A METAL COMPLEX AND USE THEREOF

Abstract

Provided are new metal complexes having phenolic and macrocyclic amino ligands as well as to their use, in particular use for bleaching catalyst for detergent compositions and oxidative crosslinking catalyst for resins, containing said metal complexes. A formulation comprises at least a detergent, a metal complex, and optionally a source of hydrogen peroxide.

Claims

1. A metal complex, having the general formula (I):
M.sub.i(L.sub.1)(L.sub.2).sub.i   (I) wherein: M is a transition metal; i is an integer ranging from 1 to 10; L.sub.1 is a ligand having the general formula (II) or (III): ##STR00009## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, or R.sub.12, independently from each other, are selected from the group comprising: H, hydrocarbyl radical, halide, —OH, —NO.sub.2, —CN, —OR′, —O—CO—R′, —COR′, —CO—OR′, —NR′R″, —CONR′R″, —NR′—COR″R′″, —NR′—CO—NR″R′″, —SO.sub.3X, —SO.sub.4X, —COOX, and at least one of R.sub.1 to R.sub.4, or one of R.sub.5 to R.sub.12 is selected from the group consisting of: —CN, —OR′, —O—CO—R′, —COR′, —CO—OR′, —NR′R″, —CONR′R″, —NR′—COR″R′″, —NR′—CO—NR″R′″, —SO.sub.3X, —SO.sub.4X or —COOX; or five or six membered ring constituted with two or more groups of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and the skeleton of aromatic ring; or five or six membered ring constituted with two or more groups of R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, optionally a —OH group, and the skeleton of aromatic ring; R′, R″ and R′″, independently from each other, are H or hydrocarbyl radical; X is selected from the group comprising H, alkali metal cation, alkaline earth metal cation or ammonium; L.sub.2 is a ligand having the formula (IV): ##STR00010## wherein: R.sub.13 is a hydrocarbyl radical, and each of the R.sub.13 groups may be the same or different; n is an integer being 1, 2 or 3; m is an integer being from 2, 3, 4 or 5.

2. The metal complex according to claim 1 wherein R.sub.13 is a C.sub.1-C.sub.30-hydrocarbyl radical.

3. The metal complex according to claim 1 wherein R.sub.13 is a C.sub.1-C.sub.15-hydrocarbyl radical.

4. The metal complex according to claim 1, wherein R.sub.13 is straight-chain, branched or carries one or more substituents.

5. The metal complex according to claim 1, wherein the substructure L.sub.2 of the formula (IV) is chosen in the group constituted by triazacycloalkanes and tetraazacycloalkanes.

6. The metal complex according to claim 1, wherein the substructure L.sub.2 of the formula (IV) is chosen in the group constituted by: 1,3,5-trimethyl-1,3,5-triazacyclohexane; 1,3,5-trimethyl-1,3,5-triazepane; 1,3,5-trimethyl-1,3,5-triazocane; 1,3,5,7-tetramethyl-1,3,5-triazocane; 1,3,6-trimethyl-1,3,6-triazocane; 1,3,5-trimethyl-1,3,5-triazonane; 1,3,6-trimethyl-1,3,6-triazonane; 1,3,6,8-tetramethyl-1,3,6-triazonane; 1,4,7-trimethyl-1,4,7-triazacyclononane; 1,3,5-trimethyl-1,3,5-triazecane; 1,3,6-trimethyl-1,3,6-triazecane; 1,3,7-trimethyl-1,3,7-triazecane; 1,3,5,7-tetramethyl-1,3,7-triazecane; 1,3,5,7,9-pentamethyl-1,3,7-triazecane; 1,3,5,7-tetramethyl-1,3,5-triazecane; 1,4,7-trimethyl-1,4,7-triazecane; 1,4,7,9-tetramethyl-1,4,7-triazecane; 1,4,7-trimethyl-1,4,7-triazacycloundecane; 1,4,8-trimethyl-1,4, 8-triazacycloundecane; 1,4,6,8-tetramethyl-1,4,8-triazacycloundecane; 1,4,7-trimethyl-1,4,7-triazacyclododecane; 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane; 1,4,7,10-tetramethyl-1,4,7-triazacyclododecane; 1,4,8-trimethyl-1,4,8-triazacyclododecane; 1,5,9-trimethyl-1,5,9-triazacyclododecan; 1,3,5,9-tetramethyl-1,5,9-triazacyclododecane; and 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane preferably 1,4,7-trimethyl-1,4,7-triazacyclononane.

