Reactive magenta dye, preparation method and application thereof

Abstract

This application relates to the field of reactive dye technology and discloses a reactive magenta dye, a preparation method, and its application. A reactive magenta dye having the general structural formula of Formula 1 or Formula 2, wherein Formula 1 is #imgabs0, Formula 2 is #imgabs1, R1 is selected from -H, -CH3, -SO3M, or -OH; R2 is a halogen element; and M is selected from Na, K, or Li. This application utilizes a specific 6-amino-2,3-dichloroquinoxaline as an active group. This group is very stable when combined with hydroxyl groups on fibers, replacing conventional vinylsulfone active groups. Compared to conventional reactive dyes, this dye exhibits superior dyeing performance. Furthermore, it can be used in combination with cyanuric chloride as a dual-active group dye, effectively improving color fixation and color fastness.

Description

Technical Field

[0001] The present application relates to the technical field of reactive dyes, and in particular to a reactive magenta dye, a preparation method and applications thereof. Background Art

[0002] Reactive dyes, also known as reactive dyes, contain active groups that react with hydroxyl groups in cellulose and amino groups in protein fibers. During dyeing, they form covalent bonds with the fibers, creating "dye-fiber" compounds. Reactive dyes offer bright colors, excellent levelness, simple dyeing methods, high color fastness, a comprehensive color spectrum, and low cost. They are primarily used for dyeing and printing fibers such as cotton, linen, viscose, silk, and wool, as well as their blends.

[0003] However, most reactive dyes currently used in China are based on cyanuric chloride and para-esters or para-ester derivatives as active groups. This results in low fixation rates, poor performance, and suboptimal dyeing performance. To improve dyeing performance, finding new, more active and stable reactive groups is an effective approach. Summary of the Invention

[0004] In order to solve at least one of the above technical problems and develop a dye that effectively improves dyeing performance, the present application provides a reactive magenta dye, a preparation method and an application thereof.

[0005] In one aspect, the present application provides a reactive magenta dye, wherein the general structural formula of the reactive magenta dye is Formula 1 or Formula 2;

[0006] Wherein, formula 1 is Formula 2 is R1 is selected from -H, -CH3, -SO3M or -OH; R2 is a halogen element; M is selected from Na, K or Li.

[0007] By adopting the above technical solution, the present application adopts a specific 6-amino-2,3-dichloroquinoxaline as the active group. Because the two chlorine atoms in the molecular structure are very active and very stable after combining with the hydroxyl groups on the fiber, after replacing the conventional vinylsulfone active group, the dyeing performance is superior to that of ordinary reactive dyes. At the same time, it can be used together with cyanuric chloride as a double-active group dye to effectively improve the color fixation rate and color fastness.

[0008] Optionally, the R1 is selected from -H and / or -SO3M; the R2 is selected from -Cl; and the M is selected from Na.

[0009] Optionally, the structure of the reactive magenta dye is Formula 3, Formula 4, Formula 5, Formula 6 or Formula 7;

[0010] Among them, formula 3 is Formula 4 is

[0011] Formula 5 is Formula 6 is Formula 7 is

[0012] By adopting the above technical solution, the present application adopts the structural formula of a specific sexual magenta dye, and the dyeing effect is more excellent.

[0013] In a second aspect, the present application provides a method for preparing a reactive magenta dye, wherein the method for preparing the reactive magenta dye having a structure of Formula 3 or Formula 6 comprises the following steps:

[0014] Step 1: Take 1-amino 8-naphthol-3, 6-disulfonic acid monosodium salt After adding water to dissolve, continue to add sodium bicarbonate to obtain the dissolved product

[0015] Step 2: After beating cyanuric chloride with an ice-water mixture, the dissolved product is added to the beated cyanuric chloride, and the temperature is controlled at 5-10° C. to obtain a condensed product. The reaction formula is as follows:

[0016]

[0017] Step 3: Take sulfonated Tobias acid or m-aminobenzenesulfonic acid, add ice and beat into a pulp, add hydrochloric acid and mix, cool to 0-10°C, and then add sodium nitrite to obtain a diazonium salt. The reaction formula is as follows:

[0018]

[0019] Step 4: Add the diazonium salt to the condensed product, add sodium bicarbonate to adjust the pH to 6.5-7.0, and control the temperature to 5-10° C. to obtain a coupled product. The reaction formula is as follows:

[0020]

[0021] Step 5: Add 6-amino-2,3-dichloroquinoxaline to the coupling product, then add water to expand the body, control the temperature to 40-50 ° C and the pH value to 6-6.5, to obtain the formula 3 or formula 6, the reaction formula is as follows:

[0022]

[0023] By adopting the above technical solution, the preparation method of Formula 3 or Formula 6 of the present application is simple to operate, can be industrialized for production, and the prepared reactive magenta dye has excellent comprehensive properties.

[0024] Optionally, in step 1, the mass ratio of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt to water is 1:(5-7); the molar ratio of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt to sodium bicarbonate is 1:(1-2).

[0025] Optionally, in step 2, the molar ratio of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt to cyanuric chloride is 1:(0.9-1.1); and the mass ratio of cyanuric chloride to ice-water mixture is 1:(5-7).

[0026] Optionally, in step three, the molar ratio of sulfonated Tobias acid or m-aminobenzenesulfonic acid, hydrochloric acid and sodium nitrite is 1:(0.8-1.2):(0.9-1.1).

[0027] Optionally, in step 4, the molar ratio of the diazonium salt to the condensation product is (1-1.2):1.

[0028] Optionally, in the step 5, the molar ratio of the coupling product to 6-amino-2,3-dichloroquinoxaline is 1:(1.1-1.3).

[0029] In a third aspect, the present application provides an application of a reactive magenta dye in the field of cotton fibers and textiles thereof, wherein the concentration (owf) of the reactive dye is 0.5-10%.

[0030] By adopting the above technical solution, the reactive magenta dye prepared in the present application can be well combined with cotton fabrics and textiles thereof, and can effectively improve the color fixation rate and color fastness.

[0031] In summary, the present invention includes at least one of the following beneficial technical effects:

[0032] 1. This application uses a specific 6-amino-2,3-dichloroquinoxaline as the active group. Because the two chlorine atoms in the molecular structure are very active, they are very stable after binding to the hydroxyl groups on the fiber. Compared with ordinary reactive dyes, the dyeing performance is superior. At the same time, it can be used together with cyanuric chloride as a dual-active group dye to effectively improve the color fixation rate and color fastness.

[0033] 2. The preparation method of the reactive magenta dye of the present application is simple to operate, can be industrialized for production, and the prepared reactive magenta dye has excellent comprehensive properties;

[0034] 3. The reactive magenta dye prepared in this application can be well combined with cotton fabrics and textiles thereof, and can effectively improve the color fixation rate and color fastness. DETAILED DESCRIPTION

[0035] The present application is further described in detail below with reference to the embodiments. Specific embodiments

[0037] The raw material models of this application are as follows. Unless otherwise specified, the raw materials of this application are all commercially available: 1-amino-8-naphthol-3, 6-disulfonic acid monosodium salt: chemical formula is Purity 97%,

[0038] Sodium bicarbonate: purity 99%;

[0039] Hydrochloric acid: volume concentration is 30-36%;

[0040] Cyanuric chloride: chemical formula is Purity 99%;

[0041] Sulfonated Tobias acid: The chemical formula is Purity 99%;

[0042] Sodium nitrite: purity 99%;

[0043] 6-amino-2,3-dichloroquinoxaline: The chemical formula is Purity 98%;

[0044] m-Aminobenzenesulfonic acid: The chemical formula is Purity ≥98%;

[0045] Para-ester: Brand, Alpha, purity 98%.

[0046] Test items and methods:

[0047] UV-visible absorption spectrum test:

[0048] The dyes prepared in the examples were prepared into solutions at a concentration of 1 gram per 500 ml of water, and ultraviolet absorption spectra were scanned in the 200-800 nm band using an ultraviolet-visible spectrophotometer at room temperature. The dye solutions of the examples were prepared into aqueous solutions with a concentration of 1 ml per 100 ml, and the visible absorption spectrum curves of the individual dyes were measured, and the absorption peak values ​​and molar extinction coefficients of the spectra were recorded.

