Dye compound as well as preparation method and application thereof
By preparing dye compounds with the structures of Formula I and Formula II, the problems of insufficient application range of azo dye compounds in terms of water fastness, sublimation fastness, color yield and dye bath pH are solved, and high-quality fiber fabric dyeing and printing effects are achieved, which are suitable for high-end textile products.
Patent Information
- Application Number
- CN202511055859.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-30
- Publication Date
- 2025-10-10
AI Technical Summary
Existing azo dye compounds have deficiencies in washing fastness, sublimation fastness, color yield and dye bath pH applicability, making it difficult to achieve high-quality dyeing and printing in a short-process, low-energy processing environment.
A dye compound with a specific structure is prepared through diazotization and coupling reaction to obtain a dye compound with the structure of formula I and formula II, which is then used in fiber fabric dyeing or printing. The reaction conditions and purification process are controlled to improve product performance.
It achieves high wash fastness, excellent color yield, a wide range of dye bath pH applications and good re-dyeing properties, reduces dyeing costs, improves dyeing process flexibility and yield, avoids color difference and color spot phenomena, and is suitable for high-end textile products.
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Figure CN120758061A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of dye chemical industry, in particular to a dye compound and a preparation method and application thereof. Background Art
[0002] Azo dye compounds are the world's largest organic dye by volume, accounting for over half of all organic dyes, due to their vibrant colors, comprehensive color spectrum, and strong tinting strength. They are widely used in exhaust dyeing, pad dyeing, and printing of polyester fibers and their blends with cotton, viscose, and other fabrics. With the expansion of polyester processing and increasing demands for energy conservation and emission reduction, the market urgently needs a new generation of products that combine fastness with cost-effectiveness.
[0003] The core of determining the application value of dyes lies in the "four properties and one degree": water fastness determines whether it will fade after repeated washing; color yield directly affects the amount and cost of dye; the wider the pH adaptability of the dye bath, the higher the tolerance for process fluctuations; re-dyeability ensures uniform reproduction during additional dyeing or repairs; and heat migration fastness prevents sublimation staining during high-temperature setting or ironing.
[0004] Therefore, the next generation of azo dye compounds must achieve high levels of wash fastness and sublimation fastness, increase color yield and expand the applicable pH range of the dye bath, and achieve uniform re-dyeing under high temperature, high pressure and hot melt conditions, thereby taking into account quality, ecological and cost advantages in a short process and low energy consumption processing environment.
[0005] In view of this, the present invention is proposed. Summary of the Invention
[0006] The object of the present invention is to provide a dye compound and a preparation method and application thereof, so as to solve at least one of the above technical problems.
[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted: The first aspect of the present invention provides a dye compound having the structure shown in Formula I:
[0008] Formula I Wherein, R1 is selected from hydrogen atom, methyl, ethyl, n-propyl or isopropyl; R2 is selected from methyl, ethyl, cyanoethyl, vinyl or allyl; R3 is selected from methyl or halogen.
[0009] Furthermore, R1 is selected from a hydrogen atom or a methyl group; R2 is selected from a methyl group, an ethyl group, a cyanoethyl group or an allyl group; and R3 is selected from a methyl group or a halogen group.
[0010] The second aspect of the present application provides a preparation method of the dye compound, wherein phenylsulfonic acid-3-aminophenyl ester, an acidic reagent and a diazotization reagent are mixed to perform a diazotization reaction to obtain a diazonium salt; the diazonium salt, a coupling component and sulfamic acid are mixed to perform a coupling reaction to obtain a coupling slurry; and the coupling slurry is subjected to crystal transformation, pressure filtration and water washing to obtain the dye compound.
[0011] Further, the acidic reagent comprises sulfuric acid or hydrochloric acid.
[0012] Further, the diazotization reagent comprises sodium nitrite or nitrosyl sulfuric acid.
[0013] Further, the coupling component has a structure shown in Formula II.
