Reactive disperse dye and dyeing process

Abstract

The present invention belongs to the technical field of textile production, and relates to an active disperse dye and a dyeing process. The active disperse dye includes a dye mother body and a bisaziridine chain segment grafted thereon, and "-OCH2-" is introduced as an electron-donating group at the para position of the aromatic ring of the bisaziridine chain segment. Dyeing process: After dissolving the active disperse dye, dye the textile; the textile is composed of one or more of natural fibers and synthetic fibers; the dyeing temperature is 85-100 °C, and the dyeing temperature is higher than the T of the synthetic fiber g . By introducing the "-OCH2-" electron-donating group at the para position of the aromatic ring of the bisaziridine chain segment, the conjugation effect and inductive effect of this group reduce the activation energy of C-N bond cleavage, enabling the efficient generation of carbene without relying on high temperature or acid-base environment, and solving the problems of harsh conditions for generating carbene from the bisaziridine chain segment in the prior art and low color fastness of the dyed textile when using supercritical CO2 fluid for dyeing.

Description

Technical Field

[0001] The present invention belongs to the technical field of textile production, and relates to a reactive disperse dye and a dyeing process. Background Art

[0002] Reactive disperse dyes containing diazirine segments are a type of special disperse dyes with diazirine groups introduced into their molecular structures. Under certain conditions, the diazirine groups can generate carbene groups, and these carbene groups can form covalent bond bindings with functional groups such as alkyl groups, amino groups, and hydroxyl groups in fiber molecules; such dyes not only possess excellent absorption spectral characteristics and thermal stability, but also effectively solve the problem of thermal migration caused by weak intermolecular forces between disperse dyes and fibers; by enhancing the binding force between the dye and the fiber, reactive disperse dyes containing diazirine segments significantly improve the dyeing properties of synthetic fibers such as polypropylene (PP), aramid, etc., and improve the depth of dyeing and color fastness, which makes them show superior application potential in the textile industry, especially in the dyeing processes of clothing, home textiles, and industrial fabrics with strict requirements for high wash resistance and high color fastness.

[0003] Literature 1 (Dyes and Pigments, 2025, 233: 112517.), Literature 2 (Dyes and Pigments, 2024, 221: 111784.), Literature 3 (Coloration Technology, 2022, 138(5): 551 - 564.), and Literature 4 (Dyes and Pigments, 2021, 194: 109555.) disclose reactive disperse dyes containing diazirine segments, and their fixation temperatures are usually between 120 - 140 °C. These dyes require relatively high temperatures to achieve the reaction between carbene and fiber alkyl groups, which is not conducive to energy conservation and emission reduction, and may cause problems such as strength damage and poor handle for synthetic fibers with low glass transition temperature (T g ) such as polylactic acid (PLA), acetate fiber, polyamide, polyurethane, etc.

[0004] Therefore, it is necessary to design a reactive disperse dye with simple conditions for the generation of carbene from diazirine segments and use it for the dyeing of textiles.

[0005] In recent years, supercritical CO 2Fluid dyeing technology has received extensive attention due to its environmental protection characteristics of energy conservation, emission reduction, and waterless dyeing. However, the dye systems and processes of existing technologies still have significant deficiencies, mainly manifested in the low color fastness of dyed textiles. For the dyeing of synthetic fibers, some existing disperse dyes have good solubility, but the color fastness of fibers or fabrics after dyeing polyester fibers is poor. For cellulose fibers (such as cotton, linen, regenerated cellulose fibers such as viscose, etc.), the fixation reactions of the fixing groups of traditional reactive dyes (such as halo-s-triazine and vinyl sulfone structures) usually require alkaline conditions, while in the supercritical CO 2 fluid system, because a small amount of water-swelling fiber needs to be added, after reacting with CO 2 to form carbonic acid, the surface of the fiber or fabric becomes acidic, resulting in a significant decrease in the fixation rate and color fastness.

[0006] Therefore, it is also necessary to design an active disperse dye and use it for supercritical CO 2 fluid dyeing to solve the above problems. Summary of the Invention

[0007] The purpose of the present invention is to solve the problems existing in the prior art and provide an active disperse dye and a dyeing process.

[0008] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0009] An active disperse dye includes a dye parent and a bis(aziridine) segment grafted thereon. The structural formula of the bis(aziridine) segment is as follows:

[0010] ;

[0011] In the formula, X is -(CH 2 ) n -, n is an integer, n≥2;

[0012] The active disperse dye does not contain water-soluble groups.

