A kind of reactive dye containing silicone base and preparation method thereof

Abstract

The present invention relates to a silicone-containing reactive dye and a preparation method thereof, belonging to the field of reactive dyes. The silicone-containing reactive dye is a compound having the following structural formula I: The dye provided by the present invention has a high color fixation rate and excellent various fastness properties during the dyeing process, greatly improving dye utilization, reducing the generation of dye liquor wastewater, and effectively compensating for the problems existing in traditional reactive dyes. The silicone-containing reactive dye has a simple structure and is relatively easy to synthesize, which facilitates its application in industrial production.

Description

Technical Field

[0001] The invention relates to a silicone-containing reactive dye and a preparation method thereof, belonging to the field of reactive dyes. Background Art

[0002] Reactive dyes are dyes that contain reactive groups in their molecules that react with cellulose or protein fibers. They have advantages such as bright colors, a complete color spectrum, high wet friction fastness, and easy application, and have been widely used in production and life. After more than 60 years of development, dye workers have developed nearly 100 reactive groups, and currently more than a dozen are widely used, among which the most widely used are halogenated triazines and vinyl sulfones. However, a fundamental problem with reactive dyes is that they undergo hydrolysis during use, and the reactive groups after hydrolysis lose their ability to fix on the fiber. The hydrolysis of the reactive groups not only directly leads to a loss of 20% to 50% of the dye, resulting in dye waste, but also reduces the fixation rate of reactive dyes on cotton fibers to only 50% to 80%, causing the problem of dye wastewater polluting the environment (Journal of Dalian University of Technology, 1999, 39(2): 235-242.).

[0003] To solve this problem, dye chemists usually introduce two or more reactive groups into the structure to improve the dye's fixation rate on fibers. Reactive dyes with two reactive groups, such as some bis-monochloro-s-triazine reactive dyes connected by a diarylamine bridge group, have a fixation rate of over 80% on cotton fibers (Dyes and Dyeing, 2014, 51(2):14-20.); the bis-β-vinyl sulfone sulfate reactive dye Reactive Black KN-B also has a fixation rate of about 70% on cotton fibers (CIESC Journal, 2019, 70(10):3704-3711).

[0004] Since heterodiactive dyes contain both halogenated s-triazine and β-vinylsulfone sulfate active groups, they have good acid and alkali stability after being fixed to fibers, so their dyed fibers have better color fastness and have a good development prospect. However, the activity of the monochloros-s-triazine active group is relatively low, requiring a temperature of 85-90°C for color fixation (Dyes and Pigments, 1989, 11(4):243-259.), while the vinylsulfone active group is more reactive and usually fixes at 60°C (Dyes and Pigments, 1998, 36(4):355-363.). The difference in activity between the two makes it difficult to improve the final color fixation rate of dyeing, which is only 65% ​​to 80%. In order to match the color fixation temperature of the two, dye scientists have tried to improve the reactivity of the halogenated s-triazine active group. One method is to replace the monochloro-s-triazine type active group with a monofluoro-s-triazine type active group. The fixation rate of such heterobi-active group dyes on cotton fibers exceeds 80% (Dyes and Dyeing, 2005, 42(2):1-4.). However, due to the strong corrosiveness and toxicity of the raw material cyanuric fluoride, its production and application are very limited. Another method is to introduce a substituent with weak electron-donating ability or strong electron-withdrawing ability on the triazine ring. This will reduce the electron cloud density of the carbon atom connected to the chlorine atom on the ring and increase the ability of the active group to undergo nucleophilic substitution reaction. At present, the main research focuses on the effects of nicotinic acid substituents, alkoxy substituents, cyanamide substituents, and sulfonamide substituents on the activity of monochloro-s-triazine. Among them, Zhang et al. prepared orange, red, and blue ethoxy-containing heterodiactive dyes by introducing alkoxy groups with weak electron-donating ability as substituents in the triazine ring. After dyeing tests, the dye uptake and reaction rates of all dyes were above 90%, and the fixation rate reached above 87% (Coloration Technology. 2019(135):336–348.). The heterodiactive dyes achieved good fixation effects, but when three or more reactive groups were introduced into the dye molecule, the dye molecule would be too large, resulting in a decrease in the diffusion and migration of the dye, leading to a decrease in the fixation rate and lift rate of the dye.

[0005] To further improve the fixation rate of reactive dyes, Zhang et al., building on their research on polymer dyes, developed a series of polyvinylamine-based macromolecules (Crosslinking Dyes [M]. New York: John Wiley & Sons Inc., 2013). The highly reactive amino groups in the polymers can be attached to chromophores and reactive groups, and can also serve as crosslinking reactive groups. By grafting chromophores that meet color and reactivity requirements, a series of full-spectrum macromolecular cross-linked dyes were created. Furthermore, these macromolecular dyes contain three or more reactive groups, which react with the fiber during the fixation reaction. Crosslinking reactions also occur between the macromolecular dyes and reactive groups not attached to the chromophore, forming crosslinked macromolecules on the fiber, achieving a nearly 100% fixation rate on the fiber. Among them, Yang Jingjing et al. used low-polymerization degree polyvinylamine prepared by Hofmann degradation of polyacrylamide as a polymer backbone to synthesize a series of polyacrylamide-co-vinylamine dyes with controllable solubility. These dyes were fixed with a crosslinker M, and the crosslinking fixation rate on cotton fibers was over 96% (Yang Jingjing. Synthesis and performance study of polyacrylamide-co-vinylamine dyes with controllable solubility [D].). Shan Bin et al. grafted dichloro-s-triazine-type chromophores onto two macromolecular backbones, poly(N-vinylformamide-co-vinylamine) and polyvinylamine-co-acrylic acid, to synthesize macromolecular self-crosslinking dyes, which achieved a fixation rate of nearly 100% for cotton fiber dyeing (Shan Bin. Synthesis and application of highly photostable polyvinylamine-based macromolecular self-crosslinking dyes [D].).