[0014] Formula II wherein R1 is selected from a hydrogen atom, a methyl group, an ethyl group, a n-propyl group or an isopropyl group; R2 is selected from a methyl group, an ethyl group, a cyanoethyl group, a vinyl group or an allyl group; and R3 is selected from a methyl group or a halogen.
[0015] Further, the diazotization reaction is performed at a temperature of-5-30℃ for 0.5-8h.
[0016] Further, the coupling reaction is performed at a temperature of 5-30℃ for 0.5-6h.
[0017] Further, the molar ratio of the phenylsulfonic acid-3-aminophenyl ester to the diazotization reagent is 1:(0.995-1.05).
[0018] Further, the molar ratio of the phenylsulfonic acid-3-aminophenyl ester to the diazotization reagent is 1:(0.995-1.05).
[0019] Further, the molar ratio of the diazonium salt to the coupling component is 1:(0.998-1.10).
[0020] Further, the molar ratio of the diazonium salt to the coupling component is 1:(0.998-1.10).
[0021] The third aspect of the present application provides application of the dye compound in dyeing or printing of fiber fabric.
[0022] Compared with the prior art, the present application has at least the following beneficial effects: The dye compound provided by the present invention has extremely high water fastness, ensuring that the fabric can still maintain a bright color after multiple washings, and has an excellent color yield, and can achieve an ideal coloring effect at a lower dye dosage, thereby effectively reducing dyeing costs. In addition, the dye has a very wide range of pH applicability in the dye bath, and can be stably used between pH 4 and 12, greatly improving the flexibility and adaptability of the dyeing process and reducing the color difference problem caused by pH fluctuations. At the same time, its heavy dyeing performance is excellent, and even in the process of repeated dyeing or repairing, the uniformity and consistency of dyeing can be guaranteed, further improving the reliability and yield of the dyeing process. Moreover, the dispersibility of the dye is also very good, and it can be evenly dispersed in the dye bath, avoiding the color spot or color flower phenomenon caused by dye aggregation, and ensuring the uniformity and stability of the dyeing process.
[0023] The preparation method provided by the present invention has the advantages of continuous process, mild reaction conditions, high product yield, few by-products, easy purification, and is suitable for large-scale industrial production.
[0024] The use of the dye compound provided by the present invention in dyeing or printing fiber fabrics, in view of the advantages of the above-mentioned dye compound, enables the dyed or printed fiber fabrics to have better dyeing effect and water fastness, and can maintain color stability for a long time. It is particularly suitable for high-end textile products with high requirements for dyeing quality and durability. DETAILED DESCRIPTION
[0025] The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention.
[0026] The first aspect of the present invention provides a dye compound having the structure shown in Formula I:
[0027] Formula I Wherein, R1 is selected from hydrogen atom, methyl, ethyl, n-propyl or isopropyl; R2 is selected from methyl, ethyl, cyanoethyl, vinyl or allyl; R3 is selected from methyl or halogen.
[0028] The dye compound provided by the application has extremely high washing fastness, ensures that the fabric can maintain bright color after multiple washing, has excellent color yield, can realize ideal coloring effect under lower dye consumption, thereby effectively reducing the dyeing cost. In addition, the dyeing bath pH of the dye is very wide, can be stably used between pH 4 to 12, greatly improves the flexibility and adaptability of the dyeing process, reduces the color difference problem caused by pH fluctuation. At the same time, the dye has excellent overdyeing performance, can ensure the uniformity and consistency of dyeing even in the process of repeated dyeing or repairing, further improves the reliability and yield of the dyeing process. Moreover, the dye has good dispersibility, can be uniformly dispersed in the dyeing bath, avoids the color spot or color flower phenomenon caused by dye aggregation, ensures the uniformity and stability of the dyeing process.
[0029] Further, R1 is selected from a hydrogen atom or a methyl group; R2 is selected from a methyl group, an ethyl group, a cyanoethyl group or an allyl group; and R3 is selected from a methyl group or a halogen.
