A Dye Compound, Its Preparation Method and Application

Abstract

The present invention belongs to the technical field of dyes, and particularly relates to a dye compound, a preparation method thereof and an application. The dye compound provided by the present invention has the structure shown in Formula I. When the dye compound of the present invention is used as a dye, it has high washing fastness, high color yield, a wide pH range of the dyeing bath (pH 4 to 12), and good re-dyeing property.

Description

Technical Field

[0001] The present invention belongs to the technical field of dyes, and particularly relates to a dye compound, a preparation method thereof, and an application thereof. Background Art

[0002] Currently, existing disperse dyes mainly include disperse red-violet, disperse red, disperse golden yellow, disperse yellow 6GSL (C.I. Disperse Yellow 114), disperse black, and disperse dark blue, as shown in (1) - (6):

[0003] (1) Red-violet:

[0004]

[0005] (2) Disperse red:

[0006]

[0007] (3) Disperse golden yellow:

[0008]

[0009] (4) Disperse yellow 6GSL (C.I. Disperse Yellow 114):

[0010]

[0011] (5) Disperse black: Prepared by blending the above dyes;

[0012] (6) Disperse dark blue: Prepared by blending the above dyes (1) - (4). However, for the above disperse dyes to dye pure polyester and polyester - ammonia blended fibers, the pH of the dye bath can only be in the range of 3.5 - 4.5, which is not easy to control, the re - dyeing property is poor, and the color - giving amount of the dye is low. Summary of the Invention

[0013] In order to solve the problems existing in the prior art, the present invention provides a dye compound, a preparation method thereof, and an application thereof. When the dye compound provided by the present invention is used as a dye, the obtained dye has the advantages of high washing fastness, high color - giving amount, a wide pH range (pH 4 - 12) of the dyeing bath, and good re - dyeing property.

[0014] To achieve the above object, the present invention provides the following technical solutions.

[0015] The present invention provides a dye compound having the structure shown in Formula I:

[0016]

[0017] R1 is

[0018]

[0019] R2 is -H, -OCH3 or -OCH2CH3; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group with 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2; R5 is -NO2 or -CN; R6 is -NO2 or -CN; R7 is -Br or -Cl; R8 is -H or -Cl;

[0020] The is a mixture of the structure with Cl substitution at the 5,6 positions and the structure with Cl substitution at the 6,7 positions.

[0021] Preferably, it has the structures shown in Formulas 1 to 13:

[0022]

[0023]

[0024] The present invention also provides a preparation method of the dye compound described in the above technical solution, including the following steps:

[0025] Mix an amino compound, an acidic reagent and a diazotizing reagent and carry out a diazotization reaction to obtain a diazo solution; the diazotizing reagent is a sodium nitrite solution or nitrosylsulfuric acid;

[0026] The amino compound has the structures shown in Formulas I-1 to I-6:

[0027]

[0028] Mix the diazo solution, a coupling component, an emulsifier, sulfuric acid and sulfamic acid and carry out a coupling reaction to obtain the dye compound;

[0029] The coupling component has the structure shown in Formula II-1:

[0030] Preferably, the temperature of the diazotization reaction is 0 to 35 °C, and the heat preservation time is 1 to 5 h.

[0031] Preferably, the temperature of the coupling reaction is 0 to 5 °C, and the heat preservation time is 1 to 20 h.

[0032] Preferably, the emulsifier includes one or more of fast T, fatty alcohol polyoxyethylene ether and polyoxyethylene sorbitan mono-fatty acid ester.

[0033] The present invention also provides a disperse dye, including a dispersant and the dye compound described in the above technical solution.

[0034] The present invention also provides an isomeric disperse dye composition, including an isomeric dye compound and a dispersant;

[0035] The isomeric dye compound has R1 as R2 is -H, -OCH3 or -OCH2CH3; R3 is -H, -CH3 or -NHCOCH3;

[0036] R4 is an alkyl group with 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2; R5 is -NO2 or -CN; R6 is -NO2 or -CN; R7 is -Br or -Cl; R8 is -H or -Cl, and it is a dye compound of formula I;

[0037] The is a mixture of the structure with Cl substitution at the 5,6 positions and the structure with Cl substitution at the 6,7 positions.

[0038] The present invention also provides a dye composition, which includes a first component and a dispersant; the first component includes one or several of a first dye compound, a second dye compound and a third dye compound;

[0039] The first dye compound has R1 as R2 and R3 are H, R4 is an alkyl group with 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2, and R7 is -Br, and it is a dye compound of the structure shown in formula I;

[0040] The second dye compound has R1 as R2 is -H, -OCH3 or -OCH2CH3; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group with 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2, and it is a dye compound of the structure shown in formula I;

[0041] The third dye compound has R1 as R5 is -NO2, R2 is -H, -OCH3 or -OCH2CH3; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group with 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2, and it is a dye compound of the structure shown in formula I.

[0042] The present invention also provides the application of the disperse dye or the dye composition described in the above technical solution in dyeing pure polyester, polyester-ammonia, polyester-cotton or nylon-ammonia fabrics.