7. The metal complex according to claim 1, wherein the metal complex is prepared by mixing metal compound, ligand L.sub.1 and ligand L.sub.2 with molar ratio of t:1:t, wherein t is ranging from the number of 1 to 10.

8. The metal complex according to claim 1, wherein the transition metal atom is selected from the group comprising V, Mn, Fe, Co, Ni and Cu.

9. A composition comprising at least: (1) a metal complex according to claim 1, (2) a source of hydrogen peroxide.

10. The composition according to claim 9, wherein the source of hydrogen peroxide is selected from the group consisting of: alkali metal peroxides, organic peroxides, inorganic persalts, and their precurors.

11. The composition according to claim 9, wherein the composition comprises from 1 to 50% by weight of the source of hydrogen peroxide, with respect to the total weight of the composition.

12. The composition according to claim 9, wherein the composition further comprises water.

13. The composition according to claim 9, wherein the composition further comprises a detergent.

14. The composition according to claim 9, wherein the composition comprises from 0.00001 to 1.0% by weight of the metal complex, with respect to the total weight of the composition.

15. A formulation comprising at least a detergent, a metal complex of formula (I) according to claim 1, and optionally a source of hydrogen peroxide.

16. The formulation according to claim 15, wherein said formulation comprises from 0.0001 to 0.1 by weight of the metal complex of formula (I) with respect to the total weight of the formulation.

17. An extemporaneous composition comprising at least: a first composition comprising at least a detergent and a metal complex of formula (I) according to claim 1, notably in a solid form, and a second composition comprising at least a source of hydrogen peroxide, separate from the first composition; the second composition being capable of being mixed with the first composition.

18. A method for treating a substrate, the method comprising treating the substrate with the metal complex of formula (I) according to claim 1.

19. A method for treating a substrate, the method comprising treating the substrate with the composition according to claim 9.

20. The method according to claim 18, wherein the substrate is fabric.

21. A method for treating a substrate, the method comprising applying to the substrate, in an aqueous medium, a composition comprising at least the metal complex of formula (I) according to claim 1.

22. A method of treating tableware comprising treating tableware with a metal complex of formula (I) according to claim 1.

23. A method of treating tableware comprising treating tableware with the composition according to claim 9.

24. A method for washing tableware, comprising treating a stained tableware with the composition according to claim 9.

25. The method according to claim 24, wherein the tableware is treated in an automatic dishwasher.

26. A method for treating a substrate, comprising at least: a) having available a composition comprising at least a detergent and a metal complex of formula (I), b) having available a source of hydrogen peroxides, separate from the composition a) c) bringing the composition a) extemporaneously into contact with the source of hydrogen peroxide, and d) bringing the mixture of c) into contact with the substrate.

27. A resin composition comprising at least: (a) a metal complex according to claim 1; (b) a resin.

28. A method of curing a resin, the method comprising curing the resin with the metal complex according to claim 1.

Description

EXPERIMENTAL PART

[0179] The disclosure will now be illustrated with working examples, which is intended to illustrate the working of disclosure and not intended to take restrictively to imply any limitations on the scope of the present disclosure. Other examples are also possible which are within the scope of the present disclosure.