[0006] However, the synthesis of macromolecular dyes requires the use of macromolecules, which increases the complexity of the synthesis process. Therefore, we considered preparing a small-molecule dye that is relatively stable under conventional storage conditions and can self-polymerize on fibers under fixation conditions to form a macromolecular dye-like dye. We achieved this goal primarily by introducing an aminosilane coupling agent, a self-polymerizing and cross-linking substituent, onto the triazine ring. Under high-temperature, alkaline fixation conditions, this siloxane-containing reactive dye not only covalently bonds to cellulose fibers through the reactive groups but also bonds with each other through polycondensation of the siloxane groups, forming a cross-linked macromolecular dye structure on the fiber. This not only fixes partially hydrolyzed dyes on the fiber, improving dye fixation, but also enhances various fastness properties of the dyed fabric. The synthesis of such a dye does not involve the synthesis of macromolecules, resulting in a simple preparation process, and its water solubility can be adjusted by adjusting the water-soluble groups in the chromophore.

[0007] Currently, relatively little research has been conducted on the introduction of siloxane groups into dye molecules. However, Yu Ning et al. (Yu Ning. Synthesis of Silicone-Containing Reactive Disperse Dyes and Study on the Coloring Properties of Silicone Rubber [D]) designed and synthesized novel yellow, red, and purple silicon-containing reactive disperse dyes specifically for silicone rubber dyeing by combining azo disperse dye chromogens with 3-aminopropylmethyldimethoxysilane and 3-aminopropyltrimethoxysilane using cyanuric chloride as a linker. During the dyeing process, the reactive silicon-containing disperse dyes covalently bond to silicone rubber via Si-O bonds, achieving silicone rubber dyeing. This colored silicone rubber exhibits vibrant and rich colors, excellent mechanical properties, and outstanding color fastness.

[0008] However, this dye is specifically designed for dyeing silicone rubber and is primarily connected to the rubber via a silicon-oxygen bond. Its dye structure is completely water-insoluble, and the reactive groups serve only as bridging groups. However, there have been no reports of combining a water-soluble colorant with a silane coupling agent via cyanuric chloride or cyanuric fluoride to prepare a novel silicone-containing reactive dye for dyeing cellulose fibers. Therefore, the present invention, based on this approach, has developed a method for preparing and applying a silicone-containing reactive dye. Summary of the Invention

[0009] To address the above-mentioned issues, the present invention aims to provide a reactive dye containing a polycondensable siloxane component in its molecule. During the fixation process, the dye not only undergoes a fixation reaction with cotton fibers but also undergoes a polymerization reaction itself, thereby increasing the dye fixation rate and improving the properties of the dyed fabric. To achieve the above-mentioned objectives, the present invention adopts the following technical solutions:

[0010] A silicone-based reactive dye is a compound having the following structural formula I:

[0011]

[0012] in,

[0013] X is selected from Cl or F;

[0014] M1, M2, and M3 are each independently selected from one of methyl, ethyl, methoxy, ethoxy, and hydroxyl groups; A is a chromophore group selected from one of the following general structural formulas II to XII:

[0015]

[0016]

[0017] in,

[0018] R1, R3, R5, R8, R9, R 10 、R 15 are each independently selected from H or sulfonic acid;

[0019] R2 is selected from methyl, sulfonic acid, urea, acetamido, hydroxyl or carboxyl;

[0020] R4 is selected from H or Cl;

[0021] R6 is selected from H, carboxyl or formamide;

[0022] R7 is selected from H, C 1-4 Alkyl or hydroxyethyl;

[0023] R 11 、R 12 Each is independently selected from H, nitro, methyl, methylsulfonyl or methoxy;

[0024] R 13 、R 14 Each is independently selected from H, cyano, hydroxy, methylsulfonyl or acetoxy;

[0025] B, C, D, and E are each independently selected from

[0026] Where: R 16 、R 17 Each is independently selected from one of H, C1-C4 alkyl, C1-C4 alkoxy, sulfonic acid, nitro, cyano, carboxyl, C1-C4 amide, halogen or β-sulfate ethyl sulfone.

[0027] In the silicone-based reactive dye of the present invention, M1, M2, and M3 contain at least two alkoxy groups or two hydroxyl groups, which can undergo polycondensation under alkaline conditions for color fixation, so that the dyes are connected by covalent bonds.

[0028] Another object of the present invention is to provide a method for preparing the above-mentioned silicone-based reactive dye, comprising the following steps:

[0029] First, a dichloro-s-triazine or difluoro-s-triazine color body structure compound containing a chromophore group is synthesized; then, an amino silane coupling agent is slowly dripped into a dichloro-s-triazine or difluoro-s-triazine color body solution at 0-15° C., the temperature is raised to 20-40° C. for a condensation reaction, and after the reaction is completed, the pH is adjusted to neutral with a buffer salt, potassium acetate is added to precipitate a solid, the solid is settled, filtered, washed with ethanol, and dried to obtain the silicone-containing reactive dye.

[0030] Preferably, the amino-based silane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane or 3-aminopropylmethyldiethoxysilane.

[0031] Preferably, the molar ratio of the amino-based silane coupling agent to the dichloro-s-triazine or difluoro-s-triazine color body structure compound is 1 to 10:1.

[0032] Preferably, the pH value of the condensation reaction between the amino-based silane coupling agent and the dichloro-s-triazine or difluoro-s-triazine color body structure compound is 2-13.

[0033] Preferably, the dichloro-s-triazine or difluoro-s-triazine chromophore structure compound is prepared by the following method:

[0034] ① Cyanuric chloride or cyanuric fluoride is subjected to a first condensation reaction with H acid, J acid, or γ acid, and then aniline and its derivatives, naphthylamine and its derivatives, thiazole and benzothiazole derivatives, and anthraquinone derivatives are diazotized and coupled with the first condensation product;

[0035] ② Cyanuric chloride or cyanuric fluoride is first coupled with 2,4-diaminobenzenesulfonic acid or m-phenylenediamine disulfonic acid, and the coupling product is diazotized; then, pyrazolone and its derivatives, pyridone and its derivatives, aniline and its derivatives and H acid coupling products, N,N-diethylaniline and its derivatives are used as coupling liquids to couple with the above diazonium salts;

[0036] ③ Aniline and its derivatives or naphthylamine and its derivatives are diazotized and then coupled with m-ureaaniline, m-aminoacetanilide, m-toluidine, m-aminobenzoic acid, m-aminophenol and m-aminobenzenesulfonic acid, followed by condensation reaction with cyanuric chloride or cyanuric fluoride;

[0037] ④ Condensation of bromoamic acid with diaminobenzene and its derivatives under the catalysis of CuCl solution to obtain a color body, which is then condensed with cyanuric chloride or cyanuric fluoride.

