Direct coupling type double-chromosome disperse dye as well as synthesis method and application thereof

Abstract

The invention provides a direct coupling type double-chromophore disperse dye as well as a synthesis method and application thereof, and belongs to the technical field of disperse dyes. Introducing a reaction active group into the coupling component I to obtain a coupling component I containing the reaction active group; directly coupling a coupling component II with a reaction site with a coupling component I containing a reaction active group to obtain a coupling component with double coupling sites; the coupling component of the double coupling sites and the diazo component are subjected to bilateral coupling, and the direct coupling type double-chromophoric disperse dye is obtained.

Description

Technical Field

[0001] This application relates to a direct-coupled dichromatic disperse dye, its synthesis method, and its application, belonging to the field of disperse dye technology. Background Technology

[0002] Disperse dyes are common insoluble dyes, primarily used for dyeing hydrophobic fibers such as polyester, nylon, and acetate. Azo-structured disperse dyes account for more than half of the disperse dye market and are a hot research topic in the dyeing field. With the advancement of the textile market towards high-end and specialized products, high-performance disperse dyes are showing a significant demand. Traditional monoazo dyes are struggling to meet the increasing performance requirements of dyed textiles, especially for blended fibers, where conventional disperse dyes are difficult to apply deeply and quickly, becoming one of the industry's pain points.

[0003] Diazo dyes are a common method for improving dye performance. Diazo dyes obtained through two-step diazo coupling achieve higher molecular weights and stronger intermolecular forces, increasing the bonding strength between the dye and the fiber. However, the synthesis process of diazo dyes is very cumbersome and inefficient. The product obtained after the first diazo coupling step is essentially a disperse dye with poor solubility. It is difficult to completely diazotize during the second diazo coupling process, resulting in an imbalance of the molar ratio during the second coupling. The crude product contains many impurities, and separation is time-consuming and labor-intensive. Coupled with the high pollution associated with the dye industry itself, the production process of diazo dyes is difficult to meet green chemistry production standards.

[0004] Dichromatic dyes are a new type of high molecular weight dye that links two identical or different chromophores together through linking groups.

[0005] Current research on dichromatic dyes primarily utilizes reactive dyes, fluorescent dyes, and natural dyes such as gardenia blue, with the two chromophores typically being azo dyes. However, these dichromatic dyes suffer from several drawbacks. The linker is often a benzene ring derivative, resulting in a large molecular weight. Furthermore, the two chromophores themselves can easily lead to excessively large molecular volumes, resulting in high melting points, difficult staining, and poor dyeing power. In addition, the structure of the linker also influences the overall application performance of the dye, introducing unpredictable factors into the dye molecule design process. Summary of the Invention

[0006] In view of this, this application provides a direct-coupled bichromatic disperse dye, its synthesis method and application. This disperse dye removes the linker portion from the bichromatic dye and uses a method in which the coupling components are directly linked in a non-conjugated structure. This solves the problems of excessively large disperse dye molecules, difficult dyeing, poor lifting power and unpredictable performance caused by the overall conjugation of existing bichromatic dyes containing linkers.

[0007] Specifically, this application is implemented through the following scheme: The applicant's primary objective is to provide a directly coupled bichromoplasmic disperse dye with the following general structural formula: , The Ar-N=N- is obtained by diazotization of the following groups: , R1, R2, and R3 are independently selected from any one of H, NO2, CN, Cl, Br, OCH3, and OCOCH3; R4, R5, R8, and R9 are independently selected from any one of H, CH3, OCH3, Cl, and Br; R6 and R7 are independently selected from any one of H, CN, CH3, Bn, OCOCH3, and COOCH3; X is either O or NH; Q, Y, and Z are independently selected from any one of C, N, and S; n = 1~5.

[0008] Specifically, the preferred structural formulas for directly coupled dichromatic disperse dyes are as follows: .

[0009] The applicant's second objective is to provide a method for synthesizing the aforementioned directly coupled dichromatic disperse dye, the steps of which are as follows: Step 1: Introduce reactive groups into coupling component 1 to obtain coupling component 1 (f) containing reactive groups.

[0010] Step 2: Coupled component 2 (g) with a reactive site is directly coupled to coupled component 1 (f) containing a reactive group to obtain a coupled component (h) with two coupling sites. The reaction formula for the coupling component (h) at the synthetic dual coupling site is expressed as follows: .

[0011] Step 3: The coupling component at the dual coupling site is bilaterally coupled with the diazo component to obtain a directly coupled dichromatic disperse dye.

