A reactive dye compound with tetraphenyl ethylene as a matrix, an intermediate, and a preparation method and application thereof
Patent Information
- Application Number
- CN202611153775.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-31
- Publication Date
- 2026-10-30
AI Technical Summary
现有常规染料骨架大多仅能提供固定数量的反应位点，若要制备不同发色强度的系列染料，需要重新设计合成全新的核心骨架，不仅合成步骤繁琐、分离纯化难度大，还大幅提升了系列染料的开发成本
[0013]与现有技术相比，本发明的有益效果在于：本发明所述的以四苯乙烯为母体的活性染料化合物具有上染率高、色光鲜艳、染色牢度优异和工业化可实施性强等特点。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of reactive dyes, and specifically relates to a class of reactive dye compounds based on tetraphenylethylene, intermediates, their preparation methods and applications. Background Technology
[0002] Reactive dyes are currently the most widely used dye category in the dyeing of cellulose fibers and modified polyamide fibers. Due to their ability to form covalent bonds with fibers, they possess wet fastness far exceeding that of acid dyes, occupying a core position in the mid-to-high-end textile fabric dyeing field. As the high-end textile industry continues to demand higher dyeing quality, the market is placing higher requirements on the color brightness, color intensity, and fixation rate of reactive dyes. Most existing conventional dye backbones can only provide a fixed number of reaction sites. To prepare a series of dyes with different color intensities, a completely new core backbone needs to be designed and synthesized. This not only involves cumbersome synthesis steps and difficult separation and purification, but also significantly increases the development cost of the series of dyes. H-acids and J-acids, as commonly used naphthalene-based dye intermediates, possess free amino groups that can be used to connect cyanuric chloride reactive groups, making them excellent building blocks for reactive dye construction. However, currently, there is a lack of core backbones that can flexibly provide different numbers of reaction sites and adapt to different numbers of intermediate grafts, making it difficult to efficiently develop a series of reactive dyes. Meanwhile, the conjugated π system of reactive dyes constructed with traditional small-molecule backbones has a limited length, generally suffering from low molar absorptivity and insufficient color intensity. Obtaining deep, rich colors requires increasing dye dosage, which raises dyeing costs and burdens wastewater treatment. Conventional methods of extending the conjugated system often sacrifice dye water solubility and easily lead to dull colors, failing to balance brightness and solubility. Currently, there are no reports on using tetraphenylethylene with different amino substitution numbers as the core backbone, introducing different numbers of H-acid / J-acid naphthalene intermediates by controlling the number of amino groups, and then grafting different numbers of cyanuric chloride reactive groups to construct a series of large conjugated reactive dyes. Developing a new series of reactive dyes that combine high development efficiency and excellent dyeing performance meets the current development needs of the textile printing and dyeing industry. Summary of the Invention
[0003] To address the existing technological gaps, the technical problem to be solved by this invention is to provide a novel reactive dye compound based on tetraphenylethylene, an intermediate, its preparation method, and its application; the reactive dye compound has the characteristics of high dyeing rate, bright color, excellent color fastness, and strong industrial feasibility.
[0004] In a first aspect, the present invention provides a reactive dye compound based on tetraphenylethylene, wherein the specific structure of the compound is shown as M1, M2, M3 or M4: .
[0005] Secondly, the present invention provides an intermediate for reactive dyes based on tetraphenylethylene, the specific structure of which is shown as D1, D2, D3 or D4: .
[0006] Thirdly, the present invention provides a method for preparing the reactive dye compound based on tetraphenylethylene as described in the first aspect, comprising the following steps: (1) Diazotize 4,4''-diamino-4',4'''-disulfonic tetraphenylethylene or 4-amino-4',4'',4'''-trisulfonic tetraphenylethylene to obtain the corresponding diazonium salt; The reaction formula is:
[0007] (2) Couple the diazonium salt obtained in step (1) with compound R1 or R2 to obtain the reactive dye intermediate based on tetraphenylethylene as described in the second aspect;
[0008] R1 R2
[0009] (3) The reactive dye compound based on tetraphenylethylene obtained in step (2) is prepared by condensing the reactive dye intermediate based on tetraphenylethylene with the condensation product of cyanuric chloride-para ester with the structure shown below.
[0010] Cyanide-para ester condensation product.
[0011] Fourthly, the present invention provides the application of the reactive dye compound based on tetraphenylethylene described in the first aspect in the printing or dyeing of fiber materials.
