oxygen species. Hydroxyl radicals are highly reactive and non-selective, leading to excessive aging of dyes and fabrics. In laundry applications, metal oxides may adhere to fabrics, causing damage.

[0010] Therefore, a great deal of research has been conducted on improving stability by using organic ligands to complex with transition metals such as manganese.

[0011] EP 0458397 B1 reports that Unilever has obtained a patent for using Mn-TMTACN as a catalyst in its bleaching system, making it the first commercially available bleaching catalyst.

[0012]

[0013] Mn-TMTACN H.D. Busch and colleagues at Procter & Gamble synthesized and studied a manganese and iron complex (WO9839098) with cross-bridged tetraaza and pentaaza macrocyclic ligands.

[0014] Siba Corporation has published two patents (WO2002088289) concerning manganese complexes and various tripyridine ligands in stain bleaching applications, which indicate that these complexes can activate hydrogen peroxide and enhance the bleaching effect on tea stains.

[0015]

[0016] Henkel claims (WO9730144) that the application of manganese complexes containing TPA ligands can achieve improved stain bleaching results.

[0017]

[0018] Other examples include Unilever's WO2002 / 072747, which reports an iron complex with a pentadentate nitrogen-based ligand.

[0019]

[0020] WO9719162 and EP86917 also reported a class of manganese Schiff base complexes.

[0021]

[0022] Although there have been numerous research reports on bleaching catalysts in the past, only a very few, such as Mn-TMTACN, have been commercialized.

[0023] However, Mn-TMTACN was eventually removed from the laundry market due to unacceptable fabric damage issues. Although it is still used as a bleaching catalyst in automatic dishwashers, the stability of its formulation storage and the problem of easily precipitated black manganese dioxide particles remain unsatisfactory.

[0024] In recent years, people have continued to search for more ideal bleaching catalysts and stabilizers.

[0025] Several papers, such as Qin Xinbo's "Synthesis of Macrocyclic Triamine-Mimetic Metal Complexes and Their Application in Low-Temperature Bleaching of Cotton Fabrics with Hydrogen Peroxide" from Donghua University in 2012, Zhu Hongjie's "Preparation and Mechanism Study of Low-Temperature Oxygen-Containing Bleaching Catalysts in Fabric Washing" from East China University of Science and Technology in 2020 (funded by Solvay), and Naomi Markham's "Development of Heterogeneous Catalysts for Bleaching in Automatic Dishwashing" (funded by Reckitt Benckiser), have evaluated different types of catalysts.

[0026] These research papers extensively studied the bleaching mechanism, establishing evaluation systems such as mulberry pigment oxidation and soiled cloth washing. Based on these systems, they conducted comparative evaluations of the bleaching performance of a series of new compounds. However, they ultimately did not obtain a better answer, and the problem of Mn-based catalyst precipitation remained unresolved. Summary of the Invention

[0027] To address the aforementioned problems, this invention provides a bimetallic complex catalyst for use in detergents, disinfectants, bleach, and other cleaning products. The complex, formed by preparing a ligand from o-vanillin and a diamine or polyamine, and further coordinating it with a metal compound, not only exhibits excellent catalytic performance but also significantly improves the stability of the catalyst in detergents and similar products by increasing the affinity between the metal ions and the ligand, as well as by enhancing the stability of the second coordinating metal. This meets practical needs and thus completes the invention.

[0028] The purpose of this invention is to provide the application of the following bimetallic complex in the field of household detergents: LMQX j Y k (Equation 1) Where M is manganese, iron, cobalt, or aluminum; Q is lithium, sodium, or potassium; X and Y are each independently selected from ligands, bridging groups, or corresponding anions; j and k are independent integers from 1 to 6; L is a ligand. The structural diagram is as follows: (Equation 2).

[0029] The bimetallic complex is an oxidation reaction catalyst.

[0030] This invention provides a method for preparing the aforementioned bimetallic complex, and compares and tests the oxidation catalytic activity of one or more of the complexes in different systems, examining the stability differences between the monometallic complexes and bimetallic complexes prepared from the ligands. Compared with the currently mainstream catalyst Mn-TMTACN, the preferred bimetallic complex catalyst exhibits good storage stability and, under a preferred pH environment, shows better stability than catalysts used in disclosed detergents, bleaching agents, and disinfectants.