[0049] Color fastness test:

[0050] According to the national standards, color fastness to rubbing GB / T 3920-2008 and color fastness to washing GB / T 3921-2008, the color fastness of dyed cotton fabric samples was measured;

[0051] The reactive dye of the embodiment was dyed according to the following formula: cotton fabric: 5g, sodium sulfate concentration: 20g / L, bath ratio: 1:20, soda ash adjusted pH = 8.0, dye concentration: 2% (owf); dyeing was carried out by 60°C heating dyeing method, and a cloth sample was obtained after this post-treatment.

[0052] Dyeing experiment of cotton fabric with reactive dyes:

[0053] The reactive dyes of Example 2 were dyed with 5g of cotton fabric, 20g / L of sodium sulfate, a bath ratio of 1:20, and a pH of 8.0 adjusted with soda ash. The dye concentration was 2% (owf). The dyeing was performed using a 60°C temperature-elevated dyeing method. After post-treatment, a fabric sample was obtained. Using Example 2 as the standard sample, the dyeing intensity and color were recorded.

[0054] Color fixation rate test:

[0055] The reactive dye solution in the embodiment was prepared by adding 5 g of cotton fabric, 20 g / L of sodium sulfate, a bath ratio of 1:20, adjusting the pH to 8.0 with soda ash, and dye concentration of 0.5-10% (owf); dyeing was performed by a 60° C. heating dyeing method, and then the color fixation rate was determined.

[0056] Examples 1-6

[0057] Example 1

[0058] A method for preparing a reactive magenta dye having a structure of Formula 3 comprises the following steps:

[0059] Step 1: Take 0.1 mol of 1-amino 8-naphthol-3, 6-disulfonic acid monosodium salt After adding 171g of water to dissolve, continue to add 8.4g of sodium bicarbonate to obtain a dissolved product

[0060] Step 2: Take 0.09 mol of cyanuric chloride After beating with 83g of ice-water mixture, the dissolved product was added dropwise to the beated cyanuric chloride, the temperature was controlled at 5°C, and the reaction was carried out for 3h to obtain a condensed product. The reaction formula is as follows:

[0061] Step 3: Take 0.1 mol of sulfonated Tobias acid After adding 100g of ice to make a slurry, add 0.08mol of hydrochloric acid and mix with stirring. After cooling to 0℃, add 0.09mol of sodium nitrite and react for 2h to obtain diazonium salt. The reaction formula is as follows:

[0062] Step 4: Add 0.1 mol of diazonium salt to 0.1 mol of the monocondensed product, add sodium bicarbonate to adjust the pH to 6.5, control the temperature to 5°C, and react for 3 hours to obtain the coupled product. The reaction formula is as follows:

[0063]

[0064] Step 5: Add 0.11 mol of 6-amino-2,3-dichloroquinoxaline to 0.1 mol of the coupling product Then add 200g of water to expand the body, control the temperature to 40℃ and pH to 6, and react for 6h to obtain Formula 3. The reaction formula is as follows:

[0065] Example 2

[0066] A method for preparing a reactive magenta dye having a structure of Formula 3 comprises the following steps:

[0067] Step 1: Take 0.1 mol of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt and dissolve it in 200 g of water, then add 12 g of sodium bicarbonate to obtain a dissolved product;

[0068] Step 2: Take 0.11 mol of cyanuric chloride and beat it with 120 g of ice-water mixture, then add the dissolved product dropwise to the beaten cyanuric chloride, control the temperature to 8°C, and react for 3 hours to obtain a condensed product;

[0069] Step 3: Take 0.1 mol of sulfonated Tobias' acid and add 100 g of ice to slurry, then add 0.1 mol of hydrochloric acid and mix well. After cooling to 3°C, add 0.1 mol of sodium nitrite and react for 2 h to obtain the diazonium salt.