[0043] The present invention provides a dye compound, which has the structure shown in formula I:

[0044]

[0045] R1 is

[0046] R2 is -H, -OCH3 or -OC2H4; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group having 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2; R5 is -NO2 or -CN; R6 is -NO2 or -CN; R7 is -Br or -Cl;

[0047] R8 is -H or -Cl;

[0048] The is a mixture of the structure with Cl substitution at the 5,6 positions and the structure with Cl substitution at the 6,7 positions.

[0049] When the dye compound provided by the present invention is used as a dye, compared with the existing high-wash fastness disperse dyes, it has the following advantages: (1) It has the same or higher wash fastness; (2) It can be dyed in an acid-alkaline (pH = 4-12) dye bath, and has a higher over-dyeing property, while the existing high-wash fastness disperse dyes can only be dyed in an acidic (pH = 3.8-4.5) dye bath and have poor over-dyeing property; (3) Different from the existing high-wash fastness disperse dyes, when the dye compound provided by the present invention is used as a dye, it can dye spandex and has a higher wash fastness, and the reduction cleaning can be omitted for dyeing spandex, while the existing high-wash fastness disperse dyes can only stain spandex and then must be removed by reduction cleaning; (4) Different from the existing high-wash fastness disperse dyes, this dye has high fastness to acidic and alkaline perspiration; (5) The N-benzyl chloride is introduced into the dye of the present invention, and it has a higher color giving property. (6) The dye of the present invention has high heat migration performance, and the fabric after dyeing can be controlled at 170 °C for heat setting and still has high wash fastness; different from the existing high-wash fastness disperse dyes that can only be heat set at 140 °C, the dye provided by the present invention improves the setting temperature and at the same time improves the setting quality. Description of the Drawings

[0050] Figure 1 is the ultraviolet spectrophotometer detection spectrum of the product obtained in Example 1;

[0051] Figure 2 is the ultraviolet spectrophotometer detection spectrum of the product obtained in Example 2;

[0052] Figure 3 is the ultraviolet spectrophotometer detection spectrum of the product obtained in Example 3;

[0053] Figure 4 is the ultraviolet spectrophotometer detection spectrum of the product obtained in Example 4;

[0054] Figure 5 is the ultraviolet spectrophotometer detection spectrum of the product obtained in Example 5;

[0055] Figure 6The ultraviolet spectrophotometer detection spectrum of the product obtained in Example 6;

[0056] Figure 7 The ultraviolet spectrophotometer detection spectrum of the product obtained in Example 7;

[0057] Figure 8 The ultraviolet spectrophotometer detection spectrum of the product obtained in Example 8;

[0058] Figure 9 The liquid chromatography detection chart of the product obtained in Example 1;

[0059] Figure 10 The liquid chromatography detection chart of the product obtained in Example 2;

[0060] Figure 11 The liquid chromatography detection chart of the product obtained in Example 3;

[0061] Figure 12 The liquid chromatography detection chart of the product obtained in Example 4;

[0062] Figure 13 The liquid chromatography detection chart of the product obtained in Example 5;

[0063] Figure 14 The liquid chromatography detection chart of the product obtained in Example 6;

[0064] Figure 15 The liquid chromatography detection chart of the product obtained in Example 7;

[0065] Figure 16 The liquid chromatography detection chart of the product obtained in Example 8;

[0066] Figure 17 The mass spectrum of the product obtained in Example 1;

[0067] Figure 18 The mass spectrum of the product obtained in Example 2. Detailed implementation manners

[0068] The present invention provides a dye compound having the structure shown in Formula I:

[0069]

[0070] R1 is

[0071] R2 is -H, -OCH3 or -OC2H4; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group having 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2; R5 is -NO2 or -CN; R6 is -NO2 or -CN; R7 is -Br or -Cl; R8 is -H or -Cl.

[0072] The is a mixture of a structure with Cl substitution at the 5,6 positions and a structure with Cl substitution at the 6,7 positions.

[0073] In the present invention, the dye compound preferably has the structures shown in Formulas 1 to 13:

[0074]

[0075]

[0076] The present invention also provides a preparation method of the dye compound described in the above technical solution, including the following steps:

[0077] Mix an amino compound, an acidic reagent and a diazotizing reagent, and then carry out a diazotization reaction to obtain a diazo solution; the diazotizing reagent is a sodium nitrite solution or nitrosylsulfuric acid;

[0078] The amino compound has the structures shown in Formulas I-1 to I-6:

[0079]

[0080] Mix the diazo solution, a coupling component, an emulsifier, sulfuric acid and sulfamic acid, and then carry out a coupling reaction to obtain the dye compound;

[0081] The coupling component has the structure shown in Formula II-1:

[0082] In the present invention, an amino compound, an acidic reagent and a diazotizing reagent are mixed and then subjected to a diazotization reaction to obtain a diazo solution.

[0083] In the present invention, the amino compound has the structures shown in Formulas I-1 to I-6:

[0084]

[0085] In the present invention, the acidic reagent includes dilute acid or concentrated sulfuric acid.