[0013] One of the purposes of the present invention is to solve the problem that the conditions for the formation of carbenes from bis(aziridine) segments in the prior art are harsh (requiring a high temperature of 120 - 140 °C). The bis(aziridine) segment of the present application (specifically, the trifluoromethylphenyl bis(aziridine) segment) can generate carbenes under ultraviolet light (365 nm) or low temperature (85 - 100 °C). This benefits from the unique chemical properties and optimized design of the bis(aziridine) segment. The C-N bond of the three-membered ring in the bis(aziridine) molecule has a relatively high tension, and this internal stress makes it easy to break and generate carbenes (R 1 -:C-R 2 ) under specific conditions. The present invention introduces "-OCH 2- As an electron-donating group, this group regulates the intramolecular electron density distribution through conjugation and inductive effects, reducing the activation energy required for the cleavage of the C-N bond, thereby significantly lowering the energy barrier for carbene generation.

[0014] The photon energy of ultraviolet light (365 nm) is approximately 3.4 eV, which can efficiently excite the π→π or n→π transition of the diaziridine molecule, causing the molecule to enter the excited state; in the excited state, the strength of the C-N bond is further weakened, and the three-membered ring decomposes into a carbene and stable nitrogen gas (N 2 ), and nitrogen gas, as a highly stable leaving group, greatly promotes the reaction in the direction of carbene formation.

[0015] The three-membered ring C-N bond in the diaziridine molecule has relatively high internal stress. When heated, the atomic thermal motion intensifies, and the internal stress can promote the cleavage of the C-N bond to generate a carbene intermediate and nitrogen gas. By introducing a "-OCH 2 -" electron-donating group at the para-position of the aromatic ring in the diaziridine segment, the conjugation and inductive effects of this group reduce the activation energy for the cleavage of the C-N bond, enabling the carbene to be generated at low temperatures.

[0016] As a preferred technical solution:

[0017] An active disperse dye as described above, wherein the dye parent contains two or more amino or hydroxyl groups to facilitate the connection of the dye parent with the diaziridine segment, etc.; the active disperse dye is an anthraquinone dye, an azo dye, a phthalocyanine dye, or a heterocyclic dye.

[0018] An active disperse dye as described above further includes a polyether segment grafted on the dye parent. The number of repeating units of the polyether segment is 2-5, i.e., -(CH 2 -CH 2 -O) m -, m = 2-5, and the end group is methyl (-CH 3 ).

[0019] The present invention also provides a dyeing process. After dissolving the dye, the textile is dyed. The dye is an active disperse dye, and the active disperse dye includes a dye parent and a diaziridine segment grafted thereon. The structural formula of the diaziridine segment is as follows:

[0020] ;

[0021] In the formula, X is -(CH 2 ) n -, n is an integer, and n ≥ 2;

[0022] The reactive disperse dye does not contain water-soluble groups. Through the structural design without water-soluble groups, the risk of hydrolysis and color fading of the reactive disperse dye on the surface of hydrophilic fibers is avoided, fundamentally improving the problems of poor washing color fastness and wet rubbing color fastness.

[0023] The textile is composed of more than one of natural fibers (such as natural cellulose fibers like cotton and linen, regenerated cellulose fibers like viscose and lyocell, protein fibers like wool and silk) and synthetic fibers (such as polyester, iterative polyester, polyamide, polyacrylonitrile, polylactic acid, polypropylene, polyurethane, etc.).

[0024] The dyeing temperature is 85 - 100 °C. The dyeing temperature is higher than the T of synthetic fibers. g and the dyeing temperature must be above the T of synthetic fibers. g Only then can the molecular chains in the amorphous region of the fiber start to thermally migrate. The thermal migration creates free volume inside the amorphous region of the fiber for the dye to adsorb and diffuse. The dyeing temperature is preferably 20 - 30 °C higher than the T of synthetic fibers. At this time, the free volume is larger, and a higher dye uptake rate and satisfactory dyeing effect can be obtained after dyeing. g

[0025] As a preferred technical solution:

[0026] In a dyeing process as described above, the dye parent contains two or more amino groups or hydroxyl groups; the reactive disperse dye is an anthraquinone dye, an azo dye, a phthalocyanine dye, or a heterocyclic dye.