[0031] Another object of the present invention is to provide a composition, which is a detergent, disinfectant or bleach, comprising the following components: The bimetallic complex described herein is in the range of 0.001 to 90 parts by weight. 0.001 to 99 parts by weight of detergent building agent, 1 to 99 parts by weight of adhesive, 0 to 40 parts by weight of encapsulating material, Other additives, in parts by weight, from 0 to 40.

[0032] The composition is a complete detergent, bleach, or a single bleaching additive containing peroxide, which is used separately as an adjunct to a non-bleaching detergent for removing colored stains from textiles or tableware.

[0033] The present invention has the following beneficial effects: (1) The bimetallic complex designed in this invention has a reasonable synthesis route, is easy to implement and control, has mild preparation conditions, is easy to synthesize, and has a high yield. The obtained bimetallic complex has outstanding bleaching catalytic effect, is non-biotoxic, and can be applied to a variety of products such as detergents, disinfectants, and bleaching agents, meeting the current market demand for washing and bleaching catalysts and having good commercial development prospects.

[0034] (2) This invention features a rational design that utilizes o-vanillin to synthesize Schiff bases, which are then chelated with two metals sequentially, significantly increasing the number of teeth in the complex and thus significantly reducing its precipitation in detergents, disinfectants, and bleaching agents. It exhibits good storage stability and, under preferred pH conditions, demonstrates better stability compared to catalysts used in disclosed detergents, bleaching agents, and disinfectants. This invention is of great significance in washing and other similar products. Attached Figure Description

[0035] Figure 1 The graph shows the carbon dioxide release curves of the L-Fe / Na bimetallic complex catalyst and the conventional catalyst Mn-TMTACN in Experimental Example 5 of the present invention. Figure 2 The diagram shows the biodegradation rate curves of the L-Fe / Na bimetallic complex and the conventional catalyst Mn-TMTACN in Experimental Example 5 of the present invention. Detailed Implementation

[0036] The present invention will now be described in detail through specific embodiments, which will more clearly and explicitly demonstrate the features and advantages of the present invention.

[0037] This invention provides the application of the following bimetallic complex in the field of household detergents: LMQX j Y k (Equation 1) Wherein: M is manganese, iron, cobalt, or aluminum; preferably, M is manganese or iron. Preferably, the oxidation state of metal M is II, III, IV, or VI.

[0038] Q is lithium, sodium, or potassium; preferably, Q is sodium or potassium.

[0039] X is a coordinating group, bridging group, or corresponding anion; preferably, X is RCOO. - Cl - H2O, O2 2- O 2- R is hydrogen or a substituted or unsubstituted C1-C8 alkyl or aryl group; more preferably, X is CH3COO - .

[0040] Y is a coordinating group, bridging group, or corresponding anion; preferably, Y is RCOO. - ClO4 - PF6 - , RSO4 - SO4 2- Cl - NO3 - R is hydrogen or a substituted or unsubstituted C1-C8 alkyl or aryl group; more preferably, Y is CH3COO- Cl - or PF6 - .

[0041] j and k are independent integers from 1 to 6; preferably, j and k are independent integers from 1 to 3. L is a ligand. The structural diagram is as follows: (Equation 2) -Z- can be -C(CH3)2-, -CH(CH3)-, -CH(OH)-, -CH(COOH)-, -CH(CH2COOH)-, -CH2CH2-, -CH(CH3)CH(CH3)-, -CH=CH-, -CH2NHCH2, -CH2N(CH3)CH2-, -CH2N(CH2COOH)CH2-, preferably -C(CH3)2-, -CH2NHCH2 or -CH2N(CH3)CH2-.

[0042] The bimetallic complex of formula (1) is an oxidation reaction catalyst.

[0043] The bimetallic complex of formula (1) is used as an oxidation reaction catalyst to prepare detergents, disinfectants or bleach.