[0012] Furthermore, as a preferred option: In step one, Add an alkaline inorganic salt to N-ethylaniline or its derivative (a) and stir to mix evenly. Then add an electrophilic reagent (b) and react to obtain intermediate (c). After mixing intermediate (c) with water and alcohol, add an inorganic base to hydrolyze it into carboxylic acid intermediate (d). Add an acyl chloride reagent (e) to carboxylic acid intermediate (d) to obtain coupling component one (f) containing a reactive group.

[0013] The reactive group is an acyl chloride or a carboxylic acid.

[0014] The alkaline inorganic salt is any one of sodium carbonate (Na2CO3), potassium carbonate (K2CO3), and lithium carbonate (Li2CO3).

[0015] The electrophilic reagent is preferably a Br / Cl substituted ester, and the acid portion can have 1 to 5 carbon atoms, preferably Br-ethyl acetate.

[0016] The alcohol is methanol, ethanol, or propanol, preferably ethanol.

[0017] The inorganic base is KOH or NaOH, preferably NaOH.

[0018] The acyl chloride reagent is any one of thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride, phosgene, diphosgene, and triphosgene.

[0019] The reaction formula for synthesizing coupling component one (f) containing reactive groups is expressed as follows: .

[0020] In step three, inorganic acid, solvent, surfactant and defoamer are added to the coupling component (h) at the dual coupling sites, stirred to dissolve, cooled to 0~5℃ in an ice bath, and diazonium salt solution (j) is slowly added dropwise under strong stirring. The mixture is stirred for 4~12h until the coupling reaction is complete, filtered, washed to obtain crude dye (k), and recrystallized to obtain pure direct-coupled dichromoplast disperse dye. The molar ratio of the diazonium salt solution to the coupling component at the dual coupling sites is 2~2.5:1.

[0021] The reaction equation for dye synthesis is expressed as follows: .

[0022] More preferably: The inorganic acids are hydrochloric acid, acetic acid, and sulfuric acid.

[0023] The solvent is at least one of methanol, ethanol, acetone, acetic acid, DMF, and water.

[0024] The surfactant is at least one of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, polyether compound, alkyl glycoside type, fatty acid glycerol monoester, fatty acid polyoxyethylene ester, sorbitan fatty acid ester, sodium alkyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium alkylbenzene sulfonate, sodium alkyl sulfonate, dispersant NNO, and dispersant MF.

[0025] The defoamer is at least one of polydimethylsiloxane (silicone oil), polymeric silicone oil, cyclic siloxane, polyoxypropylene glycerol ether, diethylhexanol, isooctanol, isoamyl alcohol, and diisobutylmethanol.

[0026] The preparation process of the diazonium salt solution is as follows: in the presence of inorganic acid, the diazonium component undergoes a diazotization reaction with sodium nitrite (NaNO2) or nitrosylsulfuric acid (NOHSO4).

[0027] Specifically, the above diazotization process can be one of the following two methods: Method 1: Add water and hydrochloric acid to the diazo component (i), heat (e.g., 70~80 ℃) to dissolve, then let it cool naturally to room temperature, cool it in an ice bath to 0~5 ℃, add sodium nitrite aqueous solution, and keep the temperature at 0~5 ℃. After the diazotization reaction is complete (the amino reagent tracks the reaction progress), add aminosulfonic acid to quench the excess sodium nitrite to obtain the diazo salt solution (j).

[0028] Method 2: Dissolve the diazo component (i) in concentrated sulfuric acid, cool it to 0-5 °C in an ice bath, add nitrosyl sulfuric acid to complete the diazotization reaction (the reaction endpoint is detected by ice water method), and obtain the diazo salt solution (j).

[0029] The reaction formula for synthesizing diazonium salt solution (j) is expressed as follows: .

[0030] The inorganic acid is at least one of hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid.

[0031] The applicant's third objective is to provide an application of the aforementioned direct-coupled dichromatic disperse dyes in dyeing, printing, or color matching.

[0032] The dye mother liquor for dyeing can be prepared using conventional methods, such as mixing the disperse dye and dispersant of this application at a mass ratio of 1:1 and grinding them evenly to prepare a dye mother liquor of 2~5 g / L.

[0033] The raw materials used in this application can be common hydrophobic fibers, such as polyester, polyester-cotton blends, nylon, polyester-spandex blends, or triacetate fibers. These raw materials can exist in various processed forms, such as fibers, fiber rolls, non-manufactured fabrics, knitted fabrics, and woven fabrics.