[0038] The beneficial effects of the present invention are as follows: the cross-linking reaction conditions of the siloxane-based reactive dyes during dyeing are consistent with the color fixation conditions of the dyes on the fibers. Therefore, when color fixation is carried out under alkaline conditions, the dyes can not only complete the color fixation reaction with the fibers, but also complete the condensation cross-linking reaction of the siloxane-based reactive dyes, so that the dye molecules are connected by covalent bonds. Partially hydrolyzed dyes or dyes that have not completed color fixation can be attached to the fiber surface through cross-linking covalent bonds between dyes, thereby improving the color fixation rate of the dyes. The dyes provided by the present invention have a high color fixation rate and excellent various fastnesses during the dyeing process, greatly improving the utilization rate of the dyes, reducing the generation of dye liquor wastewater, and making up for the problems existing in traditional reactive dyes. This type of siloxane-based reactive dye has a simple structure and is relatively easy to synthesize, which is conducive to its application in industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1is the mass spectrum of Dye1, corresponding to Example 1;

[0040] Figure 2 is the UV-visible spectrum of Dye1;

[0041] Figure 3 is the infrared spectrum of Dye1;

[0042] Figure 4 is the mass spectrum of Dye2, corresponding to Example 8;

[0043] Figure 5 is the UV-visible spectrum of Dye2;

[0044] Figure 6 is the infrared spectrum of Dye2;

[0045] Figure 7 is the mass spectrum of Dye3, corresponding to Example 15;

[0046] Figure 8 is the UV-visible spectrum of Dye3;

[0047] Figure 9 is the infrared spectrum of Dye3;

[0048] Figure 10 Figure 2: Dye1 cross-linking performance exploration diagram

[0049] Figure 11 Digital photos of cotton fibers dyed with Dye1, Dye2, and Dye3. DETAILED DESCRIPTION

[0050] The following non-limiting examples may enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0051] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are all commercially available unless otherwise specified.

[0052] A silicone-based reactive dye is a compound having the following structural formula I:

[0053]

[0054] in,

[0055] X is selected from Cl or F;

[0056] M1, M2, and M3 are each independently selected from one of methyl, ethyl, methoxy, ethoxy, and hydroxyl groups;

[0057] A is a chromophore group selected from one of the following general structural formulas II to XII:

[0058]

[0059] in,

[0060] R1, R3, R5, R8, R9, R 10 、R 15 Each is independently selected from H or sulfonic acid group; R2 is selected from methyl, sulfonic acid group, urea group, acetylamino, hydroxyl group or carboxyl group;

[0061] R4 is selected from H or Cl;

[0062] R6 is selected from H, carboxyl or formamide;

[0063] R7 is selected from H, C 1-4 Alkyl or hydroxyethyl;

[0064] R 11 、R 12 Each is independently selected from H, nitro, methyl, methylsulfonyl or methoxy;

[0065] R 13 、R 14 Each is independently selected from H, cyano, hydroxy, methylsulfonyl or acetoxy;

[0066] B, C, D, and E are each independently selected from

[0067] Where: R 16 、R 17 Each is independently selected from one of H, C1-C4 alkyl, C1-C4 alkoxy, sulfonic acid, nitro, cyano, carboxyl, C1-C4 amide, halogen or β-sulfate ethyl sulfone.

[0068] The above-mentioned preparation method of the siloxane-containing reactive dye mainly involves reaction types including condensation reaction of cyanuric chloride or cyanuric fluoride, diazotization-coupling reaction, etc.

[0069] Among them, the chromophore with the general structural formula Ⅱ is an H acid type red chromophore; Ⅲ is a J acid or γ acid type orange chromophore; Ⅳ is an H acid disazo type blue chromophore; Ⅴ is an aniline derivative as a coupling component type yellow chromophore; Ⅵ is a pyrazolone type yellow chromophore; Ⅶ is a pyridone type yellow chromophore; VIII is a bromoamic acid type blue chromophore; Ⅸ is an anthraquinone azo type blue chromophore; X is a thiazole type blue chromophore; Ⅺ is a thiazole type purple-red chromophore, and XII is an N,N-diethylaniline type orange chromophore.

[0070] The silicone-based reactive dye of the present invention preferably has a chromophore selected from one of the following compounds:

[0071] ①H acid type red chromogen

[0072]

[0073] ② J acid or γ acid type orange chromophore

[0074]

[0075]

[0076] ③H acid disazo type blue chromogen

[0077]

[0078] ④ Aniline derivatives are coupled component type yellow chromogens

[0079]

[0080] ⑤ Pyrazolone type yellow chromogen

[0081]

[0082] ⑥Pyridone type yellow chromogen

[0083]

[0084] ⑦Bromoamic acid type blue chromogen

[0085]

[0086] ⑧Anthraquinone-type blue chromophore

[0087]

[0088] ⑨Thiazole blue chromophore

[0089]

[0090] ⑩ Thiazole-type purple-red chromophore

[0091]

[0092] N,N-Diethylaniline type orange color body

[0093]

[0094] The preparation method of the silicone-containing reactive dye described herein primarily involves a condensation reaction of cyanuric chloride or cyanuric fluoride and a diazotization-coupling reaction. The method comprises the following steps: first, synthesizing a dichloro-s-triazine or difluoro-s-triazine color body structure containing the aforementioned color body; then, slowly dripping an aminosilane coupling agent into the dichloro-s-triazine or difluoro-s-triazine color body solution at 0-15°C, raising the temperature to 20-40°C to allow the condensation reaction to proceed; after completion of the reaction, adjusting the pH to neutral with a buffer salt, adding potassium acetate to precipitate a solid, settling the solid, filtering it with suction, washing it with ethanol, and drying it to produce the silicone-containing reactive dye.

[0095] Among them, the preferred amino-based silane coupling agents are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane.

[0096] Among them, the ratio of the amount of the amino-based silane coupling agent to the substance having a dichloro-s-triazine type or difluoro-s-triazine type color body structure is preferably 1 to 10:1.