[0044] Preferably, the bimetallic complex is: , , , .

[0045] This invention provides a method for preparing the aforementioned bimetallic complex. First, o-vanillin and a diamine or polyamine are refluxed in a solvent such as toluene / dichloroethane, and the resulting water is separated to obtain different Schiff base ligands in high yield. Subsequently, the ligands are complexed sequentially with organometallic salts in polar solvents such as methanol / tetrahydrofuran to obtain the target bimetallic compound. Different separation and purification methods can be used during the process depending on the specific circumstances.

[0046] This invention demonstrates that several typical metal complexes exhibit significant effects in common bleaching catalytic capacity tests (mulberry pigment oxidation, soiled cloth washing).

[0047] This invention demonstrates that a ligand-prepared bimetallic complex exhibits better stability and is less prone to precipitation in alkaline aqueous solutions compared to monometallic complexes. The bimetallic compound was compared with the currently mainstream catalyst Mn-TMTACN after prolonged standing in different sodium carbonate and sodium percarbonate aqueous solutions within a pH range of 5–12. The results also show that the preferred bimetallic complex solution is more difficult to precipitate in an environment of pH 9.5–10.5.

[0048] The bimetallic complex catalyst also showed better performance in thermal storage experiments compared with the currently mainstream catalyst Mn-TMTACN mixed with common detergent formulations.

[0049] This invention provides a composition, which is a detergent, disinfectant, or bleach, comprising the following components: The bimetallic complex is present in amounts ranging from 0.001 to 90 parts by weight, preferably 0.05-45 parts by weight, more preferably 0.08-2 parts by weight. 0.001 to 99 parts by weight of the building block substance, preferably 20-99 parts by weight, more preferably 30-99 parts by weight. The adhesive comprises 1 to 99 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight. The encapsulating material comprises 0 to 40 parts by weight, preferably 2 to 35 parts by weight, and more preferably 5 to 40 parts by weight. Other additives, in parts of weight, from 0 to 40, preferably 0.01 to 25, more preferably 0.1 to 10.

[0050] In one embodiment of the present invention, the raw materials of the composition include citrate, polyacrylate, silicate, percarbonate, carbonate, tetraacetylethylenediamine, dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, and the bimetallic complex; preferably, they include sodium citrate, sodium polyacrylate, sodium silicate nonahydrate, sodium percarbonate, sodium carbonate, tetraacetylethylenediamine (TAED), sodium dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, and the bimetallic complex.

[0051] The citrate is present in parts by weight of 35-55, preferably 40-50, and more preferably 45. The polyacrylate is 4-12 parts by weight, preferably 6-10 parts, and more preferably 8 parts; The silicate comprises 16-24 parts by weight, preferably 18-22 parts, and more preferably 20 parts by weight; The percarbonate is 2-8 parts by weight, preferably 4-6 parts, and more preferably 5 parts; The carbonate is 1-5 parts by weight, preferably 2-4 parts, and more preferably 3 parts; The tetraacetylethylenediamine is present in 1-5 parts by weight, preferably 2-4 parts, and more preferably 3 parts; The dodecylbenzene sulfonate is present in an amount of 0.1-0.7 parts by weight, preferably 0.3-0.5 parts, and more preferably 0.4 parts; The fatty alcohol polyoxyethylene ether is 11-19 parts by weight, preferably 13-17 parts, and more preferably 15 parts; The bimetallic complex is present in an amount of 0.06-0.5 parts by weight, preferably 0.08-0.3 parts, and more preferably 0.1 parts. Example

[0052] Those skilled in the art will understand that the embodiments described are merely illustrative of the invention and should not be construed as limiting the invention.