[0034] The dyeing process follows common disperse dyeing procedures, such as dyeing at a temperature of 80-140°C in the presence of a dispersant or carrier. Applicable dyeing methods include, but are not limited to, hot melt dyeing, high-temperature and high-pressure dyeing, carrier dyeing, and printing dyeing.

[0035] For printing, common thickeners are used, such as modified or unmodified natural products, or synthetic products.

[0036] The disperse dyes and dye mixtures of the present invention can impart the above-mentioned materials, especially polyester materials, with very good fastness in use, for example, good lightfastness, heat migration resistance, such as water resistance, perspiration resistance and washability, and good rubbing fastness.

[0037] The disperse dyes and dye mixtures of the present invention can also be used to prepare mixed dyes together with other dyes.

[0038] The dyes and dye mixtures mentioned above are also very suitable for dyeing hydrophobic fiber materials with supercritical CO2. Attached Figure Description

[0039] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application.

[0040] Figure 1 For dye 1 in this application 1 H-NMR spectrum; Figure 2 The infrared spectrum of dye 1 in this application; Figure 3 This is the mass spectrum of dye 1 in this application; Figure 4 The UV-Vis spectrum of dye 1 in this application is shown. Figure 5 For dye 2 in this application 1 H-NMR spectrum; Figure 6 The infrared spectrum of dye 2 in this application; Figure 7 This is the mass spectrum of dye 2 in this application; Figure 8 The UV-Vis spectrum of dye 2 in this application; Figure 9 For dye 3 in this application 1 H-NMR spectrum; Figure 10 The infrared spectrum of dye 3 in this application; Figure 11 This is the mass spectrum of dye 3 in this application; Figure 12 This is the ultraviolet-visible spectrum of dye 3 in this application. Detailed Implementation

[0041] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the technical solutions in the embodiments of this application will be further described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit the technical solutions of this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application without creative effort are within the scope of protection of this application.

[0042] Example 1

[0043] This embodiment provides a directly coupled bichromoplasmic disperse dye with the following structural formula: .

[0044] (3) The specific synthesis process is as follows: In a 100 mL round-bottom flask, N-ethylaniline (1-a) (1.24 g, 10 mmol) and Na₂CO₃ (2.71 g, 10 mmol) were added, along with DMF (20 mL) as a solvent. Br-ethyl acetate (1-b) (1.87 g, 11 mmol) was added, and the reaction was carried out at room temperature for 5 h. After the reaction, a large amount of water was added to precipitate product (1-c). The product was extracted with DCM, and then NaOH (0.6 g), ethanol (15 mL), and water (3.5 mL) were added. The mixture was stirred at room temperature to initiate a hydrolysis reaction for 2 h. After the hydrolysis reaction, the product was concentrated by rotary evaporation, extracted with DCM, and the water was removed to obtain the carboxylic acid product (1-d). The carboxylic acid product (1-d) was dissolved in DCM (20 mL), and oxalyl chloride (1-e) (1.02 mL, 11 mmol) was slowly added dropwise under ice bath conditions. After reacting for 5 h, the mixture was filtered to obtain the solid product (1-f). In DCM (30 mL), the product (1-f) and N-ethyl-N-hydroxyethylaniline (1-g) were added, followed by 5 mL of triethylamine. The reaction was carried out for 1 h, and the reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the mixture was concentrated by rotary evaporation to obtain the coupled fraction with two coupling sites (1-h).

[0045] Distilled water (40 mL), hydrochloric acid (12 mL), and p-nitroaniline (1-i) (2.79 g, 20 mmol) were added to a three-necked flask. The mixture was heated to 80 °C and stirred to dissolve. Then, the mixture was cooled to around 0 °C, and a 20% aqueous solution of sodium nitrite (1.518 g, 11 mmol) was added in one go. The reaction was allowed to proceed for 1 h. The reaction endpoint was detected using an amino reagent. Sulfamic acid (1 g) was added to remove excess sodium nitrite, yielding a diazonium salt solution (1-j).

[0046] Add the coupling component (1-h) to a 500 mL three-necked flask, add distilled water (50 mL) and hydrochloric acid (2 mL) to dissolve the coupling component, then cool to around 0 °C in an ice bath, slowly add diazonium salt solution (1-j), and after reacting for 10 h, detect the reaction intensity with H acid and thin-layer chromatography, filter, and obtain crude dye (1-k), and obtain pure dye 1 by recrystallization.