[0027] In a dyeing process as described above, during the dyeing process, ultraviolet light (365 nm) is also used to irradiate the dyeing system.

[0028] The temperature limitation during the dyeing process may not be sufficient to efficiently generate carbenes. Especially under low-temperature conditions, the generation efficiency of carbenes may be low. During the low-temperature dyeing process, ultraviolet light (365 nm) is introduced to excite the bisaziridine segment, triggering π→π or n→π transitions through photon energy (about 3.4 eV), enhancing the generation efficiency of carbenes, enabling the efficient generation of carbenes under low-temperature conditions, improving the fixation rate of the dye, and at the same time reducing the thermal damage to low-T g fibers.

[0029] In a dyeing process as described above, after the dyeing is completed, a fixation treatment is also carried out. The process of the fixation treatment is: irradiating the dyed textile under ultraviolet light (365 nm).

[0030] After the dyeing is completed, some dyes may not be completely fixed, affecting the dyeing fastness. The present invention uses ultraviolet light to further excite the residual bisaziridine segments in the dye to generate carbenes, which react covalently with the fiber, strengthening the fixation effect, improving the fixation rate, and further enhancing the color fastness of the dyed fabric (including washing, wet rubbing, and sublimation fastness).

[0031] After the dyeing is completed, or after the fixation is completed, the textile is also washed to remove the unfixed reactive disperse dye; when the textile is composed of natural fibers, the above washing is carried out in sequence of soaping, hot water washing, and cold water washing; when the textile is composed of synthetic fibers, the above washing is reduction washing.

[0032] In a dyeing process as described above, during the fixation treatment, the dyed textile is covered so that only a partial area of the dyed textile is exposed to ultraviolet light (365 nm).

[0033] When there are multiple fibers or complex fabric structures during the dyeing process, it is necessary to preferentially complete the fixation reaction in specific areas. The present invention precisely controls the carbene generation area of the bisaziridine segment through local ultraviolet light irradiation, realizes preferential fixation or fancy dyeing in specific areas, and further improves the flexibility of the dyeing process, which can be used for the functional dyeing design of patterned fabrics or composite fabrics.

[0034] In a dyeing process as described in any one of the above, the dissolved dye uses supercritical CO 2 fluid.

[0035] The second object of the present invention is to solve the problem of low color fastness of the dyed textile when using supercritical CO 2 fluid for dyeing. The bisaziridine segment in the reactive disperse dye adopted by the present invention can achieve efficient generation of carbene without relying on high temperature or acid-base environment. Especially in the weakly acidic environment of supercritical CO 2 , the carbene generation efficiency and reaction activity are not affected. At the same time, the carbene has high activity and can react with natural fibers (hydroxyl groups in cellulose fibers, amino groups in protein fibers) and synthetic fibers (alkyl groups) in the weakly acidic environment to form covalent bonds, thereby firmly fixing the dye on the textile and improving the color fastness.

[0036] In a dyeing process as described above, the steps of dyeing are as follows:

[0037] (a) Place the textile with a moisture content of 0 - 100 wt% (when the textile is composed of synthetic fibers, the moisture content is 0 wt%; when the textile is composed of natural fibers, the moisture content is 50 - 100 wt%) and the reactive disperse dye in a supercritical CO 2 fluid dyeing device, and close the device;

[0038] (b) Introduce CO 2 into the device, raise the temperature to 85 - 100 °C, and at the same time raise the pressure to 15 - 30 MPa to mix the reactive disperse dye with the supercritical CO 2 fluid;

[0039] (c) Control supercritical CO 2 The fluid is circulated in the device for 30 - 120 min (during the circulation process, the supercritical CO 2 fluid continuously dissolves the reactive disperse dye, and brings the dissolved reactive disperse dye to the surface and inside of the fiber for dyeing), then the temperature and pressure are reduced, and CO 2 and the unreacted reactive disperse dye are separated and recovered.

[0040] For a dyeing process as described in any one of the above, the reactive disperse dye further includes a polyether chain segment grafted on the dye parent body. The repeating unit number of the polyether chain segment is 2 - 5, and the end group is methyl; the textile is composed of hydrophilic fibers.

[0041] In the dye system and process of the prior art, there are still problems that the dye is not easily detached from the fluid after being dissolved in the supercritical CO 2 fluid and adsorbed onto the hydrophilic fiber, resulting in a low dye uptake rate and difficulty in dyeing dark colors.