[0053] Example 1: Synthesis of N,N'-bis(3-methoxysalicylaldehyde)bis(2,2-dimethylpropylamine-1,3-diamine) (hereinafter referred to as L1) (L1) 74 g (0.486 mol) of o-vanillin and 100 g of toluene were added to a reaction flask and stirred until dissolved. Then, a mixed solution of 24.7 g (0.242 mol) of 2,2-dimethyl-1,3-propanediamine and 25 g of toluene was added dropwise at 20-25 °C. The mixture was then heated to 84 °C under reflux, and the resulting water was collected using a water separator. After reacting for 3 hours, the solvent was removed by rotary evaporation. A small amount of methyl tert-butyl ether was dispersed by slurrying, filtered, and dried to obtain 85 g of a yellow solid of N,N'-bis(3-methoxysalicylic acid acetal)bis(2,2-dimethylpropylamine-1,3-diamine), with a molar yield of 94.8%.

[0054] ¹H NMR (500 MHz, chloroform-d): δ 14.12 (s, 2H), 8.29 (d, J = 1.4 Hz, 2H), 6.89 (dd, J = 7.8, 1.6 Hz, 2H), 6.85 (dd, J = 7.9, 1.5 Hz, 2H), 6.77 (t, J = 7.8 Hz, 2H), 3.88 (s, 6H), 3.46 (d, J = 1.2 Hz, 4H), 1.04 (s, 6H). ¹³C NMR (126 MHz, CDCl₃): δ 165.80, 152.05, 148.47, 122.92, 118.40, 117.90, 113.81. 67.31, 56.03, 36.17, 24.25.

[0055] Example 2 N1,N3-bis(3-methoxysalicylaldehyde)N-methyl-2,2-diaminodiethylamine (hereinafter abbreviated as L2) (L2) 4.69 g (0.04 mol) of o-vanillin and 100 g of dichloroethane were added to a reaction flask and stirred until dissolved. Then, 0.1 g of acetic acid was added. A mixed solution of 12.18 g (0.08 mol) of N-methyl-2,2-diaminodiethylamine and 20 g of dichloroethane was added dropwise at 20-25 °C. After reacting at 20-35 °C for 1 hour, the mixture was heated to 84 °C and refluxed. The resulting water was collected using a water separator. The reaction was stopped after 5 hours. After removing the solvent using a rotary evaporator, 15.5 g of a yellow oily liquid was obtained. This liquid was dispersed using n-hexane, filtered, and dried to obtain 14.8 g of yellow needle-like crystals of N1,N3-bis(3-methoxysalicylic acid acetal)N-methyl-2,2-diaminodiethylamine. The molar yield was 96%.

[0056] ¹H NMR (400 MHz, Chloroform-d) δ 13.98 (s, 2H), 8.26 (d, J = 1.2 Hz, 2H), 6.88 (dd, J = 7.2, 2.3 Hz, 2H), 6.79 – 6.65 (m, 4H), 3.89 (s, 6H), 3.70 – 3.58 (m, 4H), 2.78 (t, J = 6.2 Hz, 4H), 2.37 (s, 3H).

[0057] Example 3 Synthesis of N1,N3-bis(3-methoxysalicylaldehyde)diethylenetriamine (hereinafter abbreviated as L3) (L3) 50 g (0.329 mol) of o-vanillin and 115 g of dichloroethane were added to a reaction flask and stirred until dissolved. Then, a mixed solution of 16.5 g (0.16 mol) of diethylenetriamine and 20 g of dichloroethane was added dropwise at 20-30 °C. The mixture was heated to 84 °C and refluxed, and the resulting water was collected using a water separator. The reaction was stopped after 4 hours. The solvent was evaporated to obtain 64 g of crude product, which was dispersed in 50% ethanol solution, filtered, and dried to obtain 56.4 g of a yellow solid of N1,N3-bis(3-methoxysalicylic acid acetal)diethylenetriamine. Molar yield: 95%.

[0058] ¹H NMR (400 MHz, Chloroform-d) δ 13.79 (s, 2H), 8.34 (s, 2H), 6.89 (dd, J = 7.8, 1.6 Hz, 2H), 6.83 (dd, J = 7.9, 1.6 Hz, 2H), 6.76 (t, J = 7.8 Hz, 2H), 3.90 (s, 6H), 3.73 (d, J = 10.6 Hz, 3H), 3.03 (s, 4H).