[0047] (4) Characterize the obtained dye: 1) Nuclear magnetic resonance analysis: With DMSO- d Using 6 as a solvent, nuclear magnetic resonance spectrometry was performed using a Bruker AV400 nuclear magnetic resonance spectrometer. 1 H-NMR analysis, see Figure 1 As shown, the dye exhibits characteristic peaks at 1.13, 3.49, 3.76, 4.30, 4.38, 6.69, 6.92, 7.76, 7.84, and 7.90 ppm.

[0048] 2) Infrared analysis: Potassium bromide was used for tableting, and the infrared spectrum of the pure dye product was determined using a Shimadzu prestige 21FT-IR spectra. The results are shown in [Figure number missing]. Figure 2 As shown: Dyes at 858, 1076, 1142, 1246, 1331, 1391, 1508, 1603, 1761, 2872, 2909, and 2976 cm⁻¹ -1 Characteristic peaks appeared at various locations, including 2976 cm⁻¹. -1 2872 cm -1 The peak for the CH stretching vibration of methyl groups is 1761 cm⁻¹. -1 This is the carbonyl C=O stretching vibration, 1603 cm⁻¹ -1 This is a C=C stretching vibration of the benzene ring, 1508 cm⁻¹ -1 This is an asymmetric stretching vibration of -NO2, 1331 cm. -1 It is a symmetrical stretching vibration of -NO2, 1246 cm. -1 This is a CN stretching vibration, 1142 cm. -1 1076 cm -1 This is the CO stretching vibration of the ester group, 858 cm⁻¹. -1 This is a para-substitution peak for the benzene ring.

[0049] 3) Mass spectrometry analysis: Using acetonitrile as solvent, the purified dye was analyzed by mass spectrometry using a Waters UPLC / XEVO TQD high-performance liquid chromatography-mass spectrometry system. The results are shown in the figure. Figure 3 As shown: MS (+ESI): m / z (%) = 625.50 (100) [M+H+ ].

[0050] 4) Spectral absorption performance: The absorption spectrum of a 9 mg / L DMF solution of dye 1 was measured using a UV-2450 UV-Vis spectrophotometer (Shimadzu Corporation, Japan). Figure 4 As shown, its maximum absorption wavelength is 481 nm, the molar extinction coefficient is 35328 L / (mol·cm), and the full width at half maximum (FWHM) is 115 nm.

[0051] 5) Dye solution and dyeing properties: Accurately weigh 2 g of dye 1 and place it in a mortar. Add a little water, grind, transfer to a volumetric flask with a volumetric volume of 1000 mL, and obtain a 2 g / L mother liquor. After dilution, determine the particle size of the dye using a ZS90 nanoparticle size and potential analyzer (Malvern Instruments Ltd., UK).

[0052] The mother liquor was used to prepare dye solutions of different concentrations. A 1 g sample of polyester fabric was moistened and placed into the dye bath (pH=5, liquor ratio 1:20). The sealed dyeing cylinder was then installed in a high-temperature, high-pressure dyeing machine. The dye bath temperature was increased from 50℃ to 130℃ at a rate of 2℃ / min, held for 60 min, and then rapidly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was subjected to a reduction cleaning solution (2 g / L sodium carbonate, 2 g / L sodium hydrosulfite, liquor ratio 1:50) at 85℃ for 15 min, followed by drying. The dyed sample was measured using a Datacolor SF600 colorimeter under D65 light source and a 10° viewing angle. The colorimetric properties of the colors were represented using the CIELab color space. The dyeing results are shown in Table 1-1.

[0053] Table 1-1: Colorimetric properties of dye 1 .

[0054] 6) Colorfastness performance According to the ISO 105-C04 (2010) standard "Textiles - Tests for color fastness to washing", the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) was tested. According to the ISO 105 / P01 (1993) standard "Textiles - Tests for color fastness to dry heat (excluding hot pressing)", the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) was tested. According to the ISO 105-X12 (2016) standard "Textiles - Tests for color fastness to rubbing", the color fastness to dry / wet rubbing of polyester dyed fabrics with a dye concentration of 1% (owf) was tested. The results are shown in Table 1-2.

[0055] Table 1-2: Fastness properties of dye 1 .

[0056] Example 2 This embodiment provides a directly coupled bichromoplasmic disperse dye with the following structural formula: .