[0097] Among them, the pH value of the condensation reaction between the amino silane coupling agent and the dichloro-s-triazine type or difluoro-s-triazine type color body structure is preferably 2 to 13.

[0098] Among them, the preparation method of dichloro-s-triazine type or difluoro-s-triazine type color body structure mainly includes the following aspects:

[0099] ① Cyanuric chloride or cyanuric fluoride is subjected to a first condensation reaction with H acid, J acid, or γ acid, and then aniline and its derivatives, naphthylamine and its derivatives, thiazole and benzothiazole derivatives, and anthraquinone derivatives are diazotized and coupled with the first condensation product;

[0100] ②Cyanuric chloride or cyanuric fluoride is first coupled with 2,4-diaminobenzenesulfonic acid or m-phenylenediamine disulfonic acid, and the coupling product is diazotized. Subsequently, the acid coupling products of pyrazolone and its derivatives, pyridone and its derivatives, aniline and its derivatives with H acid, and N,N-diethylaniline and its derivatives are used as coupling liquids to couple with the above-mentioned diazonium salts;

[0101] ③ Aniline and its derivatives or naphthylamine and its derivatives are diazotized and then coupled with m-ureaaniline, m-aminoacetanilide, m-toluidine, m-aminobenzoic acid, m-aminophenol and m-aminobenzenesulfonic acid, followed by condensation reaction with cyanuric chloride or cyanuric fluoride;

[0102] ④ Condensation of bromoamic acid with diaminobenzene and its derivatives under the catalysis of CuCl solution to obtain a color body, which is then condensed with cyanuric chloride or cyanuric fluoride.

[0103] The silicone-containing reactive dyes of the present invention have a wide range of applications as dyes in the art, such as fiber dyeing, digital printing, inkjet printing, etc. In particular, the dyes of the present invention have a good application effect in fiber dyeing.

[0104] The fiber dyeing process is as follows: according to the chromaticity of 0.5-10%, preferably 2%, the bath ratio is 1:5-30, preferably 1:20. Use a mass fraction of 1% to 5% Na2CO3 solution or NaHCO3 solution for color fixation, preferably 2%, soak the cotton fiber in the above dye solution, one dip and one pad, two dips and two pads, or three dips and three pads, and wash the fiber after pad dyeing after baking or steaming. After soap boiling, take out the cloth sample and wash it with water, collect the washing and soaping liquid, measure its absorbance, and calculate the color fixation rate of the dye using the working curve. The color fixation rate of the dye pad dyeing is referred to the following formula:

[0105]

[0106] Where: F is the dye fixation rate, %; m0 is the original mass of the cloth sample, g; m1 is the mass of the cloth sample after padding, g; ω is the mass fraction of the dye in the initial dye solution; A is the absorbance of the water and soap solutions; V is the volume of the water and soap solutions, L; ε is the slope of the standard curve of the macromolecular dye, that is, the gram absorption coefficient of the dye, L·g -1 cm -1 .

[0107] Examples 1 to 6

[0108] Chromophores 1# to 6# correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 1.

[0109] Table 1 Structural formula of the silicone-containing reactive dyes synthesized in Examples 1 to 6

[0110]

[0111]

[0112] The specific synthesis steps are as follows:

[0113] Condensation reaction of cyanuric chloride and H acid: weigh 1.90g (0.0103mol) of cyanuric chloride and 20-30g of small ice cubes, stir mechanically at 0-5°C until emulsified, then pour 30mL of neutral aqueous solution containing 3.43g of H acid (0.01mol) into the mixture for reaction, adjust the pH to 4-5 with 10% Na2CO3 solution, and detect with Ehrlich reagent that the intersection of the seepage circle is colorless, confirming that the reaction is complete, and filter the reaction solution to remove impurities;

[0114] Diazotization of the para-ester: Adjust 30 mL of an aqueous solution containing 2.87 g of the para-ester (0.0102 mol) to neutrality with 10% NaCO solution. Add 0.73 g of sodium nitrite (0.0105 mol) and dissolve in the solution, then cool to 0-5°C. Quickly pour the mixture into 2.5 mL of 37% concentrated hydrochloric acid, cooled to 0-5°C. Keep the mixture until Congo red and starch potassium iodide test paper turn blue. After 30 minutes, use Ehrlich's reagent to detect the end point of the reaction. Destroy excess nitrous acid with sulfamic acid.

[0115] Coupling reaction: The above diazonium salt was slowly added dropwise to the condensation product of cyanuric chloride and H acid over 40 minutes. The reaction was carried out at 0-5°C. The pH was controlled at 6.5-7 with 10% Na2CO3 solution. The reaction endpoint was detected by the osmotic circle method to obtain a red dichloro-s-triazine color body solution.

[0116] Condensation reaction of dichloro-s-triazine color body with 3-aminopropyltriethoxysilane: The dichloro-s-triazine color body solution obtained above was stirred in an ice bath. 2.32 g (0.0105 mol) of 3-aminopropyltriethoxysilane was slowly added dropwise over 60 minutes. The temperature was slowly raised to 30°C to allow the condensation reaction to proceed. The pH was maintained at 7.5-8 using a 10% Na2CO3 solution throughout the reaction. The reaction was complete by thin-layer chromatography (TLC) (developing solvent: n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction, the pH of the solution was adjusted to neutral, and potassium acetate was added to precipitate the dye. The solution was filtered, and the filter cake was rinsed with ethanol to remove the potassium acetate. The resulting solid was freeze-dried to yield a red solid in 95% yield.

[0117] The red reactive dyes containing silicone groups were obtained by using o-aminobenzenesulfonic acid, aniline-2,5-disulfonic acid, p-cyanoaniline, sulfonated Tobias acid and K acid to replace the para-ester as diazo component.

[0118] Examples 7 to 14

[0119] The 7# to 14# chromophores correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 2.

[0120] Table 2 Structural formula of the silicone-containing reactive dyes synthesized in Examples 7 to 14

[0121]

[0122]

[0123] The specific synthesis steps are as follows:

[0124] Condensation reaction of cyanuric chloride and J acid: weigh 1.90g (0.0103mol) of cyanuric chloride and 20-30g of small ice cubes, stir mechanically at 0-5℃ until emulsified, then pour 30mL of neutral aqueous solution containing 2.39g of J acid (0.01mol) into the mixture for reaction, adjust the pH to 4-5 with 10% Na2CO3 solution, and detect with Ehrlich reagent that the intersection of the seepage circle is colorless, confirming that the reaction is complete;

[0125] Diazotization reaction of para-ester: the same as the preparation in Example 1.