[0059] Example 4 Preparation of the bimetallic complex L1-Fe / Na-AcOH (L1-Fe / Na-AcOH) 74 g (0.20 mol) of the prepared ligand L1 was added to 500 g of tetrahydrofuran and stirred until dissolved. Then, 34.8 g (0.20 mol) of ferrous acetate was added, and the reaction was carried out at 20-30 °C for 22 h. After filtering to remove insoluble matter, 16.4 g (0.2 mol) of sodium acetate was added, and the reaction was continued at 20-30 °C for 16 h. After the reaction was completed, most of the solvent was removed by rotary evaporation, and 250 g of methyl tert-butyl ether was added. After stirring for 0.5 h, the mixture was filtered to obtain 101.7 g of a purplish-black powder, with a molar yield of 90%.

[0060] Example 5 Preparation of the monometallic complex L2-Mn-AcOH (L2-Mn-AcOH) 7.7 g (0.02 mol) of the prepared ligand L2 was added to 30 g of anhydrous methanol and stirred until completely dissolved. Then, 5.36 g (0.02 mol) of manganese(III) acetate hydrate was added, and the mixture was stirred at room temperature for 2 h. The temperature was then raised to 64 °C and refluxed for 3 h. Subsequently, the temperature was lowered to 20-25 °C, and the mixture was filtered to obtain 10.2 g of brown solid powder. The molar yield was 92%.

[0061] Example 6 Preparation of the bimetallic complex L2-Mn / Na-AcOH (L2-Mn / Na-AcOH) 5.6 g (0.01 mol) of the prepared L2-Mn-AcOH was added to 20 g of anhydrous methanol, stirred and dispersed, and then heated to 64 °C. 4 g of sodium acetate aqueous solution (containing 0.85 g / 0.01 mol sodium acetate) was slowly added dropwise, and the reaction was continued under reflux for 5 h. The temperature was then lowered to 20-25 °C, filtered, and dried to obtain 5.8 g of a brown solid powder. The molar yield was 90%.

[0062] Example 7 Preparation of the bimetallic complex L2-Mn / K-AcOH / PF6 (L2-Mn / K-AcOH / PF6) 7.7 g (0.02 mol) of the prepared ligand L2 was added to 30 g of anhydrous methanol and stirred until completely dissolved. Then, 5.36 g (0.02 mol) of manganese(III) acetate hydrate was added, and the mixture was stirred at room temperature for 2 h. The temperature was then raised to 64 °C and refluxed for 3 h. Subsequently, 3.68 g (0.02 mol) of potassium hexafluorophosphate was added, and the mixture was refluxed at 64 °C for another 10 h. The temperature was then lowered to 20-25 °C, filtered, and dried to obtain 10.2 g of a brown solid powder. The molar yield was 92%.

[0063] Example 8: Bimetallic Complex L3-Mn / Na-AcOH (L3-Mn / Na-AcOH) 3.7 g (0.01 mol) of the prepared ligand L3 was added to 30 g of anhydrous methanol and stirred until completely dissolved. Then, 2.68 g (0.01 mol) of manganese(III) acetate hydrate was added, and the mixture was stirred at room temperature for 2 h. The temperature was then raised to 64 °C and refluxed for 3 h. Subsequently, 0.9 g (0.011 mol) of sodium acetate was added, and the mixture was refluxed for another 5 h. The temperature was then lowered to 20-25 °C, filtered, and dried to obtain 5.7 g of a brown solid powder. The molar yield was 91%.

[0064] Application Experiment Example: Application Experiment Example 1: An experiment was conducted to oxidize morin, investigating the catalytic oxidation effect of the bimetallic complex L1-Fe / Na-AcOH. The solution was prepared with 0.1 mmol of morin (2',3,4',5,7-pentahydroxyflavone), 0.5 g of sodium carbonate, and 100 mg of tetraacetylethylenediamine per liter of water, at a pH of 10.5 and a temperature of 50°C. After adding a selective bleaching catalyst and sodium percarbonate, the concentration change of morin was measured to compare the catalytic oxidation effects of L1-Fe / Na-AcOH (abbreviated as EAT, prepared in Example 4) and Mn-TMTACN (abbreviated as CAT, provided by Fujian Bonuo Anke Pharmaceutical Technology Co., Ltd.). The concentrations and amounts of sodium carbonate and bleaching catalyst are shown in Table 1, where C0 represents the initial concentration of morin and C represents the real-time concentration.