[0057] (3) The specific synthesis process is as follows: In a 100 mL round-bottom flask, N-ethylaniline (2-a) (1.24 g, 10 mmol) and Na₂CO₃ (2.71 g, 10 mmol) were added, along with DMF (20 mL) as a solvent. Br-ethyl acetate (2-b) (1.87 g, 11 mmol) was added, and the reaction was carried out at room temperature for 5 h. After the reaction, a large amount of water was added to precipitate product (2-c). The product was extracted using DCM, and then NaOH (0.6 g), ethanol (15 mL), and water (3.5 mL) were added. The mixture was stirred at room temperature to initiate a hydrolysis reaction for 2 h. After the hydrolysis reaction, the product was concentrated by rotary evaporation, extracted with DCM, and the water was removed to obtain the carboxylic acid product (2-d). The carboxylic acid product (2-d) was dissolved in DCM (20 mL), and oxalyl chloride (2-e) (1.02 mL, 11 mmol) was slowly added dropwise under ice bath conditions. After reacting for approximately 5 h, the mixture was filtered to obtain the solid product (2-f). In DCM (30 mL), the product (2-f) and N-cyanoethyl-N-hydroxyethylaniline (2-g) were added, followed by 5 mL of triethylamine. The reaction was carried out for 1 h, and the reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the product was concentrated by rotary evaporation to obtain the coupled component with two coupling sites (2-h).

[0058] Distilled water (40 mL), hydrochloric acid (12 mL), and p-nitroaniline (2-i) (2.79 g, 20 mmol) were added to a three-necked flask. The mixture was heated to 80 °C and stirred to dissolve. Then, the mixture was cooled to around 0 °C, and a 20% aqueous solution of sodium nitrite (1.518 g, 11 mmol) was added in one go. The reaction was allowed to proceed for 1 h. The reaction endpoint was detected using an amino reagent. Sulfamic acid (1 g) was added to remove excess sodium nitrite, yielding a diazonium salt solution (2-j).

[0059] Add the coupling component (2-h) to a 500 mL three-necked flask, add distilled water (50 mL) and hydrochloric acid (2 mL) to dissolve the coupling component, then cool to around 0 °C in an ice bath, slowly add diazonium salt solution (2-j), and after reacting for 10 h, detect the reaction intensity with H acid and thin-layer chromatography, filter, and obtain crude dye (2-k), and obtain pure dye 2 by recrystallization.

[0060] (4) Characterize the obtained dye: 1) Nuclear magnetic resonance analysis: With DMSO- d Using 6 as a solvent, nuclear magnetic resonance spectrometry was performed using a Bruker AV400 nuclear magnetic resonance spectrometer. 1 H-NMR analysis, see Figure 5 As shown, the dye exhibits characteristic peaks at 1.12, 2.83, 3.48, 3.83, 4.30, 4.39, 6.69, 7.03, 7.76, 7.87, 7.93, and 8.33 ppm.

[0061] 2) Infrared analysis: Potassium bromide was used for tableting, and the infrared spectrum of the pure dye product was determined using a Shimadzu prestige 21FT-IR spectra. The results are shown in [Figure number missing]. Figure 6 As shown: Dyes at 858, 1076, 1142, 1244, 1339, 1512, 1603, 1734, 2249, 2868, and 2978 cm⁻¹ -1 Characteristic peaks appeared at various locations, including 2978 cm⁻¹. -1 2868 cm -1 The peak is the CH stretching vibration peak of methyl, at 2249 cm⁻¹. -1 The vibration is a cyano C≡N stretching vibration, 1734 cm⁻¹ -1 , which is the carbonyl C=O stretching vibration, 1603 cm -1 This is a C=C stretching vibration of the benzene ring, 1512 cm⁻¹ -1 This is an asymmetric stretching vibration of -NO2, 1339 cm. -1 It is a symmetrical stretching vibration of -NO2, 1244 cm. -1 This is a CN stretching vibration, 1142 cm. -1 1076 cm -1 This is the CO stretching vibration of the ester group, 858 cm⁻¹. -1 This is a para-substitution peak for the benzene ring.

[0062] 3) Mass spectrometry analysis: Using acetonitrile as solvent, the purified dye was analyzed by mass spectrometry using a Waters UPLC / XEVO TQD high-performance liquid chromatography-mass spectrometry system. The results are shown in the figure. Figure 7 As shown: MS (+ESI): m / z (%) = 650.53 (100) [M+H + ].