[0070] Step 4: Add 0.11 mol of diazonium salt to 0.1 mol of the condensed product, add sodium bicarbonate to adjust the pH to 6.8, control the temperature to 8°C, and react for 3 h to obtain the coupled product;

[0071] Step 5: Add 0.12 mol of 6-amino-2,3-dichloroquinoxaline to 0.1 mol of the coupled product, and then add 200 g of water for expansion. Control the temperature to 45 ° C and the pH value to 6.2, and react for 6 h to obtain the formula

[0072] Example 3

[0073] A method for preparing a reactive magenta dye having a structure of Formula 3 comprises the following steps:

[0074] Step 1: Take 0.1 mol of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt and dissolve it in 240 g of water, then add 16.8 g of sodium bicarbonate to obtain a dissolved product;

[0075] Step 2: Take 0.1 mol of cyanuric chloride and beat it with 129 g of ice-water mixture, then add the dissolved product dropwise to the beaten cyanuric chloride, control the temperature at 10°C, and react for 3 hours to obtain a condensed product;

[0076] Step 3: Take 0.1 mol of sulfonated Tobias acid and add 100 g of ice to slurry, then add 0.12 mol of hydrochloric acid and mix well. After cooling to 10°C, add 0.11 mol of sodium nitrite and react for 2 hours to obtain the diazonium salt;

[0077] Step 4: Add 0.12 mol of diazonium salt to 0.1 mol of the condensed product, add sodium bicarbonate to adjust the pH to 6.5-7.0, control the temperature to 10°C, and react for 3 hours to obtain the coupled product;

[0078] Step 5: Add 0.13 mol of 6-amino-2,3-dichloroquinoxaline to 0.1 mol of the coupled product, and then add 200 g of water for expansion. Control the temperature to 50 ° C and the pH value to 6.5, and react for 6 h to obtain the formula

[0079] Example 4

[0080] A method for preparing a reactive magenta dye having a structure of Formula 6 comprises the following steps:

[0081] S1: Take 0.1 mol of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt After adding 240g of water to dissolve, continue to add 16.8g of sodium bicarbonate to obtain a dissolved product

[0082] S2: Take 0.1 mol of cyanuric chloride After beating with 83g of ice-water mixture, the dissolved product was added dropwise to the beated cyanuric chloride, the temperature was controlled at 10°C, and the reaction was carried out for 3h to obtain a condensed product. The reaction formula is as follows:

[0083] S3: Take 0.1 mol of m-aminobenzenesulfonic acid After adding 120g of ice to make a slurry, add 0.12mol of hydrochloric acid and mix with stirring. After cooling to 10°C, add 0.11mol of sodium nitrite and react for 2h to obtain diazonium salt. The reaction formula is as follows:

[0084]

[0085] S4: Add 0.1 mol of diazonium salt to 0.1 mol of the monocondensed product, add sodium bicarbonate to adjust the pH to 6.5-7.0, control the temperature to 10°C, and react for 3 h to obtain the coupled product. The reaction formula is as follows:

[0086]

[0087] S5: Add 0.13 mol of 6-amino-2,3-dichloroquinoxaline to 0.1 mol of the coupling product Then 200 g of water was added to expand the body, the temperature was controlled at 50 ° C and the pH value was 6.5, and the reaction was carried out for 6 hours to obtain Formula 6, which is as follows:

[0088] Example 5

[0089] A method for preparing a reactive magenta dye having a structure of Formula 6 comprises the following steps:

[0090] S1: 0.1 mol of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt was added to 200 g of water and dissolved, followed by adding 12 g of sodium bicarbonate to obtain a dissolved product;

[0091] S2: 0.11 mol of cyanuric chloride was slurried with 120 g of ice-water mixture, and the dissolved product was added dropwise to the slurried cyanuric chloride. The temperature was controlled at 8°C and the reaction was carried out for 3 h to obtain a condensed product.