[0065] Table 1

[0066] As can be seen from the concentration change data in Table 1, sodium percarbonate can significantly oxidize and degrade morin. Both L1-Fe / Na-AcOH (EAT) and Mn-TMTACN (CAT) can significantly increase the oxidation rate of sodium percarbonate, and the catalytic ability of L1-Fe / Na-AcOH (EAT) is relatively higher than that of Mn-TMTACN (CAT).

[0067] Application Experiment Example 2: A standard soiled cloth washing control experiment was conducted to investigate the bleaching catalytic effect of the bimetallic complex L2-Mn / Na-AcOH (prepared in Example 6). Add 1L of hard water (200 ppm Ca) to a 1L beaker, add a 50mm magnetic stir bar and start stirring. Maintain the temperature at 40°C, then add 1g of sodium carbonate, 1g of sodium percarbonate, the appropriate amount of TAED or catalyst, and four standard CFT tea-stained cloths (5 cm x 5 cm). Stir at 200 rpm for half an hour. Then remove the bleached cloths, rinse them three times with clean water, and let them air dry. Evaluate the results.

[0068] Preparation method for 250ppm hard water: Weigh 20.37g MgCl2:6H2O and 16.7g CaCl2, dissolve them in deionized water and dilute to 5L. When using, take 40ml and dilute to 1L to obtain 200ppm hard water.

[0069] The washing results of different combinations of catalysts L2-Mn / Na-AcOH, Mn-TMTACN, and TAED are shown in Table 2.

[0070] Table 2

[0071] The increase in ΔE shows that the L2-Mn / Na-AcOH bleaching catalyst prepared with the novel ligand has a good catalytic bleaching effect, comparable to the Mn-TMTACN bleaching catalyst currently on the market.

[0072] Application Experiment Example 3 Referring to Application Example 2, the amount of sodium carbonate / sodium percarbonate was adjusted to 0.5g. Everything else remained the same.

[0073] The comparative washing effects of catalysts L3-Mn / Na-AcOH and Mn-TMTACN were investigated, and the results are shown in Table 3.

[0074] Table 3

[0075] The increase in ΔE shows that the L3-Mn / Na-AcOH bleaching catalyst still exhibits good catalytic bleaching effect under different washing environments.

[0076] Application Experiment Example 4 Comparison of precipitation of different Mn complex aqueous solutions under different pH conditions Dissolve 192 mg L2-Mn / Na-AcOH, 119.5 mg Mn-TMTACN, and 116.7 mg disodium manganese ethylenediaminetetraacetate (EDTA-Mn) in 100 g of water, filter, and prepare a solution with a Mn concentration of 3 mmol / L for later use.

[0077] Dissolve 20g of sodium carbonate in 100g of water, filter, and prepare a 20% sodium carbonate aqueous solution for later use.

[0078] Three complex solutions with different manganese concentrations were mixed with different sodium carbonate solutions, and the precipitation of the complexes under different pH conditions was investigated. The results are shown in Table 4.

[0079] Table 4

[0080] The data in the table show that the bimetallic complex L2-Mn / Na-AcOH is relatively stable with the other two manganese complexes, Mn-TMTACN and EDTA-Mn, at pH 5-6. Under strongly alkaline conditions (pH 11-12), all three metal complexes precipitate rapidly. However, at pH 9.5-10.5, L2-Mn / Na-AcOH exhibits better stability than the other two metal complexes.

[0081] Application Experiment Example 5 Comparison of precipitation of different manganese complexes in the presence of washing oxidant Dissolve 192 mg L2-Mn / Na-AcOH, 167 mg L2-Mn-AcOH, and 119.5 mg Mn-TMTACN in water, filter, and prepare a solution with a Mn concentration of 3 mmol / L for later use.