[0042] The present invention can solve the above problems. The reactive disperse dye of the present invention contains a polyether chain segment, which can reduce the melting point and intermolecular crystal forces of the reactive disperse dye, increase the solubility of the reactive disperse dye in the supercritical CO 2 fluid, and can also reduce the dissolution energy consumption of the reactive disperse dye. Particularly importantly, when the reactive disperse dye contacts the hydrophilic fiber containing a small amount of water, the polyether chain segment can help the reactive disperse dye to detach from the supercritical CO 2 fluid and adsorb onto the hydrophilic fiber by forming hydrogen bonds. This property significantly improves the affinity of the water-insoluble reactive disperse dye for the hydrophilic fiber, effectively improves the dye uptake rate and realizes dark color dyeing.

[0043] The chain length of the polyether chain segment in the reactive disperse dye of the present invention is appropriate, which can avoid the problems of poor effect of the polyether chain segment in increasing the solubility of the reactive disperse dye in the supercritical CO 2 fluid and too weak affinity between the reactive disperse dye and the hydrophilic fiber due to too short a chain length, and can also avoid the problem that the diffusion ability of the reactive disperse dye in the fiber interior is weak and the polyether chain segment will wrap the reactive group, affecting its reaction with the fiber due to too long a chain length. In this way, the dye can not only be more effectively dissolved in the supercritical CO 2 fluid, facilitating the transfer during the dyeing process, but also maintain good contact with the fiber, ensuring that the dye molecules can uniformly and rapidly penetrate into the fiber interior, achieving an ideal dyeing depth and uniformity.

[0044] The present invention designs the end group of the polyether chain segment to be methyl. The terminal methyl is relatively inert and not easily participates in reactions, which helps to improve the stability and diffusion ability of the reactive disperse dye molecules.

[0045] Beneficial effects:

[0046] (1) By introducing a "-OCH 2 -" electron-donating group at the para-position of the aromatic ring in the bisaziridine segment, the conjugation effect and inductive effect of this group reduce the activation energy for the cleavage of the C-N bond, enabling the efficient generation of carbene without relying on high temperature or acidic / basic environments, thus solving the problems in the prior art that the conditions for generating carbene from the bisaziridine segment are harsh and the color fastness of the dyed textiles is low when using supercritical CO 2 fluid for dyeing.

[0047] (2) The reactive disperse dyes of the present invention contain a polyether segment, which can reduce the melting point and intermolecular forces between crystals of the reactive disperse dyes, increase the solubility of the reactive disperse dyes in supercritical CO 2 , and can also reduce the energy consumption for dissolving the reactive disperse dyes. Particularly importantly, when the reactive disperse dyes come into contact with hydrophilic fibers containing a small amount of water, the polyether segment can help the reactive disperse dyes detach from the supercritical CO 2 fluid and adsorb onto the hydrophilic fibers by forming hydrogen bonds. This property significantly improves the affinity of the water-insoluble reactive disperse dyes for hydrophilic fibers, effectively increasing the dye uptake rate and achieving dark color dyeing.

[0048] (3) The reactive disperse dyes of the present invention adopt a structural design without water-soluble groups, avoiding the risk of hydrolysis and color fading of the reactive disperse dyes on the surface of hydrophilic fibers, and fundamentally improving the problems of poor wash color fastness and wet rubbing color fastness. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 and Figure 2 are the synthesis processes of the reactive disperse dyes in Example A1;

[0050] Figure 3 are the synthesis processes of the reactive disperse dyes in Example A2;

[0051] Figure 4 are the synthesis processes of the reactive disperse dyes in Example A3;

[0052] Figure 5 are the synthesis processes of the reactive disperse dyes in Example A4;

[0053] Figure 6 are the synthesis processes of the reactive disperse dyes in Comparative Example A1;

[0054] Figure 7 are the synthesis processes of the reactive disperse dyes in Example A5;

[0055] Figure 8 are the synthesis processes of the reactive disperse dyes in Example A6. DETAILED DESCRIPTION OF THE INVENTION

[0056] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0057] The following are the test methods for relevant performance indicators in each example and comparative example:

[0058] Soaping color fastness: Determined with reference to the standard of GB / T 3921-2008;

[0059] Dry / wet rubbing color fastness: Determined with reference to the standard of GB / T 3920-2008;

[0060] Light color fastness: Determined with reference to the standard of GB / T 8426-1998;

[0061] Dry heat color fastness: Determined with reference to the standard of GB / T 5718-1997;

[0062] Dye uptake rate: Determined with reference to the standard of GB / T 23976.1-2009;

[0063] Color depth Integ value: Determined with reference to the standard of GB / T 21875-2016.