[0030] The second aspect of the application provides a preparation method of the dye compound, wherein benzene sulfonic acid-3-aminophenyl ester, an acidic reagent and a diazotization reagent are mixed to perform diazotization reaction to obtain a diazonium salt; the diazonium salt, a coupling component and sulfamic acid are mixed to perform coupling reaction to obtain a coupling slurry; and the coupling slurry is subjected to crystal transformation, pressure filtration and water washing to obtain the dye compound.
[0031] The preparation method provided by the application has continuous process, mild reaction condition, high product yield, less by-products and is easy to purify, and is suitable for large-scale industrial production.
[0032] Further, the acidic reagent includes sulfuric acid or hydrochloric acid.
[0033] And / or, the diazotization reagent includes sodium nitrite or nitrosyl sulfuric acid.
[0034] Further, the coupling component has a structure shown in Formula II:
[0035] Formula II wherein R1 is selected from a hydrogen atom, a methyl group, an ethyl group, a n-propyl group or an iso-propyl group; R2 is selected from a methyl group, an ethyl group, a cyanoethyl group, an ethenyl group or an allyl group; and R3 is selected from a methyl group or a halogen.
[0036] Further, the temperature of the diazotization reaction is-5-30℃, and the time is 0.5-8h.
[0037] Typically but not limitatively, the temperature of the diazotization reaction can be, for example, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C or 30°C, or any value within the range of -5°C to 30°C; the time of the diazotization reaction can be, for example, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, or any value within the range of 0.5h to 8h.
[0038] Furthermore, the coupling reaction temperature is 5-30° C., and the time is 0.5-6 h.
[0039] Typically but not limitatively, the coupling reaction temperature can be, for example, 5°C, 10°C, 15°C, 20°C, 25°C or 30°C, or any value within the range of 5°C to 30°C; the coupling reaction time can be, for example, 0.5h, 1h, 2h, 3h, 4h, 5h or 6h, or any value within the range of 0.5h to 6h.
[0040] Furthermore, the molar ratio of the 3-aminophenyl benzenesulfonate to the diazotizing agent is 1:(0.995-1.05).
[0041] Typically, but not limiting, the molar ratio of 3-aminophenyl benzenesulfonate to the diazotizing agent can be, for example, 1:0.995, 1:1.000, 1:1.005, 1:1.010, 1:1.015, 1:1.020, 1:1.025, 1:1.030, 1:1.035, 1:1.040, 1:1.045 or 1:1.050, or any ratio within the range of 1:(0.995-1.05).
[0042] And / or, the amount of the acidic reagent added is 50-60 wt % of the weight of the 3-aminophenyl benzenesulfonate.
[0043] Typically, but not limiting, the amount of the acidic agent added can be, for example, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt% or 60 wt% of the weight of 3-aminophenyl benzenesulfonate, or any value within the range of 50 wt% to 60 wt%.
[0044] Furthermore, the molar ratio of the diazonium salt to the coupling component is 1:(0.998-1.10).
[0045] Typically but not exclusively, the molar ratio of diazonium salt to coupling component can be, for example, 1:0.998, 1:1.000, 1:1.005, 1:1.010, 1:1.020, 1:1.030, 1:1.040, 1:1.050, 1:1.060, 1:1.070, 1:1.080, 1:1.090 or 1:1.10, or any ratio within the range of 1:(0.998-1.10).
[0046] And / or, the amount of sulfamic acid added is 0.5-2wt% of the mass of the diazonium salt.
[0047] After the coupling reaction is completed, the dye compound in the system is usually suspended in the mother liquor in the form of fine, amorphous or metastable crystals. First, the temperature of the slurry is increased to about 83-87°C at a controllable rate, so that the amorphous particles of the dye molecules are gradually rearranged into crystals with more complete crystal lattices, larger particle sizes and more stable crystal forms. The increase in temperature also reduces the viscosity of the mother liquor and promotes the dissolution of impurities, thereby simultaneously improving the purity.