Reference Products:

[0180] Tetraacetylethylenediamine (TAED): CAS 10543-57-4 [0181] 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN): CAS 96556-05-7 [0182] Sodium 2,3-dihydroxynaphthalene-6-sulfonate: CAS 135-53-5 [0183] Caffeic acid: CAS 331-39-5 [0184] Ellagic acid: CAS 476-66-4 [0185] 2,5-Dihydroxy-1,4-benzoquinone (DHBQ): CAS 615-94-1 [0186] 1,8-Dimethyl-1,4,8,11-tetraazacyclotetradecane: CAS 214078-92-9 [0187] Manganese(II) chloride tetrahydrate: CAS 13446-34-9Di[manganese (1+)], [0188] bis(octahydro-1,4,7-trimethyl-1H-1,4,7-triazonine kN.sup.1, kN.sup.4, kN.sup.7)-tri-μ-oxo-, bis[ethanoate (1-)](Dragon complex): CAS 916075-10-0 [0189] Sodium percarbonate: CAS 15630-89-4 [0190] Trisodium citrate hexahydrate: CAS 6858-44-2 [0191] Sodium carbonate: CAS 497-19-8 [0192] Sodium slicate: CAS 6834-92-0 [0193] Sodium sulfate: CAS 7757-82-6

Example 1 Preparation of Complex 1

[0194] ##STR00005##

[0195] In a schlenk reaction flask, MnCl.sub.2.4H.sub.2O (395 mg) was added inside and protected by N.sub.2 atmosphere. 100 ml Methanol was injected inside via syringe. Then TMTACN (342 mg) was injected and stirred at room temperature. In a separate beaker, the sodium 2,3-dihydroxynaphthalene-6-sulfonate (524 mg) was dissolved in 20 ml Methanol and NaOH (80 mg) was added and stirred for 2 mins. The solution was injected via syringe in the flask and the final mixture was stirred for 4 h at 40° C. The precipitate was obtained by filtration and can be recrystallized in ethanol if necessary. The complex formation was confirmed by LC-MS (m/z=464.1086).

Example 2 Preparation of Complex 2

[0196] ##STR00006##

[0197] According to the same procedure of example 1, with caffeic acid (360.3 mg) to replace sodium 2,3-dihydroxynaphthalene-6-sulfonate (524 mg) and 120 mg NaOH instead of 80 mg. The complex was confirmed by LC-MS (m/z+H)=405.1486.

Example 3 Preparation of Complex 3

[0198] ##STR00007##

[0199] According to the same procedure of example 1, with ellagic acid (302.2 mg) to replace sodium 2,3-dihydroxynaphthalene-6-sulfonate (524 mg) and 160 mg NaOH instead of 80 mg. The complex was confirmed by LC-MS (m/z=750.1990 and 375.0991).

Example 4 Preparation of Complex 4 (Diethyl-cyclam)Mn(DHBQ)(PF.SUB.6.) (Comparison Example)

[0200] ##STR00008##

[0201] According to the procedure described in U.S. Pat. No. 9,102,903B2, the complex was obtained as gray powder.

Example 5 the Laundry Bleaching Performance

[0202] Into a beaker with 1 L hard water (250 mg Ca/L) at 40° C., standard detergent GB/T 13174-2008 (2.0 g) was added and the mixture was stirred for 3 mins, at a temperature of 40° C. The complex 1 (5 mg) and sodium percarbonate (800 mg) were added, consecutively, at a temperature of 40° C. Finally, the stained fabric was added and stirred for 30 mins (200 rpm) at a temperature of 40° C. After the bleaching, the bleached fabric pieces were washed with tap water for three times at ambient temperature, squeezed and dried naturally.

[0203] The bleaching performance was evaluated by CIELAB Color i7 spectrophotometer. Color difference (ΔE) before and after bleaching is calculated with:

[00001]$\Delta E=\sqrt{{\left(\text{?}-\text{?}\right)}^2+{\left(a_{\mathrm{bleached}}-a_{\mathrm{original}}\right)}^2+{\left(b_{\mathrm{bleached}}-b_{\mathrm{original}}\right)}^2}$$\text{?}\text{indicates text missing or illegible when filed}$

[0204] Results with tea stained fabric and catalysts/activators are expressed in Table 1.