[0064] Example A1

[0065] A preparation method of an active disperse dye, the overall process is as Figures 1 to 2 shown, and the specific steps are as follows:

[0066] (1) Synthesis of intermediate 1-3;

[0067] (1.1) At room temperature, dissolve 430 mmol of 3-phenyl-3-(trifluoromethyl)-3H-diazirine and 516 mmol of N-iodosuccinimide in 150 mL of solvent A (composed of acetonitrile and trifluoroacetic acid with a volume ratio of 1:3) to obtain solution A, and cool solution A to 0 °C in an ice-water bath;

[0068] (1.2) Slowly add solution B (composed of 1032 mmol of H 2 SO 4 , 45 mL of trifluoroacetic acid and 15 mL of acetonitrile) dropwise to solution A, then slowly raise the temperature of the system to 25 °C, stir and react for 24 h, and then pour the system into an ice-water mixture containing sodium bicarbonate for neutralization;

[0069] (1.3) The aqueous phase generated in step (1.2) was successively subjected to liquid-liquid extraction (3 times, 150 mL of diethyl ether each time), the organic phases were combined, washed (2 times, 150 mL of saturated sodium thiosulfate aqueous solution at 25 °C each time), dried (using anhydrous sodium sulfate), and concentrated to obtain crude product A. Then, the crude product A was purified by a silica gel column (the eluent was pentane) to obtain intermediate 1-1 (a pale yellow or light pink liquid);

[0070] (1.4) Add 320 mmol of intermediate 1-1, 320 mL of dimethyl sulfoxide, 961.4 mmol of ethylene glycol, and 801 mmol of CsOH·H 2 O into the flask. After heating to 40 °C, bubble with argon for 15 min to remove oxygen;

[0071] (1.5) After adding copper(II) bis(2,4-pentanedionate) to the system in step (1.4) in 3 batches, monitor the reaction process by nuclear magnetic resonance fluorine spectrum ( 19 F-NMR). After the reaction is completed, add 500 mL of water to terminate the reaction; among them, the addition amount of the first batch of copper(II) bis(2,4-pentanedionate) is 80 mmol; the second batch of copper(II) bis(2,4-pentanedionate) is added 20 h after the addition of the first batch of copper(II) bis(2,4-pentanedionate), and the addition amount is 40 mmol; the third batch of copper(II) bis(2,4-pentanedionate) is added 4 h after the addition of the second batch of copper(II) bis(2,4-pentanedionate), and the addition amount is 40 mmol;

[0072] (1.6) The aqueous phase generated in step (1.5) was successively subjected to liquid-liquid extraction (4 times, 300 mL of dichloromethane each time), the organic phases were combined, washed once (3 times, 150 mL of saturated aqueous ammonia solution at 25 °C each time), washed twice (3 times, 150 mL of water each time), dried, and concentrated to obtain crude product B. Then, the crude product B was purified by a silica gel column (the eluent was a mixture of diethyl ether and pentane with a volume ratio of 1:1) to obtain intermediate 1-2 (a viscous yellow liquid);

[0073] (1.7) Dissolve 365.58 mmol of intermediate 1-2 in 600 mL of dichloromethane and cool it to 0 °C to obtain an intermediate 1-2 solution. Dissolve 548.37 mmol of triphenylphosphine in 200 mL of dichloromethane to obtain a triphenylphosphine solution. Add the triphenylphosphine solution to the intermediate 1-2 solution to obtain a mixed solution;

[0074] (1.8) 438.70 mmol of carbon tetrabromide was dissolved in 300 mL of dichloromethane and degassed to obtain a carbon tetrabromide solution. The carbon tetrabromide solution was slowly added dropwise to the mixed solution. After that, the reaction was stirred at 0 °C for 2 h and then at 25 °C for 24 h. Subsequently, the reaction system was diluted with water;

[0075] (1.9) The aqueous phase generated in step (1.8) was successively subjected to liquid-liquid extraction (3 times, 50 mL of dichloromethane each time), combined organic phases, drying (using anhydrous magnesium sulfate), filtration, and concentration to obtain crude product C. Then, crude product C was purified by a silica gel column (eluent: pentane) to obtain intermediate 1-3 (as a yellow oil);