[0092] S3: 0.1 mol of sulfonated Tobias' acid was added to 100 g of ice and slurried, followed by the addition of 0.1 mol of hydrochloric acid and stirring. After cooling to 3°C, 0.1 mol of sodium nitrite was added and the mixture was reacted for 2 h to obtain the diazonium salt.

[0093] S4: Add 0.11 mol of diazonium salt to 0.1 mol of the monocondensed product, add sodium bicarbonate to adjust the pH to 6.8, control the temperature to 8°C, and react for 3 h to obtain the coupled product;

[0094] S5: Add 0.12 mol of 6-amino-2,3-dichloroquinoxaline to 0.1 mol of the coupled product, and then add 200 g of water for expansion. Control the temperature to 45 ° C and the pH value to 6.2, and react for 6 h to obtain the formula

[0095] Example 6

[0096] A method for preparing a reactive magenta dye having a structure of Formula 6 comprises the following steps:

[0097] S1: 0.1 mol of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt was added to 240 g of water and dissolved, followed by adding 16.8 g of sodium bicarbonate to obtain a dissolved product;

[0098] S2: 0.1 mol of cyanuric chloride was slurried with 129 g of ice-water mixture, and the dissolved product was added dropwise to the slurried cyanuric chloride. The temperature was controlled at 10° C. and the reaction was carried out for 3 h to obtain a condensed product.

[0099] S3: 0.1 mol of sulfonated Tobias' acid was added to 100 g of ice and slurried, followed by the addition of 0.12 mol of hydrochloric acid and stirring. After cooling to 10°C, 0.11 mol of sodium nitrite was added and the mixture was reacted for 2 h to obtain the diazonium salt.

[0100] S4: Add 0.12 mol of diazonium salt to 0.1 mol of the monocondensed product, add sodium bicarbonate to adjust the pH to 6.5-7.0, control the temperature at 10°C, and react for 3 h to obtain the coupled product;

[0101] S5: Add 0.13 mol of 6-amino-2,3-dichloroquinoxaline to 0.1 mol of the coupled product, and then add 200 g of water for expansion. Control the temperature to 50 ° C and the pH value to 6.5, and react for 6 h to obtain the formula

[0102] Comparative Example 1

[0103] Based on Example 2, except that in step 5, an equal amount of para-ester is used to replace 6-amino-2,3-dichloroquinoxaline, the product is prepared as follows:

[0104] Comparative Example 2

[0105] Based on Example 5, except that in step 5, an equal amount of para-ester is used to replace 6-amino-2,3-dichloroquinoxaline, the product is prepared as follows:

[0106] The dyes prepared in Examples 1-6 and Comparative Examples 1-2 were subjected to visible light absorption spectrum detection. The detection results are shown in Table 1.

[0107] Table 1

[0108] project Absorption peak value Extinction coefficient Example 1 540 450 Example 2 540 451 Example 3 538 432 Example 4 540 435 Example 5 540 452 Example 6 536 446 Comparative Example 1 556 430 Comparative Example 2 550 428

[0109] The dyes prepared in Examples 2 and 5 and Comparative Examples 1-2 were subjected to dyeing tests. The test results are shown in Table 2.

[0110] Table 2

[0111]

[0112] As can be seen from Examples 2 and 5, Comparative Examples 1-2 and Table 2, the reactive dyes prepared in the present application have better color fastness. 6-amino-2,3-dichloroquinoxaline and cyanuric chloride are used together as dual-active group dyes to effectively improve the dyeing performance of the fuel. Compared with ordinary reactive dyes with conventional vinylsulfone active groups, the dyeing performance is superior.

[0113] Using Example 2 as a standard sample, the staining intensity test was performed on Example 5 and Comparative Examples 1-2. The test results are shown in Table 3.

[0114] Table 3

[0115] Example Spectrophotometry strength Total color difference Beauty Value Red-green difference Huang Lancha Example 5 100％ 98％ 0.235 -0.187 -0.156 0.276 Comparative Example 1 90％ 90％ 0.545 -0.427 -0.422 -0.124 Comparative Example 2 93％ 91％ 0.646 -0.521 -0.528 0.554

[0116] It can be seen from Examples 2 and 5, Comparative Examples 1-2 and Table 3 that Examples 2 and 5 have higher dyeing intensity and more vivid red color.