[0082] Dissolve 10g of sodium percarbonate in 100g of water, filter, and prepare a 20% sodium carbonate aqueous solution for later use.

[0083] Three different manganese complex solutions were mixed with different sodium percarbonate solutions, and the precipitation was observed. The results are shown in Table 5. Table 5

[0084] pH 9-10 is the most commonly used range for washing. The data in the table shows that the stability of the commonly used manganese catalyst Mn-TMTACN and the single-manganese complex with ligand L2 at this pH is not as good as that of the Mn / Na bimetallic complex with ligand L2.

[0085] Application Experiment Example 6: Stability of combination detergents The mixture is prepared by mixing sodium citrate, sodium polyacrylate, sodium silicate nonahydrate, sodium percarbonate, sodium carbonate, TAED, sodium dodecylbenzenesulfonate, and fatty alcohol polyoxyethylene ether (AEO3) in weights of 45 parts, 8 parts, 20 parts, 5 parts, 3 parts, 3 parts, 0.4 parts, and 15 parts, respectively.

[0086] The mixture obtained above was mixed with 0.1 parts of bleaching catalyst Mn-TMTACN (provided by Fujian Bonuo Anke Pharmaceutical Technology Co., Ltd.) and L2-Mn / Na-AcOH bimetallic complex (prepared in Example 6), and then mixed with a small amount of water and pulverized by a pulverizer to form small particles.

[0087] The prepared solid particles were grouped and placed in a constant temperature and humidity chamber, stored at 50℃ and 50% humidity, and observed weekly. The results are shown in Table 6.

[0088] Table 6

[0089] As shown in the table above, neither group of particles showed any changes after 4 weeks of storage at 40℃. Mn-TMTACN stored at 50℃ developed black spots after 2 weeks, while L2-Mn / Na-AcOH showed no signs of black spot formation. This indicates that the detergent particle composition prepared with L2-Mn / Na-AcOH exhibits stronger stability.

[0090] Application Experiment Example 7 The biodegradation percentage of the L1-Fe / Na-AcOH bimetallic complex catalyst (EAT) prepared in Example 4 and the conventional catalyst Mn-TMTACN (CAT) was determined by a third-party testing organization according to the standard composting degradation test (45 days) method.

[0091] The average biodegradation rate test results based on the released carbon dioxide are shown in Table 7. The carbon dioxide release curve and biodegradation rate curve are shown in Table 7. Figure 1 As shown in the table below: Table 7

[0092] As can be seen, both the novel L1-Fe / Na-AcOH bimetallic complex and the traditional catalyst Mn-TMTACN can achieve complete degradation.

[0093] Application Experiment Example 8 Acute oral toxicity tests and determinations were conducted on the L-Fe / Na bimetallic complex catalyst prepared in Example 2 in accordance with EC REGULATION NO 440 / 2008 Annex B.1 tris Acute Oral Toxicity – Acute Toxicity Staging Method (May 31, 2008) and the United Nations Recommendation on the Transport of Dangerous Goods – Model Regulations (23rd) (Volume I). SD rats were used in the tests. The experimental animals were fasted overnight before gavage. Three animals (female) were used for each dose group, with doses of 300 mg / kg, 300 mg / kg, 2000 mg / kg, and 2000 mg / kg body weight, respectively. Based on the test results, the acute oral toxicity LD50 value of the test sample was >2000 mg / kg (rat), indicating that the sample is not an oral toxicant.

[0094] Acute dermal toxicity tests were conducted on the L-Fe / Na bimetallic complex catalyst prepared in Example 2 in accordance with EC REGULATION NO 440 / 2008 Annex B.3 Acute toxicity (dermal) (May 31, 2008) and the United Nations Recommendation on the Transport of Dangerous Goods - Model Regulations (23rd) (Volume I). Twenty-four hours prior to the test, the hair on the test sites of the experimental animals was shaved, ensuring that at least 10% of the body surface area was exposed to the toxic substance. Ten animals (half male and half female) were exposed at a dose of 2000 mg / kg bw for 24 hours. No animal deaths or signs of poisoning were observed during the test. Based on the test results, under the current test conditions, the acute dermal toxicity LD50 of the test sample was [not specified]. 50 Value >2000 mg / kg (rabbit).