TABLE-US-00001 TABLE 1 ΔE (C-H028) Bleaching agents (Tea stained) Detergent (2.0 g) 25.7 TAED (400 mg) Sodium percarbonate (800 mg) Detergent (2.0 g) 11.5 Detergent (2.0 g) 19.6 Sodium percarbonate (800 mg) Detergent (2.0 g) 24.9 TMTACN (5 mg) Sodium percarbonate (800 mg) Detergent (2.0 g) 27.9 Complex 1(5 mg) Sodium percarbonate (800 mg) Detergent (2.0 g) 26.1 Complex 2 (5 mg)Sodium percarbonate (800 mg) Detergent (2.0 g) 29.2 Complex 3 (5 mg)Sodium percarbonate (800 mg) Detergent (2.0 g) 27.3 Dragon complex (5 mg)Sodium percarbonate (800 mg) Detergent (2.0 g) 20.7 Complex 4 (comparison example) (5 mg)Sodium percarbonate (800 mg)

[0205] Tea stained fabric reference: CFT B.V C-H028 standard material Tea—Circular Stain Ø=5 cm on Woven Cotton.

[0206] It appears the composition permits to obtain better bleaching properties on fabrics while using a significant lower amount metal complex (5 mg) of the invention in comparison with TAED (400 mg) known as a reference on the market and even better than the dragon complex of super high price with the drawback of fabric damage.

Example 6 the Laundry Bleaching Performance

[0207] Into a beaker with 1 L hard water (250 mg Ca/L) at 40° C., optionally 2.0 g of standard detergent GB/T 13174-2008 was added and the mixture was stirred for 3 mins, at a temperature of 40° C. The complex 3 (5 mg) and sodium percarbonate (800 mg) were added, consecutively, at a temperature of 40° C. Finally, the stained fabric was added and stirred for 30 mins (200 rpm) at a temperature of 40° C. After the bleaching, the bleached fabric pieces were washed with tap water for three times at ambient temperature, squeezed and dried naturally.

[0208] Results with tea stained fabrics and complex 3 are expressed in Table 2.

TABLE-US-00002 TABLE 2 ΔE Formulations (Tea stained) Water only 2 Water and detergent 11.5 Water, sodium percarbonate and no detergent 14.3 Water, complex 3, sodium percarbonate and no detergent 23.8

[0209] It appears the composition of the invention permits to obtain higher bleaching properties on fabrics without detergent in comparison with the bleaching agent alone.

Example 7 the Auto Dishwashing Bleaching Performance

[0210] The dish washing procedure follows the IKW test method (reference: Nitsch, Ch, and G. Huttmann. SOFW JOURNAL 128.5 (2002): 23-29.).

The Homemade Tea Cups Preparation Procedure:

[0211] Mix 2 litres of synthetic water and bring it to the boil. Pour boiling water on 30 g of tea in an open container and leave it to brew for 5 minutes. Then pour the tea through a strainer into another temperature-controlled vessel.

[0212] The clean cups are filled with 100 ml of tea such that the temperature of the tea in the cups is 85° C. The initial temperature of the poured tea is about 93° C. Remove 20 ml of tea every 5 minutes with a pipette until all the cups are empty (5 times). This process is then repeated once more with freshly brewed tea.

[0213] The components of the auto dishwashing (hereinafter ADW) formulation are presented in Table 3, and firstly the components in solid state (Trisodium citrate hexahydrate, sodium carbonate, sodium silicate, Mirapol® Surf-S Pfree Powder, sodium percarbonate, sodium sulfate) were mixed sufficiently and put into the ADW machine washing product chamber. Then the components in liquid form (Antarox LF54 and Rhodoline 111) were weighed into the rince aid chamber in ADW machine.

TABLE-US-00003 TABLE 3 Component g Trisodium citrate hexahydrate (Sinopharm.) 30 Sodium carbonate (Sigma-Aldrich) 20 Sodium silicate (Sigma-Aldrich) 10 Mirapol ® Surf-S Pfree Powder (Solvay) 1 Sodium percarbonate (Alfa-Aesaer) 8 Rhodoline 111 (Solvay) 8 Antarox LF54 (Solvay) 3 Sodium sulfate (Sigma-Aldrich) 10

[0214] The ballast soil preparation was described in Nitsch, Ch, and G. Huttmann. SOFW JOURNAL 128.5 (2002): 23-29. The composition is in Table 4.