[0086] In the present invention, the diazotizing reagent is preferably a sodium nitrite solution or nitrosylsulfuric acid; the mass concentration of the nitrosylsulfuric acid is preferably 40-45%, more preferably 40-41%.

[0087] In the present invention, the mass ratio of the amino compound to the diazotizing reagent is preferably 20-35:30-40, more preferably 25-30:32-35. In the present invention, when the acidic reagent is concentrated sulfuric acid, the dosage ratio of the amino compound to concentrated sulfuric acid is preferably 20-35 g:30-50 mL, more preferably 25-30 g:30-50 mL.

[0088] In the present invention, the temperature of the diazotization reaction is preferably 0 to 35 °C, and the heat preservation time is preferably 1 to 5 h.

[0089] After obtaining the diazo solution, in the present invention, the diazo solution, coupling component, emulsifier, sulfuric acid, and aminosulfonic acid are mixed and then subjected to a coupling reaction to obtain the dye compound.

[0090] In the present invention, the emulsifier preferably includes one or more of Fast T, fatty alcohol polyoxyethylene ether, and polyoxyethylene sorbitan mono-fatty acid ester, and more preferably fatty alcohol polyoxyethylene ether.

[0091] In the present invention, the molar ratio of the diazonium salt to the coupling component in the diazo solution is preferably 1:0.95 to 1.02, and more preferably 1:0.98. In the present invention, the mass ratio of the coupling component, emulsifier, sulfuric acid, and aminosulfonic acid is preferably (20 to 40):5:(10 to 15):(1 to 2), and more preferably (20 to 40):5:(10 to 15):(1 to 1.5).

[0092] In the present invention, the temperature of the coupling reaction is preferably 0 to 5 °C, and more preferably 2 °C.

[0093] The present invention also provides a disperse dye, which includes a dispersant and the dye compound described in the above technical solution.

[0094] In the present invention, the dispersant preferably includes dispersant MF and / or sodium lignosulfonate, and more preferably dispersant MF and sodium lignosulfonate. In the present invention, the mass ratio of the dispersant to the dye compound is preferably 1 to 2:1.

[0095] The present invention also provides a dye composition, which includes a first component and a dispersant; the first component includes one or more of a first dye compound, a second dye compound, and a third dye compound.

[0096] In the present invention, the first dye compound is a dye compound of the structure shown in Formula I where R1 is R2 and R3 are H, R4 is an alkyl group having 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2, and R7 is -Br;

[0097] In the present invention, the second dye compound is a dye compound of the structure shown in Formula I where R1 is R2 is -H, -OCH3 or -OCH2CH3; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group having 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2;

[0098] In the present invention, the third dye compound has R1 as R5 is -NO2, R2 is -H, -OCH3 or -OCH2CH3; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group having 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2, and is a dye compound having the structure shown in Formula I.

[0099] When the dye compound provided by the present invention is used as a dye, it includes chromatograms such as yellow-brown, red, purple, and blue, and at the same time, chromatograms such as high-wash fast black and dark blue can be blended.

[0100] The dye of the present invention can also be blended with high-wash fast disperse golden yellow HWA-R, disperse golden yellow JWF-3R (C.I. Disperse Yellow 246), and yellow 6GSL (C.I. Disperse Yellow 114) to form chromatograms of black, dark blue, brown, and green.

[0101] The present invention also provides the application of the above-mentioned disperse dye or dye composition in dyeing pure polyester, polyester-ammonia, polyester-cotton or nylon-ammonia fabrics.

[0102] The technical solutions provided by the present invention will be described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention.

[0103] Example 1

[0104] Preparation of:

[0105] Dissolve 20.2 g of 5-nitro-3-aminobenzisothiazole in 30 mL of concentrated sulfuric acid, cool to 2 °C, and dropwise add 32.5 g of a nitrosylsulfuric acid solution with a mass concentration of 41% at 2 °C. Keep warm for 2 h for diazotization reaction to obtain 107.3 g of diazo solution.

[0106] Mix 26 g of N-ethyl-N-o-chlorobenzyl-m-toluidine, 5 g of polyoxyethylene sorbitan monofatty acid ester, 10 g of sulfuric acid, and 1.5 g of amidosulfonic acid, and beat into a pulp for 1 h. Then add an appropriate amount of crushed ice, and dropwise add the above-mentioned diazo solution at 2 °C. Keep warm for 12 h for coupling reaction; after the coupling reaction, filter the system obtained from the coupling reaction, and wash the obtained solid phase to neutral to obtain 44.7 g of dye compound.

[0107] Example 2

[0108] Preparation of:

[0109] Dissolve 26.2 g of 2,4-dinitro-6-bromoaniline in 30 mL of concentrated sulfuric acid, control the temperature at 15 °C, dropwise add 33.5 g of a nitrosylsulfuric acid solution with a mass concentration of 40%, and keep warm for 2 h for diazotization reaction to obtain 114.3 g of diazo solution.

[0110] 25.0 g of N-ethyl-N-p-chlorobenzylaniline, 5 g of fatty alcohol polyoxyethylene ether, 10 g of sulfuric acid and 1.5 g of aminosulfonic acid were combined and slurried for 1 h, then an appropriate amount of crushed ice was added, and the above diazonium solution was added dropwise at 2 °C, and the temperature was maintained for 8 h for the coupling reaction; after the coupling reaction, the mixture was filtered and washed with water until neutral to obtain 47.9 g of a dye compound.