[0076] (2) Synthesis of intermediate 2-1;

[0077] (2.1) 3.77 mmol of 1,5-dihydroxyanthraquinone was dissolved in 15 mL of DMF to obtain a 1,5-dihydroxyanthraquinone solution. 11.31 mmol of anhydrous potassium carbonate (to remove moisture) was added to the 1,5-dihydroxyanthraquinone solution and stirred for 30 min;

[0078] (2.2) Under argon protection, 5.66 mmol of diethylene glycol-2-bromoethyl methyl ether was added to the system of step (2.1). After stirring at 60 °C for 6 h, the reaction progress was monitored by thin-layer chromatography (silica gel TLC, eluent: a mixture of ethyl acetate and n-hexane with a volume ratio of 1:1). After the reaction ended, the reaction system was cooled to room temperature, and the reaction was terminated with 50 mL of ice water;

[0079] (2.3) The aqueous phase generated in step (2.2) was successively subjected to liquid-liquid extraction (3 times, 50 mL of ethyl acetate each time), combined organic phases, washing (using a saturated sodium chloride aqueous solution at 25 °C), drying (using anhydrous sodium sulfate), and concentration to obtain crude product D. Then, crude product D was purified by a silica gel column (eluent: a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3) to obtain intermediate 2-1;

[0080] (3) Synthesis of the reactive disperse dye;

[0081] (3.1) 2.1 mmol of intermediate 2-1 was dissolved in 10 mL of acetonitrile to obtain an intermediate 2-1 solution. 6.3 mmol of anhydrous potassium carbonate was added to the intermediate 2-1 solution and stirred for 30 min;

[0082] (3.2) Under argon protection, 2.5 mmol of intermediate 1-3 was added to the system of step (3.1). After stirring and reacting at 50 °C for 8 h, the reaction progress was monitored by thin-layer chromatography (silica gel TLC, eluent: a mixture of dichloromethane and methanol with a volume ratio of 9:1). After the reaction was completed, the reaction system was cooled to room temperature and diluted with 30 mL of water;

[0083] (3.3) The aqueous phase generated in step (3.2) was successively subjected to liquid-liquid extraction (3 times, 20 mL of dichloromethane each time), combined organic phases, washing (with saturated sodium chloride aqueous solution at 25 °C), drying, and concentration to obtain crude product E. Then, the crude product E was purified by silica gel column chromatography (eluent: a mixture of dichloromethane and methanol with a volume ratio of 95:5) to obtain the reactive disperse dye (denoted as anthraquinone dye A1).

[0084] Example A2

[0085] A preparation method of a reactive disperse dye, the overall process is as Figure 3 shown, and the specific steps are as follows:

[0086] (1) Synthesis of intermediate 1-3 ( );

[0087] The synthesis process is basically the same as that of Example A1, except that: step (1.4) is: 320 mmol of intermediate 1-1, 320 mL of dimethyl sulfoxide, 961.4 mmol of propylene glycol, and 801 mmol of CsOH·H 2 2O were added to the flask. After heating to 42 °C, argon was bubbled for 15 min to remove oxygen;

[0088] (2) Synthesis of intermediate 3-1;

[0089] (2.1) 4.4 mmol of 4-amino-4'-hydroxyazobenzene was dissolved in 20 mL of acetonitrile to obtain a 4-amino-4'-hydroxyazobenzene solution. 13.2 mmol of anhydrous potassium carbonate was added to the 4-amino-4'-hydroxyazobenzene solution and stirred for 30 min;

[0090] (2.2) Under argon protection, 6.6 mmol of 1-bromo-2-(2-methoxyethoxy)ethane was slowly added to the system of step (2.1). After stirring and reacting at 60 °C for 6 h, the reaction progress was monitored by thin-layer chromatography (silica gel TLC, eluent: a mixture of ethyl acetate and n-hexane with a volume ratio of 1:1). After the reaction was completed, the reaction system was cooled to room temperature and the reaction was terminated with 50 mL of ice water;

[0091] (2.3) The aqueous phase generated in step (2.2) was successively subjected to liquid-liquid extraction (3 times, 30 mL of ethyl acetate each time), the organic phases were combined, washed (with saturated sodium chloride aqueous solution at 25 °C), dried (with anhydrous sodium sulfate), and concentrated to obtain the crude product F. Then, the crude product F was purified by silica gel column (the eluent was a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3) to obtain the intermediate 3-1;