[0048] Subsequently, hot pressure filtration is carried out: the slurry passes through the filter cloth under mechanical pressure, the mother liquor and soluble impurities pass through the filter cloth to become the filtrate, and the dye crystals that have undergone crystal transformation and particle coarsening are intercepted to form the filter cake; the filter cake is replaced with a small amount of hot wash water to remove the residual mother liquor, and finally a high-purity dye filter cake with low moisture content, uniform crystal form, easy drying and grinding is obtained.
[0049] The third aspect of the present application provides the use of the dye compound in dyeing or printing of fiber fabrics.
[0050] The use of the dye compound in dyeing or printing of fiber fabrics provided by the present application has the advantages of the above-mentioned dye compound, so that the fiber fabric after dyeing or printing has better dyeing effect and washing fastness, can maintain color stability for a long time, and is particularly suitable for high-end textile products with high requirements for dyeing quality and durability.
[0051] The present application will be further described by specific examples and comparative examples, but it should be understood that these examples are only for a more detailed description and should not be understood as limiting the present application in any form. In the examples and comparative examples of the present application, the raw materials used are not specified, and the conventional conditions or the conditions recommended by the manufacturer are used. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased on the market.
[0052] Example 1 This example provides a dye compound, and the preparation method is as follows: 1. Preparation of sodium nitrite solution: Add 2000 kg of water into the preparation kettle, add 390 kg of sodium nitrite while stirring, and stir at room temperature for 1 hour to obtain sodium nitrite solution.
[0053] 2. Diazo Reaction: Add 6000 kg of water to the diazo coupling kettle, add 760 kg of concentrated sulfuric acid while stirring, control the temperature at 55-65°C, add 1360 kg of 3-aminophenyl benzenesulfonate, and beat at 55-65°C for 3 hours. Add 7000 kg of ice, cool to -5-0°C, add sodium nitrite solution, control the temperature at 0-5°C, and react for 3 hours.
[0054] 3. Coupling reaction: Control the temperature at 5-10°C and evenly add 1522 kg of N-methyl-N-bromobenzylaniline and 30 kg of aminosulfonic acid into the diazo coupling kettle to carry out coupling reaction. After reaching the end point, stir at 5-15°C for 4 hours.
[0055] 4. Heating, crystallization and filter pressing: heating to 83-87° C., keeping the temperature for 4 hours and then filter pressing, washing with 50-60° C. water until the pH of the washing liquid is 6-7, blowing air, and unloading to obtain the dye compound.
[0056] Examples 2-8 According to the preparation method of Example 1, the groups in the dye compound were adjusted to obtain a dye compound with a corresponding structure. The specific experimental data and product data are shown in Table 1.
[0057] Table 1
[0058] Comparative Example 1 This comparative example provides 100 g of C.I. Disperse Yellow 114.
[0059] Test Example 1 Dispersion performance was tested according to GB / T 5541-2007, "Determination of High-Temperature Dispersion Stability - Double-Paper Filtration Method." 100g of each dye from the Examples and Comparative Examples was used to prepare a disperse dye suspension (pH 5.5) containing 0.25g / L EDTA. The suspension was then uniformly dispersed using an electromagnetic stirrer. The suspension was preheated and tested for low-temperature dispersibility at 70°C and for high-temperature dispersibility at 130°C.
[0060] The suspension was poured into a Büchner funnel (120 mm in diameter) filled with double-layer filter paper. The filtrate volume and time were recorded under vacuum pump filtration. The dispersion grade was evaluated by the morphology of the filter paper residue and the filtrate flow rate. The obtained data are recorded in Table 2.