[0012] The fiber material can be one or a blend of several of the following: cellulose fiber material, protein fiber material, and synthetic fiber material. The cellulose fiber material includes cotton, linen, viscose, etc., the protein fiber material includes wool and silk, and the synthetic fiber material includes nylon, etc. Suitable dyeing processes include: dip dyeing, pad dyeing, cold padding, etc.
[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: the reactive dye compound based on tetraphenylethylene described in the present invention has the characteristics of high dyeing rate, bright color, excellent color fastness and strong industrial feasibility. Detailed Implementation
[0014] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0015] Example 1
[0016] Step 1, diazotization of 4-amino-4',4'',4'''-trisulfonate tetraphenylethylene
[0017] 1.17 g (0.002 mol) of 4-amino-4',4'',4'''-trisulfonicotetraphenylene (TST) and 0.14 g (0.0021 mol) of sodium nitrite were dissolved in 5 mL of deionized water, and the system temperature was controlled at 0–5 °C. 10 mL of deionized water and 1.5 mL (37%) of concentrated hydrochloric acid were added to a three-necked flask, and the mixture was stirred for 5 minutes under ice-water bath temperature control to stabilize the system temperature at 0–5 °C. Then, the sodium nitrite mixture was slowly added dropwise to the reaction system, and the reaction was maintained at low temperature for 30 minutes. Finally, an appropriate amount of aminosulfonic acid was added to eliminate excess sodium nitrite, yielding a diazonium salt solution containing compound 1, which was stored in an ice-water bath for later use.
[0018]
[0019] In the second step, the product in (1) is coupled with 1-amino-8-naphthol-3,6-disulfonic acid to prepare purple dye intermediate D1.
[0020] 1-Amino-8-naphthol-3,6-disulfonic acid (0.639 g, 0.002 mol) was dissolved in deionized water (10 mL), and the pH of the solution was adjusted to 7.0 ± 0.2 with sodium carbonate solution (10%). Diazonium salt solution was slowly added under controlled temperature (5-10 ℃), maintaining the pH of the reaction solution around 7.0 throughout. After 2 h of reaction, the pH of the reaction solution was adjusted to neutral. The solution was concentrated by rotary evaporation, and the concentrate was added dropwise to ethanol (50 mL) to precipitate crystals. The crystals were then vacuum dried (60 ℃, 12 h) to obtain the purple reactive dye intermediate D1. The 1H NMR spectrum of this dye intermediate is as follows: 1 H NMR(400MHz,D2O) δ:7.96 (s, 1H), 7.5~7.3 (m, J = 8.4 Hz, 7H), 7.24 (s, 1H), 7.02 (d, J= 1.5 Hz, 1H), 7.05 – 6.88 (m, 7H), 6.83 (s, 1H).
[0021]
[0022] Step 3: The above dye intermediate D1 is condensed with the para-ester-cyanuric chloride primary condensation product to prepare reactive dye.
[0023] Cyanuronic acid (0.368 g, 0.002 mol) was dispersed in 10 mL of ice-cold deionized water and mechanically stirred for 10 min to form a homogeneous low-temperature suspension, maintaining the system temperature at 0-5℃ throughout the process. Para-ester (0.570 g, 0.002 mol) solid was slowly added to the suspension and stirred for 5 min to ensure homogeneity. Then, a pre-prepared 5% sodium carbonate-baking soda solution was slowly added dropwise to the reaction system, strictly controlling the pH value between 6.0 and 6.5, and the reaction was maintained at 0-5℃ for 2 h. The reaction endpoint was determined by TLC monitoring until the para-ester completely disappeared. The dye intermediate D1 (1.834 g, 0.002 mol) obtained in step (2) was dissolved in 10 ml of water and added to the primary condensation solution. The pH value was adjusted to 6.5-7, and the temperature was slowly raised to 40 °C for secondary condensation. The reaction was kept at this temperature for 4 hours. The reaction was monitored by TLC until the primary condensation product disappeared. The reaction product was concentrated by rotary vacuum and recrystallized with ethanol to obtain the purple reactive dye M1, with a maximum absorption wavelength of 564 nm (aqueous solution).
[0024]
[0025] Example 2
[0026] Step 1, diazotization of 4,4''-diamino-4',4'''-disulfonicotetraphenylene
[0027] 1.04 g (0.002 mol) of 4,4''-diamino-4',4'''-disulfonic tetraphenylethylene and 0.28 g (0.0021 mol) of sodium nitrite were dissolved in 10 mL of deionized water, and the system temperature was maintained at 0–5 °C. 10 mL of deionized water and 3 mL (37%) of concentrated hydrochloric acid were added to a three-necked flask, and the mixture was stirred for 5 minutes in an ice-water bath to stabilize the system temperature at 0–5 °C. Then, the sodium nitrite mixture was slowly added dropwise to the reaction system, and the reaction was maintained at a low temperature for 45 minutes. Finally, an appropriate amount of aminosulfonic acid was added to eliminate excess sodium nitrite, yielding a diazonium salt solution containing compound 2, which was stored in an ice-water bath for later use.