[0111] Example 3

[0112] Preparation of:

[0113] 20.2 g of 5-nitro-3-aminobenzisothiazole was dissolved in 30 mL of concentrated sulfuric acid, cooled to 2 °C, and 32.5 g of a 41% mass concentration of nitrosylsulfuric acid solution was added dropwise at 2 °C, and the temperature was maintained for 2 h for the diazotization reaction to obtain 107.3 g of a diazonium solution.

[0114] 37.2 g of N-cyanoethyl-N-p-chlorobenzyl-2-methoxy-5-acetamidoaniline, 5 g of fatty alcohol polyoxyethylene ether, 15 g of sulfuric acid and 1.5 g of aminosulfonic acid were mixed and slurried for 1 h, then an appropriate amount of crushed ice was added, and the above diazonium solution was added dropwise at 2 °C, and the temperature was maintained for 17 h for the coupling reaction; after the coupling reaction, the system obtained from the coupling reaction was filtered, and the solid phase obtained was washed with water until neutral to obtain 51.8 g of a dye compound.

[0115] Example 4

[0116] (i.e., R1 is Preparation of the structure of formula 1 where R2 is H, R3 is CH3, and R4 is C2H5):

[0117] 32.5 g of a 41% mass concentration of nitrosylsulfuric acid solution was added to 50 mL of concentrated sulfuric acid, cooled to 2 °C, and 22.2 g of 5,6-dichlorobenzothiazole was added to the above solution at 2 °C, and the temperature was maintained for 1 hour for the diazotization reaction to obtain 91 g of a diazonium solution;

[0118] 26 g of N-ethyl-N-o-chlorobenzyl-m-toluidine, 5 g of fatty alcohol polyoxyethylene ether, 15 g of sulfuric acid and 1 g of aminosulfonic acid were mixed and slurried for 1 h, then an appropriate amount of crushed ice was added, and the above diazonium solution was added dropwise at 2 °C, and the temperature was maintained for 3 h for the reaction; after the coupling reaction, the system obtained from the coupling reaction was filtered and washed with water until neutral to obtain 46.6 g of a dye compound.

[0119] Example 5

[0120] Preparation of:

[0121] Dissolve 24.7 g of 2-cyano-4-nitro-6-bromoaniline in 20 mL of concentrated sulfuric acid, cool to 2 °C, and dropwise add 33.5 g of a 40% mass concentration nitrosylsulfuric acid solution at 2 °C. Keep the temperature at 2 °C for 2 hours for the diazotization reaction to obtain 94.6 g of diazo solution.

[0122] Mix 25.5 g of N-ethyl-N-p-chlorobenzyl-m-toluidine, 5 g of fatty alcohol polyoxyethylene ether, 10 g of sulfuric acid, and 1.5 g of aminosulfonic acid, then slurry for 1 h. Then add an appropriate amount of crushed ice, and dropwise add the above diazo solution at 2 °C. Keep the temperature at 2 °C for 6 h for the coupling reaction; after the coupling reaction, filter and wash with water until neutral to obtain 49.7 g of dye compound.

[0123] Example 6

[0124] Preparation:

[0125] Dissolve 30.2 g of 2,6-dibromo-4-nitroaniline in 35 mL of concentrated sulfuric acid, control the temperature at 30 °C and dropwise add 33.7 g of a 40% mass concentration nitrosylsulfuric acid solution. Keep the temperature at 30 °C for 3 hours for the diazotization reaction to obtain 127.6 g of diazo solution.

[0126] Mix 24.1 g of N-methyl-N-p-chlorobenzylaniline, 5 g of fatty alcohol polyoxyethylene ether, 10 g of sulfuric acid, and 1.5 g of aminosulfonic acid, then slurry for 1 h. Then add an appropriate amount of crushed ice, and dropwise add the above diazo solution at 2 °C. Keep the temperature at 2 °C for 12 h for the coupling reaction; after the coupling reaction, filter and wash with water until neutral to obtain 52.7 g of dye compound.

[0127] Example 7

[0128] Preparation:

[0129] Dissolve 30.2 g of 2,6-dibromo-4-nitroaniline in 35 mL of concentrated sulfuric acid, control the temperature at 25 - 35 °C and dropwise add 33.7 g of a 40% mass concentration nitrosylsulfuric acid solution. Keep the temperature at 25 - 35 °C for 3 hours for the diazotization reaction to obtain 127.6 g of diazo solution.

[0130] Mix 26.5 g of N-ethyl-N-p-chlorobenzyl-m-toluidine, 5 g of fatty alcohol polyoxyethylene ether, 10 g of sulfuric acid, and 1.5 g of aminosulfonic acid, then slurry for 1 h. Then add an appropriate amount of crushed ice, and dropwise add the above diazo solution at 2 °C. Keep the temperature at 2 °C for 16 h for the coupling reaction; after the coupling reaction, filter and wash with water until neutral to obtain 54.4 g of dye compound.