[0061] Table 2
[0062] As can be seen from Table 1, the high and low temperature dispersibility of Examples 1-8 of the present invention is good, all lower than 15", which is significantly better than the low temperature dispersibility of 15" and the high temperature dispersibility of 17" in Comparative Example 1.
[0063] Test Example 2 100 g of each dye of the embodiment and comparative example was taken to prepare a disperse dye suspension containing 0.25 g / L EDTA (pH = 5.5) to dye polyester fiber or polyester amine fiber fabric. The dyeing temperature was 130°C. Each disperse dye was dyed under five pH conditions: 1, 4, 8, 12, and 13.
[0064] Test Example 3 The dyed fabric samples obtained in Test Example 2 were tested for their wash resistance, perspiration resistance, sunlight resistance, sublimation color fastness, dye uptake, and re-dyeing properties according to ISO 105 C10 C(3), ISO 105 E04, ISO 105 B02, GB / T 5718-1997, GB / T 9337-2009, and GB / T 10663-2014 standards. The test results are shown in Table 3.
[0065] Table 3
[0066] As can be seen from the results in Table 3, the disperse dyes obtained from the dye compounds of the present invention have a wide dyeing range, and have good washing fastness, perspiration fastness, sublimation fastness (210°C×30s), sunlight fastness (50h), dye uptake and re-dyeing properties within the pH range of 4-12. In the comparative examples, good application indicators are only achieved at pH=8.
[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A dye compound, characterized in that It has the structure shown in formula I: Formula I Wherein, R1 is selected from hydrogen atom, methyl, ethyl, n-propyl or isopropyl; R2 is selected from methyl, ethyl, cyanoethyl, vinyl or allyl; R3 is selected from methyl or halogen.
2. The dye compound according to claim 1, characterized in that R1 is selected from a hydrogen atom or a methyl group; R2 is selected from a methyl group, an ethyl group, a cyanoethyl group or an allyl group; R3 is selected from a methyl group or a halogen group.
3. A method for preparing the dye compound according to claim 1 or 2, characterized in that: 3-Aminophenyl benzenesulfonate, an acidic reagent and a diazotizing reagent are mixed and subjected to a diazotization reaction to obtain a diazonium salt; the diazonium salt, a coupling component and aminosulfonic acid are mixed and subjected to a coupling reaction to obtain a coupling slurry; the coupling slurry is crystallized, filtered and washed with water to obtain the dye compound.
4. The preparation method according to claim 3, characterized in that The acidic reagent includes sulfuric acid or hydrochloric acid; And / or, the diazotization reagent includes sodium nitrite or nitrosyl sulfuric acid.
5. The preparation method according to claim 3, characterized in that The coupling component has the structure shown in Formula II: Formula II Wherein, R1 is selected from hydrogen atom, methyl, ethyl, n-propyl or isopropyl; R2 is selected from methyl, ethyl, cyanoethyl, vinyl or allyl; R3 is selected from methyl or halogen.
6. The preparation method according to any one of claims 3 to 5, characterized in that The temperature of the diazotization reaction is -5 to 30° C., and the time is 0.5 to 8 hours.
7. The preparation method according to any one of claims 3 to 5, characterized in that The coupling reaction temperature is 5-30° C. and the reaction time is 0.5-6 h.
8. The preparation method according to any one of claims 3 to 5, characterized in that The molar ratio of the 3-aminophenyl benzenesulfonate to the diazotizing agent is 1:(0.995-1.05); And / or, the amount of the acidic reagent added is 50-60 wt % of the weight of the 3-aminophenyl benzenesulfonate.
9. The preparation method according to any one of claims 3 to 5, characterized in that The molar ratio of the diazonium salt to the coupling component is 1:(0.998-1.10); And / or, the amount of aminosulfonic acid added is 0.5-2wt% of the mass of the diazonium salt.
10. Use of the dye compound according to claim 1 or 2, or the dye compound prepared by the preparation method according to any one of claims 3 to 9, in dyeing or printing fiber fabrics.