[0126] Coupling reaction: Slowly add the above diazonium salt dropwise to the condensation product of cyanuric chloride and J acid over 40 minutes. The reaction is carried out at 0-5°C. The pH is controlled at 6.5-7 with 10% Na2CO3 solution. The reaction endpoint is detected by the ring penetration method to obtain an orange dichloro-s-triazine color body solution.

[0127] Condensation reaction of dichloro-s-triazine color body with 3-aminopropyltriethoxysilane: The dichloro-s-triazine color body solution obtained above was stirred in an ice bath. 2.32 g (0.0105 mol) of 3-aminopropyltriethoxysilane was slowly added dropwise over 60 minutes. The temperature was slowly raised to 30°C for the condensation reaction. The pH was maintained at 7.5-8 using a 10% Na2CO3 solution throughout the reaction. The reaction was complete by thin-layer chromatography (TLC) (developing solvent: n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction, the pH of the solution was adjusted to neutral, and potassium acetate was added to precipitate the dye. The solution was filtered, and the filter cake was rinsed with ethanol to remove the potassium acetate. The resulting solid was freeze-dried to yield an orange solid in 84% yield.

[0128] Sulfonated para-ester, o-aminobenzenesulfonic acid, and sulfonated Tobias acid were used instead of para-ester as diazo components to obtain corresponding silicone-containing reactive dyes 8# to 10#; γ-acid was used instead of J acid as condensation component to obtain corresponding orange silicone-containing reactive dyes 11# to 14#.

[0129] Examples 15 to 18

[0130] The chromophores 15# to 18# correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 3.

[0131] Table 3 Structural formula of the silicone-containing reactive dyes synthesized in Examples 15 to 18

[0132]

[0133]

[0134] The specific synthesis steps are as follows:

[0135] Diazotization reaction of para-ester: the same as the preparation in Example 1.

[0136] Acid coupling reaction of para-ester diazonium salt with H acid: 30 mL of neutral aqueous solution containing 3.43 g (0.01 mol) of H acid was slowly added dropwise to the above diazonium salt over 2 h, the reaction temperature was maintained at 0-5 ° C, the pH value was maintained at 1-2, and the end point of the reaction was detected by ring penetration to obtain the product of the coupling of the para-ester and the ortho-position of the amino group of H acid.

[0137] Condensation reaction of cyanuric chloride and 2,4-diaminobenzenesulfonic acid: weigh 1.90g (0.0103mol) of cyanuric chloride and 20-30g of small ice cubes, mechanically stir at 0-5°C until emulsified, then pour 30mL of a neutral aqueous solution containing 1.88g of 2,4-diaminobenzenesulfonic acid (0.01mol) into the mixture for reaction, adjust the pH to 4-5 with 10% Na2CO3 solution, and confirm by thin layer chromatography that the 2,4-diaminobenzenesulfonic acid is completely consumed, and the reaction is complete;

[0138] Diazotization of the condensation product of cyanuric chloride and 2,4-diaminobenzenesulfonic acid: Adjust the pH of the above product to 7-7.5. Add 0.73g of sodium nitrite (0.0105 mol) and dissolve it in the above solution, then cool it to 0-5°C. Quickly pour the mixture into 2.5mL of 37% concentrated hydrochloric acid cooled to 0-5°C to allow the reaction to proceed. Continue the reaction until Congo red and starch potassium iodide test paper turn blue. After 30 minutes, use Ehrlich's reagent to detect the end point of the reaction. Destroy the excess nitrous acid with sulfamic acid.

[0139] Second coupling reaction: The above diazonium salt was slowly added dropwise to the above first coupling product over 40 minutes, and the reaction was carried out at 0-5°C. The pH was controlled at 6.5-7 with 10% Na2CO3 solution. Thin layer chromatography was used to determine whether the reactants were completely consumed to obtain a blue dichloro-s-triazine color body solution.

[0140] Condensation reaction of dichloro-s-triazine color body with 3-aminopropyltriethoxysilane: The dichloro-s-triazine color body solution obtained above was stirred in an ice bath. 2.32 g (0.0105 mol) of 3-aminopropyltriethoxysilane was slowly added dropwise over 60 minutes. The temperature was slowly raised to 30°C to allow the condensation reaction to proceed. The pH was maintained at 7.5-8 using a 10% Na2CO3 solution throughout the reaction. The reaction was complete by thin-layer chromatography (TLC) (developing solvent: n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction, the pH of the solution was adjusted to neutral, and potassium acetate was added to precipitate the dye. The solution was filtered, and the filter cake was rinsed with ethanol to remove the potassium acetate. The resulting blue solid was freeze-dried to yield 87% yield.

[0141] By using o-aminobenzenesulfonic acid and p-nitroaniline instead of the para-ester as the diazo component, the corresponding blue reactive dyes containing silicone groups 16# to 17# were obtained; by using m-phenylenediamine disulfonic acid instead of 2,4-diaminoaniline as the condensation component, the corresponding blue reactive dye containing silicone groups 18# was obtained.

[0142] Examples 19 to 22

[0143] The chromophores 19# to 22# correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 4.

[0144] Table 4 Structural formula of the silicone-containing reactive dyes synthesized in Examples 19 to 22

[0145]

[0146] The specific synthesis steps are as follows:

[0147] Diazotization reaction of para-ester: the same as the preparation in Example 1.

[0148] Coupling reaction: The above diazonium salt was slowly added dropwise to 30 mL of an aqueous solution containing 1.51 g of m-ureaaniline (0.01 mol) over 40 min. The reaction was carried out at 0-5°C. The pH was controlled at 6.5-7 with 10% Na2CO3 solution. The reaction endpoint was detected by the ring seepage method.

[0149] Condensation reaction of cyanuric chloride and coupling product: Weigh 1.90 g (0.0103 mol) of cyanuric chloride and 20-30 g of small ice cubes, mechanically stir at 0-5°C until emulsified, then add the coupling product for condensation reaction. Adjust the pH to 4-5 with 10% Na2CO3 solution. Complete reaction is confirmed by thin layer chromatography to obtain a yellow dichloro-s-triazine color body solution.