[0131] Example 8

[0132] Preparation:

[0133] Dissolve 20.7 g of 2,6-dichloro-4-nitroaniline in 25 mL of concentrated sulfuric acid, and dropwise add 33.5 g of a nitrosylsulfuric acid solution with a mass concentration of 40% at room temperature (10 - 35°C). Keep the temperature for 3 hours for the diazotization reaction to obtain 99.7 g of diazo solution.

[0134] Slurry 23.3 g of N-methyl-N-(4-chlorobenzyl)aniline, 5 g of fatty alcohol polyoxyethylene ether, 10 g of sulfuric acid, and 1.5 g of aminosulfonic acid together for 1 hour, then add an appropriate amount of crushed ice, and dropwise add the above diazo solution at 2°C. Keep the temperature for 14 h for the coupling reaction; after the coupling reaction, filter and wash with water until neutral to obtain 44.1 g of dye compound.

[0135] The products obtained in Examples 1 - 8 of the present invention were detected by ultraviolet spectrophotometer and liquid chromatography, where Figures 1 - 8 are the ultraviolet spectrophotometer detection spectra of the products obtained in Examples 1 - 8 respectively; Figures 9 - 16 are the liquid chromatography detection diagrams of the products obtained in Examples 1 - 8 respectively; It can be seen from Figures 1 - 16 that: The preparation methods of Examples 1 - 8 successfully prepared the products with the corresponding structures. In addition, Figures 9 - 16 the spectral information is shown in Tables 1 - 8 respectively.

[0136] Table 1 Figure 9 Chromatographic information

[0137] Retention time Area Height Label Concentration Area % 1 2.357 3497 499 v 0.000 0.149 2 2.582 24537 2860 v 0.000 1.044 3 2.682 14722 2492 v 0.000 0.627 4 2.860 45330 6783 v 0.000 1.929 5 3.027 37665 5726 v 0.000 1.603 6 3.205 18707 2335 v 0.000 0.796 7 3.401 12310 1182 v 0.000 0.524 8 3.606 8747 874 v 0.000 0.372 9 3.837 14831 1671 v 0.000 0.631 10 4.047 34651 3345 v 0.000 1.475 11 4.573 5804 603 v 0.000 0.247 12 4.737 4863 611 v 0.000 0.207 13 4.884 9416 696 v 0.000 0.401 14 5.267 17922 1477 v 0.000 0.763 15 5.537 8657 683 v 0.000 0.368 16 5.835 13244 911 v 0.000 0.564 17 6.057 4698 427 v 0.000 0.200 18 6.419 16817 1206 v 0.000 0.716 19 7.158 1999489 165992 v 0.000 85.098 20 8.270 10289 320 v 0.000 0.438 21 8.624 6194 268 v 0.000 0.264 22 9.337 15592 828 v 0.000 0.664 23 10.965 1047 62 0.000 0.045 24 11.643 10834 582 0.000 0.461 25 13.329 9770 433 0.000 0.416 Total 2349632 202867 0.000 100

[0138] Table 2 Figure 10 Chromatographic information

[0139]

[0140]

[0141] Table 3 Figure 11 Chromatographic information

[0142]

[0143]

[0144] Table 4 Figure 12 Chromatographic information

[0145] Retention time Area Height Label Concentration Area % 1 2.505 7441 723 v 0.000 0.405 2 2.655 45209 8161 v 0.000 2.461 3 2.755 56266 6926 v 0.000 3.063 4 3.048 43465 4811 v 0.000 2.366 5 3.262 28528 2238 v 0.000 1.553 6 3.493 10483 1437 v 0.000 0.571 7 3.676 13296 1648 v 0.000 0.724 8 3.845 45807 4713 v 0.000 2.494 9 4.262 44416 4816 v 0.000 2.418 10 4.504 9212 1011 v 0.000 0.502 11 4.691 11522 796 v 0.000 0.627 12 4.942 6307 642 v 0.000 0.343 13 5.303 28669 2220 v 0.000 1.561 14 5.713 18378 1359 v 0.000 1.000 15 5.990 18472 1628 v 0.000 1.006 16 6.304 18113 1241 v 0.000 0.986 17 6.585 18216 1118 v 0.000 0.992 18 7.091 5502 246 v 0.000 0.300 19 8.001 9718 777 v 0.000 0.529 20 8.366 775357 57156 v 0.000 42.210 21 9.249 617447 41549 v 0.000 33.613 22 10.308 1840 106 v 0.000 0.100 23 10.578 3259 193 v 0.000 0.177 Total 1836922 145515 100.00

[0146] Table 5 Figure 13 Chromatographic information

[0147]

[0148]