[0117] The dyes prepared in Examples 2 and 5 and Comparative Examples 1-2 were tested for color fixation rate. The test results are shown in Table 4.

[0118] Table 4

[0119]

[0120] As shown in Table 4, the reactive magenta dye prepared in this application has an excellent fixing effect on cotton fabrics. As active groups, there are two active chlorine atoms in its molecular structure, which are very stable after combining with the hydroxyl groups on the fiber and can effectively improve the color fixing effect.

[0121] The above are all preferred embodiments of the present application, and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the principles of the present application should be included in the scope of protection of the present application.

Claims

1. A reactive magenta dye, characterized in that The general structural formula of the reactive magenta dye is Formula 1 or Formula 2; Wherein, formula 1 is Formula 2 is R1 is selected from -H, -CH3, -SO3M or -OH; R2 is a halogen element; M is selected from Na, K or Li.

2. A reactive magenta dye according to claim 1, characterized in that, The R1 is selected from -H and / or -SO3M; the R2 is selected from -Cl; and the M is selected from Na.

3. A reactive magenta dye according to claim 2, characterized in that, The structure of the reactive magenta dye is Formula 3, Formula 4, Formula 5, Formula 6 or Formula 7; Among them, formula 3 is Formula 4 is Formula 5 is Formula 6 is Formula 7 is 4. A method for preparing the reactive magenta dye according to claim 3, characterized in that: The preparation method of the reactive magenta dye when the structure is Formula 3 or Formula 6 comprises the following steps: Step 1: Take 1-amino 8-naphthol-3, 6-disulfonic acid monosodium salt After adding water to dissolve, continue to add sodium bicarbonate to obtain the dissolved product Step 2: After beating cyanuric chloride with an ice-water mixture, the dissolved product is added to the beated cyanuric chloride, and the temperature is controlled at 5-10° C. to obtain a condensed product. The reaction formula is as follows: Step 3: Take sulfonated Tobias acid or m-aminobenzenesulfonic acid, add ice and beat into a pulp, add hydrochloric acid and mix, cool to 0-10°C, and then add sodium nitrite to obtain a diazonium salt. The reaction formula is as follows: Step 4: Add the diazonium salt to the condensed product, add sodium bicarbonate to adjust the pH to 6.5-7.0, and control the temperature to 5-10° C. to obtain a coupled product. The reaction formula is as follows: Step 5: Add 6-amino-2,3-dichloroquinoxaline to the coupling product, then add water to expand the body, control the temperature to 40-50 ° C and the pH value to 6-6.5, to obtain the formula 3 or formula 6, the reaction formula is as follows:

5. The preparation method of reactive magenta dye according to claim 4, wherein In the step 1, the mass ratio of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt to water is 1:(5-7); the molar ratio of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt to sodium bicarbonate is 1:(1-2).

6. The preparation method of reactive magenta dye according to claim 4, wherein In the step 2, the molar ratio of 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt to cyanuric chloride is 1:(0.9-1.1); the mass ratio of cyanuric chloride to ice-water mixture is 1:(5-7).

7. The preparation method of reactive magenta dye according to claim 4, wherein In the step 3, the molar ratio of sulfonated Tobias acid or m-aminobenzenesulfonic acid, hydrochloric acid and sodium nitrite is 1: (0.8-1.2): (0.9-1.1).

8. The preparation method of reactive magenta dye according to claim 4, wherein In the step 4, the molar ratio of the diazonium salt to the condensation product is (1-1.2):

1.

9. The preparation method of reactive magenta dye according to claim 4, wherein In the step 5, the molar ratio of the coupling product to 6-amino-2,3-dichloroquinoxaline is 1:(1.1-1.3).

10. Use of the reactive magenta dye according to any one of claims 1 to 3 in the field of cotton fibers and textiles thereof, characterized in that: The concentration (owf) of the reactive magenta dye is 0.5-10%.

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