[0150] Condensation reaction of dichloro-s-triazine color body with 3-aminopropyltriethoxysilane: The dichloro-s-triazine color body solution obtained above was stirred in an ice bath. 2.32 g (0.0105 mol) of 3-aminopropyltriethoxysilane was slowly added dropwise over 60 minutes. The temperature was slowly raised to 30°C for the condensation reaction. The pH was maintained at 7.5-8 using a 10% Na2CO3 solution throughout the reaction. The reaction was complete by thin-layer chromatography (TLC) (developing solvent: n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction, the pH of the solution was adjusted to neutral, and potassium acetate was added to precipitate the dye. The solution was filtered, and the filter cake was rinsed with ethanol to remove the potassium acetate. The resulting solid was freeze-dried to yield a yellow solid in 86% yield.

[0151] The corresponding yellow reactive dyes containing silicone groups 20# to 22# were obtained by using sulfonated para-ester, o-aminobenzenesulfonic acid and sulfonated Tobias acid to replace the para-ester as diazo component.

[0152] Examples 23 to 26

[0153] Chromophores 23# to 26# correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 5.

[0154] Table 5 Structural formula of the silicone-containing reactive dyes synthesized in Examples 23 to 26

[0155]

[0156]

[0157] The specific synthesis steps are as follows:

[0158] Condensation reaction of cyanuric chloride and 2,4-diaminobenzenesulfonic acid: the same as the preparation in Example 15.

[0159] Diazotization reaction of the condensation product of cyanuric chloride and 2,4-diaminobenzenesulfonic acid: the same as the preparation in Example 15.

[0160] Coupling reaction: The above diazonium salt was slowly added dropwise over 40 min to 30 mL of a neutral aqueous solution containing 2.54 g of 1-(4-sulfonic acid phenyl)-3-methyl-5-pyrazolone (0.01 mol). The reaction was carried out at 0-5°C. The pH was controlled at 6.5-7 with 10% Na2CO3 solution. The reaction endpoint was detected by the osmotic circle method to obtain a yellow dichloro-s-triazine color body solution.

[0161] Condensation reaction of dichloro-s-triazine color body with 3-aminopropyltriethoxysilane: The dichloro-s-triazine color body solution obtained above was stirred in an ice bath. 2.32 g (0.0105 mol) of 3-aminopropyltriethoxysilane was slowly added dropwise over 60 minutes. The temperature was slowly raised to 30°C to allow the condensation reaction to proceed. The pH was maintained at 7.5-8 using a 10% Na2CO3 solution throughout the reaction. The reaction was complete by thin-layer chromatography (TLC) (developing solvent: n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction, the pH of the solution was adjusted to neutral, and potassium acetate was added to precipitate the dye. The solution was filtered, and the filter cake was rinsed with ethanol to remove the potassium acetate. The resulting solid was freeze-dried to yield a yellow solid in 82% yield.

[0162] By using 2,5-dichloropyrazolone instead of 1-(4-sulfonic acid phenyl)-3-methyl-5-pyrazolone as the coupling component, the corresponding yellow reactive dye containing silicone base 24# is obtained; by using m-phenylenediamine disulfonic acid instead of 2,4-diaminoaniline as the condensation component, the corresponding yellow reactive dye containing silicone base 25# to 26# are obtained.

[0163] Examples 27-28

[0164] The 27#~28# chromophores correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 6.

[0165] The method is the same as that of Example 25, except that pyridone is used instead of pyrazolone in Example 25 to obtain the corresponding yellow silicone-containing reactive dyes 27# to 28#. Other conditions are the same as those of Example 25.

[0166] Table 6 Structural formula of the silicone-containing reactive dyes synthesized in Examples 27 to 28

[0167]

[0168] Examples 29-30

[0169] The 29#~30# chromophores correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 7.

[0170] Table 7 Structural formula of the silicone-containing reactive dyes synthesized in Examples 29 to 30

[0171]

[0172]

[0173] The specific synthesis steps are as follows:

[0174] In a 100 mL four-necked flask equipped with a stirrer and a thermometer, 3.82 g of bromoamic acid (0.01 mol) and 40 mL of water were added, and the mixture was heated to 90° C. while stirring to dissolve. 20 mL of an aqueous solution containing 1.84 g of m-phenylenediamine monosulfonic acid (0.01 mol) was added. Under good stirring, an appropriate amount of CuCl solution was added at 85° C. as a catalyst. The pH value of the reaction was adjusted to 8-9 with 10% sodium carbonate solution. The reaction was allowed to proceed for 1 hour. After the reaction was completed, a certain amount of activated carbon was added for adsorption, and the mixture was hot filtered. The filtrate was treated, salted out, filtered, and dried to obtain the pre-dye product.

[0175] Condensation reaction: Weigh 1.90g (0.0103mol) of cyanuric chloride and 20-30g of small ice cubes, mechanically stir at 0-5°C until emulsified, then slowly add 40mL of an aqueous solution (0.01mol) containing the pre-dye product dropwise to the above-mentioned slurry, adjust the pH to 4-5 with a 10% mass fraction of Na2CO3 solution, and detect the reaction end point by the ring seepage method. After the reaction is completed, a blue dichloro-s-triazine color body solution is obtained.

[0176] Condensation reaction of dichloro-s-triazine color body with 3-aminopropyltriethoxysilane: The dichloro-s-triazine color body solution obtained above was stirred in an ice bath. 2.32 g (0.0105 mol) of 3-aminopropyltriethoxysilane was slowly added dropwise over 60 minutes. The temperature was slowly raised to 30°C to allow the condensation reaction to proceed. The pH was maintained at 7.5-8 using a 10% Na2CO3 solution throughout the reaction. The reaction was complete by thin-layer chromatography (TLC) (developing solvent: n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction, the pH of the solution was adjusted to neutral, and potassium acetate was added to precipitate the dye. The solution was filtered, and the filter cake was rinsed with ethanol to remove the potassium acetate. The resulting blue solid was freeze-dried to yield 85% yield.