[0149] Table 6 Figure 14 Chromatographic information

[0150] Retention time Area Height Label Concentration Area % 1 1.312 6414 1305 V 0.00 0.122 2 1.423 7801 806 0.00 0.149 3 2.019 1788 338 0.00 0.034 4 2.285 4696 376 V 0.00 0.090 5 2.530 1500 247 V 0.00 0.029 6 2.656 2395 353 V 0.00 0.046 7 2.750 1706 297 V 0.00 0.033 8 2.944 30188 4768 V 0.00 0.576 9 3.111 13412 1547 V 0.00 0.256 10 3.424 6944 877 V 0.00 0.132 11 3.616 17548 1986 V 0.00 0.335 12 3.899 11649 1366 V 0.00 0.222 13 4.073 8473 934 V 0.00 0.162 14 4.359 8234 557 V 0.00 0.157 15 4.754 10189 954 V 0.00 0.194 16 5.012 14118 1412 V 0.00 0.269 17 5.353 1275 106 V 0.00 0.024 18 5.980 7563 466 V 0.00 0.144 19 6.504 1811 160 V 0.00 0.035 20 6.871 4922 418 V 0.00 0.094 21 7.907 5923 414 0.00 0.113 22 8.488 1114 69 0.00 0.021 23 8.808 1247 85 V 0.00 0.024 24 9.633 5041755 303320 0.00 96.152 25 10.778 11578 522 V 0.00 0.221 26 11.624 14517 507 V 0.00 0.277 27 14.457 2397 98 0.00 0.046 28 16.543 2344 82 0.00 0.045 Total 1836922 145515 0.00 100.00

[0151] Table 7 Figure 15 Chromatographic information

[0152] Retention time Area Height Label Concentration Area % 1 2.430 5946 918 V 0.00 0.155 2 2.540 7935 1273 V 0.00 0.207 3 2.688 44545 7255 V 0.00 1.162 4 2.877 24159 3676 V 0.00 0.630 5 3.077 27769 3583 V 0.00 0.724 6 3.276 8457 1295 V 0.00 0.221 7 3.384 8318 1279 V 0.00 0.217 8 3.507 18300 1232 V 0.00 0.477 9 3.958 5522 826 V 0.00 0.144 10 4.086 18392 1491 V 0.00 0.480 11 4.415 4314 565 V 0.00 0.113 12 4.614 20906 2175 V 0.00 0.545 13 4.875 5519 394 V 0.00 0.144 14 5.244 17034 977 V 0.00 0.444 15 5.768 2853 270 V 0.00 0.074 16 5.932 2650 299 V 0.00 0.069 17 6.272 3568941 369304 V 0.00 93.085 18 7.036 6003 467 V 0.00 0.157 19 7.270 8668 659 V 0.00 0.226 20 7.542 6025 379 V 0.00 0.157 21 8.005 1146 87 V 0.00 0.030 22 8.410 6402 491 V 0.00 0.167 23 9.455 5495 357 0.00 0.143 24 9.755 2085 161 V 0.00 0.054 25 12.624 1111 63 0.00 0.029 26 13.236 5566 279 V 0.00 0.145 Total 1836922 145515 0.00 100.00

[0153] Table 8 Figure 16 Chromatographic information

[0154]

[0155]

[0156] The present invention also performed mass spectrometry detection on the products obtained in Example 1 and Example 2, as shown in Figure 17 and 18 , further verifying that the preparation methods of Example 1 and Example 2 successfully obtained the products with the corresponding structures.

[0157] Application Example 1

[0158] Add 20 g of the dye compound of Example 1, 28 g of MF dispersant, 12 g of sodium lignosulfonate dispersant, and 90 g of water to a sand mill, and then grind it with glass sand until the degree of dispersion reaches level 4. Take 80 °C drying of the ground slurry to obtain a commercial dye with a dyeing strength of 200%, and dye polyester fabric in bright blue.

[0159] Application Example 2

[0160] The difference from Application Example 1 is only that: the dye compound of Example 1 is replaced with the dye compound of Example 2.

[0161] Application Example 3

[0162] The difference from Application Example 1 is only that: the dye compound of Example 1 is replaced with the dye compound of Example 3.

[0163] Application Example 4

[0164] The difference from Application Example 1 is only that: the dye compound of Example 1 is replaced with the dye compound of Example 4.

[0165] Application Example 5

[0166] The difference from Application Example 1 is only that: the dye compound of Example 1 is replaced with the dye compound of Example 5.

[0167] Application Example 6

[0168] The difference from Application Example 1 is only that the dye compound in Example 1 is replaced with the dye compound in Example 6.

[0169] Application Example 7

[0170] The difference from Application Example 1 is only that the dye compound in Example 1 is replaced with the dye compound in Example 7.

[0171] Application Example 8

[0172] The difference from Application Example 1 is only that the dye compound in Example 1 is replaced with the dye compound in Example 8.

[0173] Application Example 9

[0174] 8 g of the dye compound in Example 2, 3 g of the dye compound in Example 6, 2 g of the dye compound in Example 7, 20 g of the dye compound in Example 9, 40 g of MF, 17 g of sodium lignosulfonate, and 200 mL of water were added to a sand mill, and then ground with glass sand until the diffusion degree reached level 5. 80 °C of the ground slurry was dried to obtain a commercial dye with a dyeing strength of 300%, and the polyester fabric was dyed black.