[0028]
[0029] In the second step, the product in (1) is coupled with 1-amino-8-naphthol-3,6-disulfonic acid to prepare the purple dye D2.
[0030] 1-Amino-8-naphthol-3,6-disulfonic acid (1.278 g, 0.004 mol) was dissolved in deionized water (20 mL), and the pH of the solution was adjusted to 7.0 ± 0.2 with sodium carbonate solution (10%). Diazonium salt solution was slowly added under controlled temperature (5-10 ℃), maintaining the pH of the reaction solution around 7.0 throughout. After 2 h of reaction, the pH of the reaction solution was adjusted to neutral, and the solution was concentrated by rotary evaporation. The concentrate was added dropwise to ethanol (50 mL) to precipitate crystals, which were then dried under vacuum (60 ℃, 12 h) to obtain the purple dye D2. The yield was 85%, and the purity was 95%. The 1H NMR spectrum of this dye intermediate is as follows: 1 H NMR (400 MHz, D2O) δ:7.64 (dd, J = 20.4, 8.2 Hz, 8H), 7.46 (s, 2H), 7.30 – 7.13 (m, 10H), 7.05 (s, 2H).
[0031]
[0032] Step 3: The above dye intermediate D2 is condensed with the para-ester-cyanuric chloride primary condensation product to prepare reactive dye.
[0033] Cyanuronic acid (0.368 g, 0.002 mol) was dispersed in 10 mL of ice-cold deionized water and mechanically stirred for 10 min to form a homogeneous low-temperature suspension, maintaining the system temperature at 0-5℃ throughout the process. Para-ester (0.570 g, 0.002 mol) solid was slowly added to the suspension and stirred for 5 min to ensure homogeneity. Then, a pre-prepared 5% sodium carbonate-baking soda solution was slowly added dropwise to the reaction system, strictly controlling the pH value between 6.0 and 6.5, and the reaction was maintained at 0-5℃ for 2 h. The reaction endpoint was determined by TLC monitoring until the para-ester completely disappeared. The dye intermediate D2 (1.183 g, 0.001 mol) obtained in step (2) was dissolved in 10 ml of water and added to the primary condensation solution. The pH value was adjusted to 6.5-7, and the temperature was slowly raised to 40 °C for secondary condensation. The reaction was kept at this temperature for 4 hours. The reaction was monitored by TLC until the primary condensation product disappeared. The reaction product was concentrated by rotary vacuum and recrystallized with ethanol to obtain the reactive dye M2, with a maximum absorption wavelength of 584 nm (aqueous solution).
[0034]
[0035] Example 3
[0036] Step 1, diazotization of 4-amino-4',4'',4'''-trisulfonate tetraphenylethylene
[0037] 1.17 g (0.002 mol) of 4-amino-4',4'',4'''-trisulfonicotetraphenylene (TST) and 0.14 g (0.0021 mol) of sodium nitrite were dissolved in 5 mL of deionized water, and the system temperature was controlled at 0–5 °C. 10 mL of deionized water and 1.5 mL (37%) of concentrated hydrochloric acid were added to a three-necked flask, and the mixture was stirred for 5 minutes under ice-water bath temperature control to stabilize the system temperature at 0–5 °C. Then, the sodium nitrite mixture was slowly added dropwise to the reaction system, and the reaction was maintained at low temperature for 30 minutes. Finally, an appropriate amount of aminosulfonic acid was added to eliminate excess sodium nitrite, yielding a diazonium salt solution containing compound 1, which was stored in an ice-water bath for later use.
[0038]
[0039] In the second step, the product in (1) is coupled with 7-amino-4-hydroxy-2-naphthalenesulfonic acid to prepare the red intermediate D3.