[0177] By using p-phenylenediamine instead of m-phenylenediamine monosulfonic acid and keeping other conditions the same, the corresponding blue silicone-containing reactive dye 30# can be obtained.

[0178] Examples 31-32

[0179] The 31#~32# chromophores correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 8.

[0180] Table 8 Structural formula of the silicone-containing reactive dyes synthesized in Examples 31 to 32

[0181]

[0182] The specific synthesis steps are as follows:

[0183] Condensation reaction of cyanuric chloride and H acid: the same as the preparation in Example 1.

[0184] Diazotization reaction: Weigh 3.30g of 1-(4-aminophenylamino)-4-hydroxyanthraquinone (0.01mol), add 20mL of water and 2.5mL of 37% concentrated hydrochloric acid, heat to 70-80°C and stir until completely dissolved. Rapidly cool to 0-5°C and add 0.73g of sodium nitrite (0.0105mol). After addition, the solution should remain acidic as detected by Congo red reagent and turn blue on starch potassium iodide paper. After 30 minutes of reaction, use Ehrlich reagent to detect the reaction endpoint, and destroy the excess sodium nitrite with aminosulfonic acid.

[0185] Coupling Reaction: Slowly add the above-mentioned diazonium salt dropwise to a reaction mixture of cyanuric chloride and H-acid over 40 minutes. The reaction is carried out at 0-5°C. The pH is controlled at 6.5-7 using a 10% Na2CO3 solution. The reaction endpoint is detected by the osmotic circle method to obtain a blue dichloro-s-triazine color-forming solution. After the reaction is completed, potassium acetate is added to precipitate the dye. The solution is filtered, and the filter cake is rinsed with ethanol to remove the potassium acetate. The solution is then dried to obtain a blue solid.

[0186] Condensation reaction of dichloro-s-triazine color body with 3-aminopropyltriethoxysilane: The dichloro-s-triazine color body solution obtained above was stirred in an ice bath. 2.32 g (0.0105 mol) of 3-aminopropyltriethoxysilane was slowly added dropwise over 60 minutes. The temperature was slowly raised to 30°C for the condensation reaction. The pH was maintained at 7.5-8 using a 10% Na2CO3 solution throughout the reaction. The reaction was complete by thin-layer chromatography (TLC) (developing solvent: n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction, the pH of the solution was adjusted to neutral, and potassium acetate was added to precipitate the dye. The solution was filtered, and the filter cake was rinsed with ethanol to remove the potassium acetate. The resulting blue solid was freeze-dried to yield 54% yield.

[0187] Examples 33 to 38

[0188] The 33# to 38# chromophores correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 9.

[0189] The method was the same as in Example 1, except that different thiazole and benzothiazole derivatives were used instead of the para-ester as the diazo component to obtain the corresponding blue silicone-containing reactive dyes 33#-34# and purple silicone-containing reactive dyes 35#-38#. Other conditions were the same as in Example 1.

[0190] Table 9 Structural formula of the silicone-containing reactive dyes synthesized in Examples 33 to 38

[0191]

[0192]

[0193] Examples 39 to 42

[0194] The 39# to 42# chromophores correspond to the preparation of silicone-based reactive dyes, and their specific structures are shown in Table 10.

[0195] The method was the same as in Example 25, except that different N,N-diethylaniline derivatives were used instead of 1-(4-sulfonate phenyl)-3-methyl-5-pyrazolone as the coupling component to obtain the corresponding orange silicone-containing reactive dyes 39# to 42#. Other conditions were the same as in Example 25.

[0196] Table 10 Structural formula of the silicone-containing reactive dyes synthesized in Examples 39 to 42

[0197]

[0198] Examples 43 to 84

[0199] The preparation method of monofluoro-s-triazine type silicone-containing reactive dye is the same as that of Examples 1 to 42, except that cyanuric fluoride is used instead of cyanuric chloride as the reactant, and the other conditions are the same as those of Examples 1 to 42.

[0200] Example 85

[0201] Taking the dye Dye1 synthesized in Example 1 as an example, the cross-linking performance of the siloxane-containing dye under fixation conditions was explored.

[0202] The dye was discharged from the pad-dyed and dried fabric sample, and the dye after fixation and the original dye were analyzed by thin layer chromatography to determine the fixation status. The specific implementation details are as follows:

[0203] A dye solution of 20 g / L Dye1 dye and 20 g / L Na2CO3 was prepared. Fabric samples were padded in the dye solution and then baked at 60°C for 10 minutes. The dried fabric samples were chopped and then subjected to high-concentration urea and DMF, respectively, for high-temperature immersion and color discharge at 90°C. The color of the liquid after color discharge was still very light, making thin-layer chromatography analysis impossible.

[0204] Example 86

[0205] Taking the dye Dye1 synthesized in Example 1 as an example, the cross-linking performance of the siloxane-containing dye under fixation conditions was explored.

[0206] The dyed fabric samples were replaced with silica gel plates coated with dye solution for drying and steaming. The dye after fixation and the original dye were analyzed by thin layer chromatography to determine the fixation status. The specific implementation details are as follows:

[0207] A solution of 20g / L dye and 20g / L Na2CO3 was evenly coated on a silica gel plate. The plate was then baked at 60°C for 10 minutes and then steamed for 30 minutes, simulating the drying and steaming process of a dyed fabric sample. The silica gel powder was scraped off and ultrasonically dispersed evenly. Thin-layer chromatography was used to analyze the small-molecule siloxane-containing dye and the dye after the fixation process. The Rf value of the small-molecule siloxane-containing red dye was 0.58, while the Rf value of the dye after the fixation process was 0. This confirms that siloxane dyes can condense after drying and steaming to form a cross-linked macromolecular dye structure. Due to the larger molecular weight of the cross-linked product, its polarity is reduced, resulting in an Rf value of 0.