[0175] Application Example 10

[0176] 18 g of the dye compound in Example 2, 1.8 g of the dye compound in Example 7, 7.2 g of the dye compound in Example 9, 30 g of dispersant MF, 13 g of sodium lignosulfonate, and 130 mL of water were added to a sand mill, and then ground with glass sand until the diffusion degree reached level 4. 80 °C of the ground slurry was dried to obtain a commercial dye with a dyeing strength of 300%, and the polyester fabric was dyed dark blue.

[0177] Color yield test

[0178] Test Example 1-1

[0179] 0.3 g of the commercial dye in Application Example 1 was taken, and 10 g of polyester-ammonia knitted fabric (containing 9% spandex, i.e., 91% polyester + 9% spandex) was added to a dye bath at the pH specified in Table 1. The temperature was raised to 130 °C and dyed for 40 minutes, then cooled to 80 °C, soaped, rinsed, and dried to obtain a pure polyester fabric in blue.

[0180] Test Example 1-2

[0181] The difference from Test Example 1-1 is only that the commercial dye in Application Example 1 is replaced with the commercial dye in Application Example 2.

[0182] Test Example 1-3

[0183] The difference from Test Example 1-1 is only that the commercial dye compound in Application Example 1 is replaced with the commercial dye in Example 6.

[0184] Test Examples 1-4

[0185] The difference from Test Example 1-1 is only that: the commercial dye in Application Example 1 is replaced with the commercial dye in Example 8.

[0186] Test Example 1-5

[0187] The difference from Test Example 1-1 is only that: the commercial dye in Application Example 1 is replaced with the commercial dye in Example 9.

[0188] Comparative Test Example 1-a

[0189] The difference from Test Example 1-1 is only that: the commercial dye in Application Example 1 is replaced with red light blue. The structural formula is:

[0190]

[0191] Comparative Test Example 1-b

[0192] The difference from Test Example 1-1 is only that: the commercial dye in Application Example 1 is replaced with high-wash fastness disperse dye black JWF-XH.

[0193] Table 9 Relative color yield of Test Examples and Comparative Test Examples in dye baths with different pH values

[0194]

[0195] As can be seen from Table 9: The dyes provided by the present invention have a wider pH range of dye bath use and can be dyed in a dye bath with a pH of 4 to 12.

[0196] Washing fastness test:

[0197] Test Example 2-1

[0198] According to AATCC TM 61-2009 "Colorfastness to Washing: Rapid Method A2", the colorfastness to washing of the commercial dye in Application Example 2 was tested.

[0199] Test Example 2-2

[0200] The difference from Test Example 2-1 is only that: the commercial dye in Example 2 is replaced with the commercial dye in Application Example 7.

[0201] Comparative Test Example 2-a

[0202] The difference from Test Example 8 is only that: the commercial dye in Example 2 is replaced with red light blue dye, and the structural formula is (1):

[0203] The washing fastness test results of Test Examples 2-1 to 2-2 and Comparative Test Example 2-a are shown in Table 10.

[0204] Table 10 Wash Fastness Test Results

[0205]

[0206] As can be seen from Table 2: By comparing the test examples, it can be seen that the dye of the example has good soaping fastness and can avoid reduction cleaning.

[0207] Light Fastness Test, Six-Fiber Staining and Sublimation Fastness Test - Dyeing Fastness Test Example 3-1 on Pure Polyester Fabric

[0208] According to GB / T8427.2008 "Textiles - Colorfastness to Artificial Light: Xenon Arc" and GB / T6152-1997 "Textiles - Colorfastness to Heat Pressing", the light fastness test and sublimation fastness test were carried out on the commercial dye filter of Application Example 1;

[0209] Test Example 3-2

[0210] The difference from Test Example 3-1 is only that: the commercial dye filter cake of Application Example 1 is replaced with the commercial dye of Application Example 3.

[0211] Test Example 3-3

[0212] The difference from Test Example 3-1 is only that: the commercial dye of Application Example 1 is replaced with the commercial dye of Application Example 4.

[0213] Test Example 3-4

[0214] The difference from Test Example 3-1 is only that: the commercial dye of Application Example 1 is replaced with the commercial dye of Application Example 5.

[0215] Test Example 3-5

[0216] The difference from Test Example 3-1 is only that: the commercial dye of Application Example 1 is replaced with the commercial dye of Application Example 7.

[0217] Test Example 3-6

[0218] The difference from Test Example 3-1 is only that: the commercial dye of Application Example 1 is replaced with the commercial dye of Application Example 9.

[0219] Comparative Test Example 3-a

[0220] The difference from Test Example 3-1 is only that: the commercial dye of Application Example 1 is replaced with high-wash fastness disperse dye red light blue, structural formula (1):

[0221] Comparative Test Example 3-b

[0222] The difference from Test Example 3-1 is only that: the commercial dye in Application Example 1 is replaced by high-wash fastness disperse dye black JWF-XH.

[0223] The results of the light fastness test and sublimation fastness test for Test Examples 3-1 to 3-6, Comparative Test Example 3-a, and Comparative Test Example 3-b are shown in Table 11.