[0063] 4) Spectral absorption performance: The absorption spectrum of an 8 mg / L DMF solution of dye 2 was measured using a UV-2450 UV-Vis spectrophotometer (Shimadzu Corporation, Japan). Figure 8As shown, its maximum absorption wavelength is 468 nm, the molar extinction coefficient is 60500 L / (mol·cm), and the full width at half maximum (FWHM) is 113 nm.

[0064] 5) Dye solution and dyeing properties: Accurately weigh 2 g of dye 2 and place it in a mortar. Add a little water, grind, transfer to a volumetric flask with a volumetric volume of 1000 mL, and obtain a 2 g / L mother liquor. After dilution, determine the particle size of the dye using a ZS90 nanoparticle size and potential analyzer (Malvern Instruments Ltd., UK).

[0065] The mother liquor was used to prepare dye solutions of different concentrations. A 1 g sample of polyester fabric was moistened and placed into the dye bath (pH=5, liquor ratio 1:20). The sealed dyeing cylinder was then installed in a high-temperature, high-pressure dyeing machine. The dye bath temperature was increased from 50℃ to 130℃ at a rate of 2℃ / min, held for 60 min, and then rapidly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was subjected to a reduction cleaning solution (2 g / L sodium carbonate, 2 g / L sodium hydrosulfite, liquor ratio 1:50) at 85℃ for 15 min, followed by drying. The dyed sample was measured using a Datacolor SF600 colorimeter under D65 light source and 10° viewing angle conditions. The colorimetric properties of the colors were represented using the CIELab color space. The dyeing results are shown in Table 2-1.

[0066] Table 2-1: Colorimetric properties of dye 2 .

[0067] 6) Colorfastness performance According to the ISO 105-C04 (2010) standard "Textiles - Tests for color fastness to washing", the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) was tested. According to the ISO 105 / P01 (1993) standard "Textiles - Tests for color fastness to dry heat (excluding hot pressing)", the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) was tested. According to the ISO 105-X12 (2016) standard "Textiles - Tests for color fastness to rubbing", the color fastness to dry / wet rubbing of polyester dyed fabrics with a dye concentration of 1% (owf) was tested. The results are shown in Table 2-2.

[0068] Table 2-2: Fastness properties of dye 2 .

[0069] Example 3 This embodiment provides a directly coupled bichromoplasmic disperse dye with the following structural formula: .

[0070] (3) The specific synthesis process is as follows: In a 100 mL round-bottom flask, N-ethylaniline (3-a) (1.24 g, 10 mmol) and Na₂CO₃ (2.71 g, 10 mmol) were added, along with DMF (20 mL) as a solvent. Br-ethyl acetate (3-b) (1.87 g, 11 mmol) was added, and the reaction was carried out at room temperature for 5 h. After the reaction, a large amount of water was added to precipitate product (3-c). The product was extracted with DCM, and then NaOH (0.6 g), ethanol (15 mL), and water (3.5 mL) were added. The mixture was stirred at room temperature to initiate a hydrolysis reaction for 2 h. After the hydrolysis reaction, the product was concentrated by rotary evaporation, extracted with DCM, and the water was removed to obtain the carboxylic acid product (3-d). The carboxylic acid product (3-d) was dissolved in DCM (20 mL), and oxalyl chloride (3-e) (1.02 mL, 11 mmol) was slowly added dropwise under ice bath conditions. After reacting for 5 h, the mixture was filtered to obtain the solid product (3-f). In DCM (30 mL), the product (3-f) and N-methylaniline (3-g) were added, followed by 5 mL of triethylamine. The reaction was carried out for 1 h, and the reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the mixture was concentrated by rotary evaporation to obtain the coupled fraction with two coupling sites (3-h).

[0071] Sulfuric acid (10 mL) and 3-amino-5-nitrobenzisothiazole (3-i) (3.96 g, 20 mmol) were added to a three-necked flask. The temperature was lowered to around 0 °C, and nitrosylsulfuric acid (4 mL, 40%) was slowly added dropwise. The reaction was allowed to proceed for 2 h, and the reaction endpoint was determined by the ice-water method to obtain a diazonium salt solution (3-j).

[0072] Add the coupling component (3-h) to a 500 mL three-necked flask, add distilled water (50 mL) and hydrochloric acid (2 mL) to dissolve the coupling component, then cool to around 0 °C in an ice bath, slowly add diazonium salt solution (3-j), and after reacting for 10 h, detect the reaction intensity with H acid and thin-layer chromatography, filter, and obtain crude dye (3-k), and obtain pure dye 3 by recrystallization.