TABLE-US-00004 TABLE 4 Constituents Raw material wt. % Fat Vegetable oil (e.g. Aro, Metro) 31.6 Margarine (e.g. Homann, 6.3 Allgäu-Margarine) Lard (e.g. Laru, Lagensiepen, &Ruckebier) 6.3 Deep-frying fat (e.g. 6.3 Aro, Metro, semi-liquid) Protein Whole egg (e.g. Wiesenhof) 15.8 Cream (e.g. Debic, UHT, cream, 32% fat)) 9.4 Whole milk, pasteurized, 3.5% fat 6.3 Other powdered Potato starch (e.g. 2.2 solid Superior LXJ 72, Emsland) Gravy (e.g. Knorr) 1.7 Wheat flour (e.g. Diamant-Mehl, type 405) 0.6 Quark powder (e.g. Dr. Otto Suwelack, 0.6 Billerbeck) Benzoic acid > 99.9% (chemical supplier) 0.3 Other Tomato ketchup (e.g. Kühne) 6.3 Mustard (e.g. Löwensenf“Extrascharf”) 6.3

[0215] In the auto dishwasher (Siemens SK23E210TI), 9 g homemade ADW formulation powder and 10 mg Mn complex were added in the detergent container, the tea stained tea cups and 50 g frozen ballast soil in small bottle were put inside the dishwasher. The Eco-50° C. program was chosen.

[0216] After the prewash (20 mins), the detergent container was opened automatically and After 15 mins period, the bleached tea cup was rinsed and dried naturally for visually evaluation (mark 0-10 indicated no performance to excellent performance).

[0217] The Table 5 gave the ADW performance for different catalysts/activators for two different bleaching periods.

TABLE-US-00005 TABLE 5 Composition Performance after 15 mins bleaching Homemade Formulation 9 g 5 TAED 0.5 g Homemade Formulation 9 g 8 Dragon complex 10 mg Homemade Formulation 9 g 8 Complex 1 10 mg Homemade Formulation 9 g 5 TMTACN 10 mg Homemade Formulation 9 g 7 Complex 2 10 mg Homemade Formulation 9 g 9 Complex 3 10 mg Homemade Formulation 9 g 5 Complex 4 10 mg Homemade Formulation 9 g 3

Example 8 the Auto Dishwashing Bleaching Performance

[0218] Instead of Homemade ADW formulation in Example 7, the ‘Finish® Quantum’ tablet without catalyst (‘Finish® Quantum’ Base, ˜11 g) has also been used as base formulation to evaluate the auto dishwashing performance of different complexes.

[0219] The procedure is the same in Example 7 and the results are presented in Table 6.

TABLE-US-00006 TABLE 6 Composition Performance after 15 mins bleaching ‘Finish ® Quantum’ Base 7 TAED 0.5 g ‘Finish ® Quantum’ Base 9 Dragon complex 10 mg ‘Finish ® Quantum’ Base 9 Complex 1 10 mg ‘Finish ® Quantum’ Base 7 TMTACN 10 mg ‘Finish ® Quantum’ Base 8 Complex 2 10 mg ‘Finish ® Quantum’ Base 10 Complex 3 10 mg ‘Finish ® Quantum’ Base 6 Complex 4 10 mg ‘Finish ® Quantum’ Base 5

[0220] Obviously, the complexes prepared increased significantly the bleaching performance of homemade ADW formulation and showed better performance than TAED, and for complex 3, even better performance obtained than dragon complex.

Example 9 the Curing Performance

[0221] The performance of coating comprising manganese complexes as the oxidative crosslinking catalyst was evaluated based on the waterborne alkyd paints purchased from ‘Chengyang Waterborne’.

[0222] Under mechanic stirring, 10 mg corresponding additive was added into 100 g alkyd paints and stirred for 10 mins at 500 rpm. Then a 30 μm thickness film was applied on the glass surface and the drying time was recorded on the BYK drying time recorder BYK 2710.

[0223] The results were shown in Table 7.

TABLE-US-00007 TABLE 7 Additive Drying time No additional catalyst 12 h Complex 1 8 h Complex 2 8 h Complex 3 6 h

[0224] It can be seen that the oxidative crosslinking catalyst shows excellent performances in comparison with the paint without the oxidative crosslinking catalyst and increase the curing much faster.