[0040] 0.478 g (0.002 mol) of 7-amino-4-hydroxy-2-naphthalenesulfonic acid was dissolved in 20 mL of deionized water, and the pH was adjusted to 7.0 ± 0.2 with 10% sodium carbonate solution. Diazonium salt solution was slowly added under controlled temperature (5-10 °C), maintaining the pH of the reaction solution around 7.0 throughout. After 2 h of reaction, the pH was adjusted to neutral, and the solution was concentrated by rotary evaporation. The concentrate was added dropwise to 50 mL of ethanol to precipitate crystals, which were then dried under vacuum (60 °C, 12 h) to obtain the red dye intermediate D3. The yield was 85%, and the purity was 95%. The 1H NMR spectrum of this dye intermediate was as follows: 1 H NMR(400MHz,D2O) δ:7.98 (d, J = 2.0 Hz, 1H), 7.5~7.3 (m, J = 8.4 Hz, 8H), 7.26 (s, 1H), 7.04 (d,J = 1.6 Hz, 1H), 7.05 – 6.88 (m, 7H), 6.90 (dd, J = 8.2, 2.0 Hz, 1H).
[0041]
[0042] Step 3: The above dye intermediate D3 is condensed with the para-ester-cyanuric chloride primary condensation product to prepare reactive dye.
[0043] Cyanuronic acid (0.368 g, 0.002 mol) was dispersed in 10 mL of ice-cold deionized water and mechanically stirred for 10 min to form a homogeneous low-temperature suspension, maintaining the system temperature at 0-5℃ throughout the process. Para-ester (0.570 g, 0.002 mol) solid was slowly added to the suspension and stirred for 5 min to ensure homogeneity. Then, a pre-prepared 5% sodium carbonate-baking soda solution was slowly added dropwise to the reaction system, strictly controlling the pH value between 6.0 and 6.5, and the reaction was maintained at 0-5℃ for 2 h. The reaction endpoint was determined by TLC monitoring until the para-ester completely disappeared. The dye intermediate D3 (1.674 g, 0.002 mol) obtained in step (2) was dissolved in 10 ml of water and added to the primary condensation solution. The pH value was adjusted to 6.5-7, and the temperature was slowly raised to 40 °C for secondary condensation. The reaction was kept at this temperature for 4 hours. The reaction was monitored by TLC until the primary condensation product disappeared. The reaction product was concentrated by rotary vacuum and recrystallized by adding ethanol to obtain the reactive dye M3, with a maximum absorption wavelength of 514 nm (aqueous solution).
[0044]
[0045] Example 4
[0046] Step 1, diazotization of 4,4''-diamino-4',4'''-disulfonicotetraphenylene
[0047] 1.04 g (0.002 mol) of 4,4''-diamino-4',4'''-disulfonic tetraphenylethylene and 0.28 g (0.0021 mol) of sodium nitrite were dissolved in 10 mL of deionized water, and the system temperature was maintained at 0–5 °C. 10 mL of deionized water and 3 mL (37%) of concentrated hydrochloric acid were added to a three-necked flask, and the mixture was stirred for 5 minutes in an ice-water bath to stabilize the system temperature at 0–5 °C. Then, the sodium nitrite mixture was slowly added dropwise to the reaction system, and the reaction was maintained at a low temperature for 45 minutes. Finally, an appropriate amount of aminosulfonic acid was added to eliminate excess sodium nitrite, yielding a diazonium salt solution containing compound 2, which was stored in an ice-water bath for later use.
[0048]
[0049] In the second step, the product in (1) is coupled with 7-amino-4-hydroxy-2-naphthalenesulfonic acid to prepare intermediate D4.
[0050] 0.957 g (0.004 mol) of 7-amino-4-hydroxy-2-naphthalenesulfonic acid was dissolved in 20 mL of deionized water, and the pH was adjusted to 7.0 ± 0.2 with 10% sodium carbonate solution. Diazonium salt solution was slowly added under controlled temperature (5-10 °C), maintaining the pH of the reaction solution around 7.0 throughout. After 2 h of reaction, the pH was adjusted to neutral, and the solution was concentrated by rotary evaporation. The concentrate was added dropwise to 50 mL of ethanol to precipitate crystals, which were then dried under vacuum (60 °C, 12 h) to obtain the red dye intermediate D4. The yield was 85%, and the purity was 95%. The 1H NMR spectrum of this dye intermediate was as follows: 1 H NMR (400 MHz, D2O)δ: 7.62 (dd, J = 20.2, 8.0 Hz, 8H), 7.44 (s, 2H), 7.30 – 7.12 (m, 10H), 7.03(s, 2H), 6.95 (d, J = 8.1 Hz, 2H), 6.82 (d, J = 7.9 Hz, 2H).
[0051]
[0052] Step 3: The above dye intermediate D4 is condensed with the para-ester-cyanuric chloride primary condensation product to prepare reactive dye M4.