[0092] (3) Synthesis of the reactive disperse dye;

[0093] (3.1) Dissolve 2.5 mmol of the intermediate 3-1 in 15 mL of DMF to obtain the intermediate 3-1 solution, and add 7.5 mmol of anhydrous potassium carbonate to the intermediate 3-1 solution;

[0094] (3.2) Under argon protection, add 3.0 mmol of the intermediate 1-3 to the system of step (3.1), stir evenly, and then stir at 50 °C for 8 h. After that, monitor the reaction progress by thin-layer chromatography (silica gel TLC, the developing agent was a mixture of dichloromethane and methanol with a volume ratio of 9:1). After the reaction was completed, cool the reaction system to room temperature and dilute it with 30 mL of water;

[0095] (3.3) The aqueous phase generated in step (3.2) was successively subjected to liquid-liquid extraction (3 times, 20 mL of dichloromethane each time), the organic phases were combined, washed (with saturated sodium chloride aqueous solution at 25 °C), dried (with anhydrous sodium sulfate), and concentrated to obtain the crude product G. Then, the crude product G was purified by silica gel column (the eluent was a mixture of dichloromethane and methanol with a volume ratio of 95:5) to obtain the reactive disperse dye (denoted as azo dye A2).

[0096] Example A3

[0097] A preparation method of a reactive disperse dye, the overall process is as Figure 4 shown, and the specific steps are as follows:

[0098] (1) Synthesis of the intermediate 1-3 ( )

[0099] The synthesis process was basically the same as that of Example A1, with the only difference being that in step (1.4): add 320 mmol of the intermediate 1-1, 320 mL of dimethyl sulfoxide, 961.4 mmol of 1,5-pentanediol and 801 mmol of CsOH·H 2 O to the flask, heat to 50 °C, and then bubble with argon for 15 min to remove oxygen;

[0100] (2) Synthesis of the intermediate 4-1;

[0101] (2.1) Dissolve 2.5 mmol of copper(II) (tetraaminophthalocyanine) in 30 mL of dichloromethane to obtain a copper(II) (tetraaminophthalocyanine) solution. Add 18 mmol of anhydrous potassium carbonate to the copper(II) (tetraaminophthalocyanine) solution and stir for 30 min;

[0102] (2.2) Under argon protection, slowly add 3.75 mmol of methyl-pentaethylene glycol-bromide dropwise to the system in step (2.1). After the addition is complete, stir at 70 °C for 12 h, and then monitor the reaction progress by thin-layer chromatography (silica gel TLC, eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:1). After the reaction is completed, cool the reaction system to room temperature and terminate the reaction with 50 mL of ice water;

[0103] (2.3) The aqueous phase generated in step (2.2) is successively subjected to liquid-liquid extraction (3 times, 30 mL of ethyl acetate each time), combine the organic phases, wash (with a saturated sodium chloride aqueous solution at 25 °C), dry (with anhydrous sodium sulfate), and concentrate to obtain the crude product H. Then, purify the crude product H through a silica gel column (eluent is a mixture of dichloromethane and methanol with a volume ratio of 95:5) to obtain the intermediate 4-1;

[0104] (3) Synthesis of the reactive disperse dye;

[0105] (3.1) Dissolve 1.7 mmol of the intermediate 4-1 in 20 mL of dichloromethane to obtain an intermediate 4-1 solution. Add 2.2 mmol of the intermediate 1-3 and 18 mmol of anhydrous potassium carbonate to the intermediate 4-1 solution and stir for 30 min;

[0106] (3.2) Under argon protection, stir the system in step (3.1) at 50 °C for 12 h, and then monitor the reaction progress by thin-layer chromatography (silica gel TLC, eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:1). After the reaction is completed, cool the reaction system to room temperature and terminate the reaction with 50 mL of ice water;

[0107] (3.3) The aqueous phase generated in step (3.2) is successively subjected to liquid-liquid extraction (3 times, 30 mL of ethyl acetate each time), combine the organic phases, wash (with a saturated sodium chloride aqueous solution at 25 °C), dry (with anhydrous sodium sulfate), and concentrate to obtain the crude product I. Then, purify the crude product I through a silica gel column (eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3) to obtain the reactive disperse dye (denoted as phthalocyanine dye A3).