[0073] (4) Characterize the obtained dye: 1) Nuclear magnetic resonance analysis: With DMSO- d Using 6 as a solvent, nuclear magnetic resonance spectrometry was performed using a Bruker AV400 nuclear magnetic resonance spectrometer. 1 H-NMR analysis, see Figure 9 As shown, the dye exhibits characteristic peaks at 1.25, 1.84, 3.25, 3.60, 3.71, 4.25, 6.84, 6.97, 7.55, 7.64, 7.78, 7.96, 8.04, 8.30, 8.60, and 8.69 ppm.

[0074] 2) Infrared analysis: Potassium bromide was used for tableting, and the infrared spectrum of the pure dye product was determined using a Shimadzu prestige 21FT-IR spectra. The results are shown in [Figure number missing]. Figure 10 As shown: Dyes at 858, 1076, 1142, 1244, 1339, 1512, 1603, 1734, 2249, 2868, and 2978 cm⁻¹ -1 Characteristic peaks appeared at various locations, including 2978 cm⁻¹. -1 2868 cm -1 The peak is the CH stretching vibration peak of methyl, at 2249 cm⁻¹. -1 The vibration is a cyano C≡N stretching vibration, 1734 cm⁻¹ -1 , which is the carbonyl C=O stretching vibration, 1603 cm -1 This is a C=C stretching vibration of the benzene ring, 1512 cm⁻¹ -1 This is an asymmetric stretching vibration of -NO2, 1339 cm. -1 It is a symmetrical stretching vibration of -NO2, 1244 cm. -1 This is a CN stretching vibration, 1142 cm. -1 1076 cm -1 This is the CO stretching vibration of the ester group, 858 cm⁻¹. -1 This is a para-substitution peak for the benzene ring.

[0075] 3) Mass spectrometry analysis: Using acetonitrile as solvent, the purified dye was analyzed by mass spectrometry using a Waters UPLC / XEVO TQD high-performance liquid chromatography-mass spectrometry system. The results are shown in the figure. Figure 11 As shown: MS (+ESI): m / z (%) = 738.24 (100) [M+H + ].

[0076] 4) Spectral absorption performance: The absorption spectrum of an 8 mg / L DMF solution of dye 3 was measured using a UV-2450 UV-Vis spectrophotometer (Shimadzu Corporation, Japan). Figure 12 As shown, its maximum absorption wavelength is 564 nm, the molar extinction coefficient is 48379 L / (mol·cm), and the full width at half maximum (FWHM) is 122 nm.

[0077] 5) Dye solution and dyeing properties: Accurately weigh 2 g of dye 3 and place it in a mortar. Add a little water, grind, transfer to a volumetric flask with a volumetric volume of 1000 mL, and obtain a 2 g / L mother liquor. After dilution, determine the particle size of the dye using a ZS90 nanoparticle size and potential analyzer (Malvern Instruments Ltd., UK).

[0078] The mother liquor was used to prepare dye solutions of different concentrations. A 1 g sample of polyester fabric was moistened and placed into the dye bath (pH=5, liquor ratio 1:20). The sealed dyeing cylinder was then installed in a high-temperature, high-pressure dyeing machine. The dye bath temperature was increased from 50℃ to 130℃ at a rate of 2℃ / min, held for 60 min, and then rapidly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was subjected to a reduction cleaning solution (2 g / L sodium carbonate, 2 g / L sodium hydrosulfite, liquor ratio 1:50) at 85℃ for 15 min, followed by drying. The dyed sample was measured using a Datacolor SF600 colorimeter under D65 light source and a 10° viewing angle. The colorimetric properties of the colors were represented using the CIELab color space. The dyeing results are shown in Table 3-1.

[0079] Table 3-1: Colorimetric properties of dye 3 .

[0080] 6) Colorfastness performance According to the ISO 105-C04 (2010) standard "Textiles - Tests for color fastness to washing", the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) was tested. According to the ISO 105 / P01 (1993) standard "Textiles - Tests for color fastness to dry heat (excluding hot pressing)", the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) was tested. According to the ISO 105-X12 (2016) standard "Textiles - Tests for color fastness to rubbing", the color fastness to dry / wet rubbing of polyester dyed fabrics with a dye concentration of 1% (owf) was tested. The results are shown in Table 3-2.

[0081] Table 3-2: Fastness properties of dye 3 .