[0208] Examples 87 to 90

[0209] Taking the three silicone-containing reactive dyes Dye1, Dye2, and Dye3 synthesized in Examples 1, 8, and 15 as examples, cotton fibers were dyed. The structural formulas of Dye1, Dye2, and Dye3 are as follows:

[0210]

[0211] The comparative dye was used to dye the cotton fiber under the same experimental conditions. The structure of the comparative dye Dye4 is as follows:

[0212]

[0213] Dyeing experiment: Weigh the above three silicone-based reactive dyes and comparative dyes to prepare a 20g / L solution, and add 2% sodium bicarbonate solution as a fixing agent. Take accurately weighed cotton fiber (2g) and soak it in 50mL of dye solution, immerse and roll it, then bake and dry the cloth sample at 60℃ and steam it for 30min. After dyeing, wash the cloth sample with water and collect the residual liquid to measure the absorbance. Place the washed cloth sample in 0.2% soap solution, boil it at 95℃ for 10min, take out the cloth sample and wash it thoroughly with water, collect the residual liquid, and measure its absorbance. In addition, the dye fixation rate is measured based on the dye concentration in the dye solution, the cloth sample liquid rate and the dye absorption coefficient. The color fixation rate of dye roller dyeing refers to the following formula:

[0214]

[0215] Where: F is the dye fixation rate, %; m0 is the original mass of the cloth sample, g; m1 is the mass of the cloth sample after padding, g; ω is the mass fraction of the dye in the initial dye solution; A is the absorbance of the water and soap solutions; V is the volume of the water and soap solutions, L; ε is the slope of the standard curve of the macromolecular dye, that is, the gram absorption coefficient of the dye, L·g -1 cm -1 .

[0216] According to the above dyeing conditions, the dyeing results of the above 4 dyes are shown in Table 11.

[0217] Table 11 Fixation rate and color fastness of dyeing

[0218]

[0219] Conclusion: The present invention develops a new silicone-based reactive dye and applies it to the dyeing of cellulose fibers. The dyeing results show that compared with traditional reactive dyes, this dye has higher fixation rate and staining fastness, reduces production costs, and reduces environmental pollution during the dye application process. It has the value of industrial production and application.

Claims

1. A method for dyeing fibers using silicone-based reactive dyes, characterized in that: To a solution of a silicon-containing reactive dye having a mass fraction of 0.5 to 10%, 1% to 5% by mass of Na2CO3 or NaHCO3 is added as a fixing agent, and cotton fibers are soaked in the dye solution at a bath ratio of 1:5 to 30, and the dyeing is performed by one dip and one padding, two dips and two paddings, or three dips and three paddings. The pad-dyed fibers are then baked or steamed, washed, soaped, washed again, and dried to obtain a dyed fabric sample, wherein: The silicone-based reactive dye is a compound having the following structural formula I: Formula I in, X is selected from Cl or F; M1, M2, and M3 are each independently selected from one of methyl, ethyl, methoxy, ethoxy, and hydroxyl groups; A is a chromophore group selected from one of the following general structural formulas II to XII: Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ Ⅶ Ⅷ Ⅸ Ⅹ Ⅺ Ⅻ in, R1, R3, R5, R8, R9, R 10 、R 15 is a sulfonic acid group; R2 is selected from methyl, sulfonic acid, urea, acetamido, hydroxyl or carboxyl; R4 is selected from H or Cl; R6 is selected from H, carboxyl or formamide; R7 is selected from H, C 1-4 Alkyl or hydroxyethyl; R 11 、R 12 Each is independently selected from H, nitro, methyl, methylsulfonyl or methoxy; R 13 、R 14 Each is independently selected from H, cyano, hydroxy, methylsulfonyl or acetoxy; B, C, D, and E are each independently selected from or Where: R 16 、R 17 Each is independently selected from one of H, C1~C4 alkyl, C1~C4 alkoxy, sulfonic acid, nitro, cyano, carboxyl, C1~C4 amide, halogen or β-sulfate ethyl sulfone; The silicone-containing reactive dye is prepared according to the following method: first, a dichloro-s-triazine or difluoro-s-triazine color body structure compound containing a chromophore group is synthesized; then, an amino silane coupling agent is slowly dripped into a dichloro-s-triazine or difluoro-s-triazine color body solution at 0-15°C, the temperature is raised to 20-40°C for a condensation reaction, and after the reaction is completed, the pH is adjusted to neutral with a buffer salt, potassium acetate is added to precipitate a solid, the solid is settled, filtered, washed with ethanol, and dried to obtain the silicone-containing reactive dye.

2. The method according to claim 1, characterized in that The M1, M2, and M3 contain at least two alkoxy groups or two hydroxyl groups.

3. The method according to claim 2, characterized in that The alkoxy or hydroxyl groups in M1, M2 and M3 can undergo condensation polymerization under alkaline conditions for color fixation, so that the dyes are connected by covalent bonds.

4. The method according to claim 1, wherein The amino silane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane or 3-aminopropylmethyldiethoxysilane.

5. The method according to claim 1, wherein The amount ratio of the amino silane coupling agent to the dichloro-s-triazine type or difluoro-s-triazine type color body structure compound is 1-10:

1.

6. The method according to claim 1, wherein The pH value of the condensation reaction between the amino silane coupling agent and the dichloro-s-triazine type or difluoro-s-triazine type color body structure compound is 2-13.

7. The method according to claim 1, characterized in that The dichloro-s-triazine or difluoro-s-triazine color body structure compound is prepared according to the following method: S1, cyanuric chloride or cyanuric fluoride is subjected to a first condensation with H acid, J acid, or γ acid, and then aniline and its derivatives, naphthylamine and its derivatives, thiazole and benzothiazole derivatives, or anthraquinone derivatives are diazotized and coupled with the first condensation product; S2, cyanuric chloride or cyanuric fluoride is first coupled with 2,4-diaminobenzenesulfonic acid or m-phenylenediamine disulfonic acid, and the coupling product is diazotized; then the acid coupling product of pyrazolone and its derivatives, pyridone and its derivatives, aniline and its derivatives with H acid, N,N -Diethylaniline and its derivatives as coupling liquids to carry out coupling reaction with the above-mentioned diazonium salts; S3, diazotizing aniline and its derivatives or naphthylamine and its derivatives, coupling with m-ureaaniline, m-aminoacetanilide, m-toluidine, m-aminobenzoic acid, m-aminophenol and m-aminobenzenesulfonic acid, and then condensing with cyanuric chloride or cyanuric fluoride; S4, condensing bromoamic acid with diaminobenzene and its derivatives under the catalysis of CuCl solution to obtain a color body, and then condensing the bromoamic acid with cyanuric chloride or cyanuric fluoride.

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