[0224] Table 11 Results of the light fastness test and sublimation fastness test on pure polyester fabric

[0225]

[0226] Light fastness test and sublimation fastness test - Color fastness to dyeing on polyester-spandex fabric (9% spandex)

[0227] Test Example 4-1

[0228] According to GB / T8427.2008 "Textiles - Tests for colour fastness - Colour fastness to artificial light: Xenon arc" and GB / T6152-1997 "Textiles - Tests for colour fastness - Colour fastness to heat pressing", the light fastness test and sublimation fastness test of the commercial dye in Application Example 2 were carried out on polyester-spandex fabric.

[0229] Test Example 4-2

[0230] The difference from Test Example 4-1 is only that: the commercial dye in Application Example 2 is replaced by the commercial dye in Application Example 6.

[0231] Test Example 4-3

[0232] The difference from Test Example 4-1 is only that: the commercial dye in Application Example 2 is replaced by the commercial dye compound in Application Example 8.

[0233] Test Example 4-4

[0234] The difference from Test Example 4-1 is only that: the commercial dye in Application Example 2 is replaced by the commercial dye in Application Example 10.

[0235] Comparative Test Example 4-a

[0236] The difference from Test Example 4-1 is only that: the commercial dye in Application Example 2 is replaced by high-wash fraction red:

[0237]

[0238] Comparative Test Example 4-b

[0239] The difference from Test Example 4-1 is only that: the commercial dye in Application Example 2 is replaced by high-wash fastness disperse red light blue, and the structural formula is (1)

[0240] The dyeing fastness test results of Test Examples 4-1 to 4-4 and Comparative Test Examples 4-a to 4-b on polyester-ammonia fabrics (9% spandex) are shown in Table 12.

[0241] Table 12 Dyeing fastness test results on polyester-ammonia fabrics (9% spandex)

[0242]

[0243] In summary: First, for the dyes of the present invention, the six-fiber staining and water immersion fastness of polyester and polyester-ammonia blended fabrics are both above level 4, reaching or exceeding those of ordinary high-wash dispersion dyes.

[0244] Second, for the high-wash dispersion dyes of the present invention in single color and combined colors, when dyeing polyester and polyester-ammonia blended fabrics, different from the currently used high-wash dispersion dyes, the reduction cleaning process can be omitted, saving time, raw materials and energy, and reducing the dyeing cost.

[0245] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, not all of them. Other embodiments can be obtained based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A dye compound, characterized in that It has a structure shown in Formula 6, Formula 11 or Formula 12:

2. The method for preparing a dye compound according to claim 1, characterized in that: The following steps are involved: An amino compound, an acidic reagent and a diazotizing reagent are mixed and then subjected to a diazotizing reaction to obtain a diazo liquid; the diazotizing reagent is a sodium nitrite solution or nitrosyl sulfuric acid; when the dye compound has a structure shown in Formula 6, the amino compound has a structure shown in Formula I-3, and R5 in Formula I-3 is -CN; when the dye compound has a structure shown in Formula 11, the amino compound has a structure shown in Formula I-3, and R5 in Formula I-3 is -NO2; when the dye compound has a structure shown in Formula 12, the amino compound has a structure shown in Formula I-5, and R7 in Formula I-5 is -Br; The diazo liquid, coupling component, emulsifier, sulfuric acid and aminosulfonic acid are mixed and then subjected to coupling reaction to obtain the dye compound; When the dye compound has the structure shown in Formula 6, the coupling component is N-ethyl-N-p-chlorobenzyl-m-toluidine; when the dye compound has the structure shown in Formula 11, the coupling component is N-ethyl-N-p-chlorobenzylaniline; when the dye compound has the structure shown in Formula 12, the coupling component is N-ethyl-N-p-chlorobenzyl-m-toluidine.

3. The preparation method according to claim 2, characterized in that: The temperature of the diazotization reaction is 0-35° C., and the insulation time is 1-5 hours.

4. The preparation method according to claim 2, characterized in that: The coupling reaction temperature is 0-5°C, and the insulation time is 1-20h.

5. The preparation method according to claim 2, characterized in that: The emulsifier includes one or more of quick T, fatty alcohol polyoxyethylene ether and polyoxyethylene sorbitan monofatty acid ester.

6. A disperse dye, characterized in that: The invention comprises a diffusing agent and the dye compound according to claim 1 or the dye compound prepared by the preparation method according to claim 2.

7. A dye composition, characterized in that It includes a first component and a diffusing agent; the first component includes a first dye compound, a second dye compound and a third dye compound; The first dye compound R1 is A dye compound having a structure represented by formula I, wherein R2 and R3 are H, R4 is an alkyl group having 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2, and R7 is -Br; The second dye compound is R1 R2 is -H, -OCH3 or -OCH2CH3; R3 is -H, -CH3 or -NHCOCH3; R4 is an alkyl group having 1 to 4 carbon atoms, -C2H4CN or -CH2CH=CH2, and the dye compound has a structure shown in formula I; The third dye compound is a dye compound with a structure shown in Formula 11; 8. Use of the disperse dye according to claim 6 or the dye composition according to claim 7 in dyeing pure polyester, polyester-ammonia, polyester-cotton or nylon-ammonia fabrics.

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