[0082] The above-described embodiments are merely illustrative of several feasible implementations of the present invention, and their descriptions are relatively specific and detailed. However, they should not be construed as limiting the scope of the present invention, nor are the embodiments intended to limit the scope of protection in the claims of the present invention. For those skilled in the art, various modifications and improvements can be made without departing from the concept of the present invention. All equivalent implementations or changes that do not depart from the present invention should be included in the technology of the present invention.

Claims

1. A direct-coupled dichromatic disperse dye, characterized in that, The general structural formula of directly coupled dichromatic disperse dyes is as follows: , in: Ar-N=N- is obtained by diazotization of the following groups: , R1, R2, and R3 are independently selected from any one of H, NO2, CN, Cl, Br, OCH3, and OCOCH3; R4, R5, R8, and R9 are independently selected from any one of H, CH3, OCH3, Cl, and Br; R6 and R7 are independently selected from any one of H, CN, CH3, Bn, OCOCH3, and COOCH3; X is either O or NH; Q, Y, and Z are independently selected from any one of C, N, and S; n=1~5。 2. The direct-coupled dichromatic disperse dye according to claim 1, characterized in that, The structural formula of a direct-coupled dichromatic disperse dye is any one of the following: .

3. A method for synthesizing the direct-coupled dichromatic disperse dye as described in claim 1, characterized in that... The steps are as follows: Step 1: Introduce reactive groups into coupling component 1 to obtain coupling component 1 containing reactive groups; Step 2: The second coupling component with the reactive site is directly coupled to the first coupling component containing the reactive group to obtain the coupling component with two coupling sites. Step 3: The coupling component at the dual coupling site undergoes bilateral coupling with the diazo component to obtain a directly coupled dichromoplasmic disperse dye. The structural formula of the coupling component containing the reactive group is: , The structural formula of the coupling component two with the reaction site is: , The structural formula of the coupling component at the dual coupling site is: , The diazo component can be any of the following structures: .

4. The method for synthesizing a direct-coupled dichromatic disperse dye according to claim 3, characterized in that: In step one, an alkaline inorganic salt is added to N-ethylaniline or its derivatives and stirred until homogeneous. Then, an electrophilic reagent is added, and the reaction yields an intermediate. The intermediate is then mixed with water and alcohol, and an inorganic base is added for hydrolysis to a carboxylic acid intermediate. An acyl chloride reagent is added to the carboxylic acid intermediate to obtain a coupling component containing a reactive group. The structural formula of the N-ethylaniline or its derivative is: , The electrophilic reagent has the following structural formula: , The intermediate structure is as follows: , The structural formula of the carboxylic acid intermediate is: .

5. The method for synthesizing a direct-coupled dichromatic disperse dye according to claim 4, characterized in that: The acyl chloride reagent is any one of thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride, phosgene, diphosgene, and triphosgene.

6. The method for synthesizing a direct-coupled dichromatic disperse dye according to claim 3, characterized in that: In step three, inorganic acid, surfactant, and defoamer are added to the coupling component at the dual coupling sites, stirred to dissolve, cooled to 0-5°C in an ice bath, and then diazonium salt solution is slowly added dropwise under strong stirring. The mixture is stirred for 4-12 hours until the coupling reaction is complete. The mixture is then filtered, washed, and recrystallized to obtain a directly coupled dichromatic disperse dye. The molar ratio of the diazonium salt solution to the coupling component at the dual coupling sites is 2-2.5:

1. After the reaction is complete, the mixture is removed from the list of products.

7. The method for synthesizing a directly coupled dichromatic disperse dye according to claim 6, characterized in that, The preparation process of the diazonium salt solution is as follows: in the presence of inorganic acid, the diazonium component undergoes a diazotization reaction with sodium nitrite or nitrosylsulfuric acid.

8. The method for synthesizing a direct-coupled dichromatic disperse dye according to claim 6, characterized in that: The surfactant is at least one of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, polyether compound, alkyl glycoside type, fatty acid glycerol monoester, fatty acid polyoxyethylene ester, sorbitan fatty acid ester, sodium alkyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium alkylbenzene sulfonate, sodium alkyl sulfonate, dispersant NNO, and dispersant MF.

9. The method for synthesizing a direct-coupled dichromatic disperse dye according to claim 6, characterized in that: The defoamer is at least one of polydimethylsiloxane, polymeric silicone oil, cyclic siloxane, polyoxypropylene glycerol ether, diethylhexanol, isooctanol, isoamyl alcohol, and diisobutylmethanol.

10. The use of the direct-coupled dichromatic disperse dye of claim 1 in dyeing, printing or color matching.

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