[0053] Cyanuronic acid (0.368 g, 0.002 mol) was dispersed in 10 mL of ice-cold deionized water and mechanically stirred for 10 min to form a homogeneous low-temperature suspension, maintaining the system temperature at 0-5℃ throughout the process. Para-ester (0.570 g, 0.002 mol) solid was slowly added to the suspension and stirred for 5 min to ensure homogeneity. Then, a pre-prepared 5% sodium carbonate-baking soda solution was slowly added dropwise to the reaction system, strictly controlling the pH value between 6.0 and 6.5, and the reaction was maintained at 0-5℃ for 2 h. The reaction endpoint was determined by TLC monitoring until the para-ester completely disappeared. The dye intermediate D4 (1.022 g, 0.001 mol) obtained in step (2) was dissolved in 10 ml of water and added to the primary condensation solution. The pH was adjusted to 6.5-7, and the temperature was slowly raised to 40 °C for secondary condensation. The reaction was maintained at this temperature for 4 hours. The reaction was monitored by TLC until the primary condensation product disappeared. The reaction product was concentrated by rotary vacuum and recrystallized by adding ethanol to obtain the reactive dye M. 4， The maximum absorption wavelength is 512 nm (in aqueous solution).
[0054]
[0055] Staining Example 5
[0056] The four reactive dye compounds prepared in Examples 1-4, which were not commercially available, were used to dye cotton, viscose, wool, and nylon fabrics using an immersion dyeing method. The dye dosage for each compound was 2% (owf).
[0057] The dyeing and finishing process for cotton and viscose is the same: dyeing bath ratio 1:20, dyeing at room temperature, heating at 2°C / min to 40°C, holding at that temperature for 10 minutes, adding sodium sulfate (20g / L), holding at that temperature for 20 minutes, then heating at 2°C / min to 60°C, holding at that temperature for 10 minutes, then adding soda ash (10g / L), holding at that temperature for 40 minutes, and the dyeing is complete. After dyeing, the fabric is washed with hot water, soaped, washed with hot water, washed with cold water, and then dried.
[0058] The dyeing and finishing processes for wool and nylon are the same: a dyeing bath ratio of 1:20, dyeing at room temperature, heating at 2°C / min to 40°C, holding for 10 minutes, adding acetic acid (2g / L), holding for 20 minutes, then heating at 2°C / min to 95°C, holding for 10 minutes, adding baking soda (13g / L), and holding for 40 minutes to complete the dyeing process. After dyeing, the fabric is washed with hot water, soaped, washed with hot water again, washed with cold water, and then dried.
[0059] The rubbing resistance, washing resistance, and light fastness of dyed fabrics were characterized according to ISO 105-X12, ISO 105-C10, and ISO 105-B02. The K / S values of the dyed fabric samples were measured using a Datacolor 800 colorimeter with a D65 light source and a 10° viewing angle.
[0060] The corresponding data are shown in Table 1. It can be seen that the dyeing rate and fixation rate of the four dyes are good, and the various fastness properties are good, which makes them valuable for application, especially in dyeing cotton, viscose and wool fabrics.
[0061] Table 1. Dye uptake and various fastness properties of four dyes during immersion.
Claims
1. A reactive dye compound based on tetraphenylethylene, characterized in that: The specific structures of the reactive dye compounds based on tetraphenylethylene are shown in M1, M2, M3, or M4: 。 2. A reactive dye intermediate based on tetraphenylethylene, characterized in that: The specific structures of the reactive dye intermediates based on tetraphenylethylene are shown in D1, D2, D3, or D4: 。 3. A method for preparing a reactive dye compound based on tetraphenylethylene as described in claim 1, characterized in that: The preparation method includes the following steps: (1) Diazotize 4,4''-diamino-4',4'''-disulfonic tetraphenylethylene or 4-amino-4',4'',4'''-trisulfonic tetraphenylethylene to obtain the corresponding diazonium salt; (2) Couple the diazonium salt obtained in step (1) with compound R1 or R2 to obtain the reactive dye intermediate based on tetraphenylethylene as described in claim 2; R1 R2 (3) The reactive dye compound based on tetraphenylethylene obtained in step (2) is prepared by condensing the reactive dye intermediate based on tetraphenylethylene with the condensation product of cyanuric chloride-para ester with the structure shown below. Cyanide-para ester condensation product.
4. The application of the reactive dye compound based on tetraphenylethylene as described in claim 1 in the printing or dyeing of fiber materials.
5. The application as described in claim 4, characterized in that: The fiber material is a blend of one or more of the following: cellulose fiber material, protein fiber material, and synthetic fiber material.
6. The application as described in claim 5, characterized in that: The cellulose fiber materials include cotton, linen, and viscose; the protein fiber materials include wool and silk; and the synthetic fiber materials include nylon.