[0095] Acute inhalation toxicity tests were conducted on the L-Fe / Na bimetallic complex catalyst prepared in Example 2 in accordance with EC REGULATION NO 440 / 2008 Annex B.2 Acute Toxicity (Inhalation) (March 18, 2014) and the United Nations Recommendation on the Transport of Dangerous Goods - Model Regulation (23rd) (Volume I). SD rats were used in the test, with dynamic inhalation exposure. Before the test, the experimental animals were placed in a fixed device and placed in an oral-nasal exposure tower. Ten animals (half male and half female) were exposed to a test dose concentration of 5.1217 mg / L for 4 hours. Based on the test results, under the current test conditions, the LC50 of the rat dynamic acute inhalation toxicity of the test sample was... 50 Value > 5.1217 mg / L (4h), i.e., LC50 50Value >20.4868 mg / L (1h) (rat, animal). This sample is not classified as an inhalation toxicant.

[0096] The present invention has been described in detail above with reference to specific embodiments and / or exemplary examples, as well as the accompanying drawings. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. Application of the following bimetallic complexes in the field of household detergents: LMQX j Y k (Equation 1) in: M is manganese, iron, cobalt, or aluminum; Q is lithium, sodium, or potassium; X and Y are each independently selected from ligands, bridging groups, or corresponding anions; j and k are independent integers from 1 to 6; L is a ligand. The structural diagram is as follows: (Equation 2).

2. According to claim 1, the bimetallic complex is an oxidation reaction catalyst.

3. According to the use of claim 1, X is RCOO. - Cl - H2O, O2 2- O 2- R is hydrogen or a substituted or unsubstituted C1-C8 alkyl or aryl group; Y is RCOO - ClO4 - PF6 - , RSO4 - SO4 2- Cl - NO3 - R is hydrogen or a substituted or unsubstituted C1-C8 alkyl or aryl group; Among them, -Z- is -C(CH3)2-, -CH(CH3)-, -CH(OH)-, -CH(COOH)-, -CH(CH2COOH)-, -CH2CH2-, -CH(CH3)CH(CH3)-, -CH=CH-, -CH2NHCH2, -CH2N(CH3)CH2-, -CH2N(CH2COOH)CH2-; The oxidation state of metal M is II, III, IV or VI.

4. As claimed in claim 1, in particular j and k are each independent integers from 1 to 3.

5. The use according to claim 1, wherein M is manganese or iron, and Q is sodium or potassium.

6. The use according to claim 3, wherein X is specifically CH3COO - .

7. The use according to claim 3, particularly Y being CH3COO - Cl - or PF6 - .

8. In the use of claim 3, the particular -Z- is -C(CH3)2-, -CH2NHCH2 or -CH2N(CH3)CH2-.

9. The use according to any one of claims 1 to 8, wherein the bimetallic complex of formula (1) is used to prepare detergents, disinfectants or bleach.

10. A composition, which is a detergent, disinfectant or bleach, comprising the following components: a) Bimetallic complexes of the following formula in the range of 0.001 to 90 parts by weight. LMQX j Y k (Equation 1) Where M is manganese, iron, cobalt, or aluminum; Q is lithium, sodium, or potassium; X and Y are each independently selected from ligands, bridging groups, or corresponding anions; j and k are independent integers from 1 to 6; L is a ligand. The structural diagram is as follows: (Equation 2) -Z- is -C(CH3)2-, -CH(CH3)-, -CH(OH)-, -CH(COOH)-, -CH(CH2COOH)-, -CH2CH2-, -CH(CH3)CH(CH3)-, -CH=CH-, -CH2NHCH2, -CH2N(CH3)CH2-, -CH2N(CH2COOH)CH2-, b) 0.001 to 99 parts by weight of a building block agent, c) 1 to 99 parts by weight of adhesive, d) 0 to 40 parts by weight of encapsulating material, e) 0 to 40 parts by weight of other additives.

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