[0108] Example A4

[0109] A preparation method of a reactive disperse dye, the overall process is as Figure 5As shown below, the specific steps are as follows:

[0110] (1) Synthesis of intermediate 1-3 ( )

[0111] The synthesis process is basically the same as that in Example A1, with the only difference being that in step (1.4): 320 mmol of intermediate 1-1, 320 mL of dimethyl sulfoxide, 961.4 mmol of 1,4-butanediol, and 801 mmol of CsOH·H 2 O were added to the flask. After heating to 45 °C, argon was bubbled for 15 min to remove oxygen;

[0112] (2) Synthesis of intermediate 5-3

[0113] (2.1) 3.4 mmol of 2-amino-4,6-dibromobenzothiazole was dissolved in 10 mL of water to obtain a 2-amino-4,6-dibromobenzothiazole solution. After adding 5 mL of 37% hydrochloric acid aqueous solution thereto, it was cooled to 0 - 5 °C in an ice-water bath;

[0114] (2.2) 7.2 mmol of NaNO 2 was dissolved in 5 mL of water. After stirring at 0 - 5 °C for 15 min, the reaction progress was monitored by thin-layer chromatography (silica gel TLC, eluent was a mixture of dichloromethane and methanol with a volume ratio of 9:1). After the reaction ended, intermediate 5-1 was obtained;

[0115] (2.3) 4.8 mmol of N,N-diethyl-p-phenylenediamine was dissolved in 50 mL of water to obtain an N,N-diethyl-p-phenylenediamine solution. After adjusting the pH value of the solution to 8 - 9, 3.4 mmol of intermediate 5-1 was slowly dropped into it. After stirring at 0 - 5 °C for 1 h, the reaction progress was monitored by thin-layer chromatography (silica gel TLC, eluent was a mixture of ethyl acetate and n-hexane with a volume ratio of 1:1). After the reaction ended, the reaction product was filtered, the solid product was collected, washed successively with cold ethanol, vacuum dried, and then purified by silica gel column chromatography (eluent was a mixture of ethyl acetate and n-hexane with a volume ratio of 1:2) to obtain intermediate 5-2;

[0116] (2.4) 2.8 mmol of intermediate 5-2 was dissolved in 10 mL of dichloromethane to obtain an intermediate 5-2 solution. 21.56 mmol of anhydrous potassium carbonate was added to the intermediate 5-2 solution and stirred evenly;

[0117] (2.5) Dissolve 4.2 mmol of triethylene glycol monomethyl ether in 10 mL of dichloromethane to obtain a triethylene glycol monomethyl ether solution. Slowly add the triethylene glycol monomethyl ether solution to the system in step (2.4), then continue to add 0.2 mmol of palladium chloride and 0.4 mmol of triphenylphosphine. After stirring and reacting at 50 °C for 24 h, monitor the reaction progress by thin-layer chromatography (silica gel TLC, the developing agent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3). After the reaction is completed, cool to room temperature and terminate the reaction with 50 mL of water;

[0118] (2.6) The aqueous phase generated in step (2.5) is successively subjected to liquid-liquid extraction (3 times, 30 mL of dichloromethane each time), combine the organic phases, wash (with a saturated sodium chloride aqueous solution at 25 °C), dry (using anhydrous sodium sulfate), and concentrate to obtain the crude product J. Then, purify the crude product J through a silica gel column (the eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3) to obtain the intermediate 5-3;

[0119] (3) Synthesis of the reactive disperse dye;

[0120] (3.1) Dissolve 2.4 mmol of the intermediate 5-3 in 10 mL of dichloromethane to obtain an intermediate 5-3 solution. Add 18 mmol of anhydrous potassium carbonate to the intermediate 5-3 solution and stir evenly;

[0121] (3.2) Dissolve 2.9 mmol of the intermediate 1-3 in 10 mL of dichloromethane and slowly add it dropwise to the system in step (3.1). Stir for 30 min, then under argon protection, stir and react at 50 °C for 24 h. Monitor the reaction progress by thin-layer chromatography (silica gel TLC, the developing agent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3). After the reaction is completed, cool the reaction system to room temperature and terminate the reaction with 50 mL of ice water;

[0122] (3.3) The aqueous phase generated in step (3.2) is successively subjected to liquid-liquid extraction (3 times, 30 mL of dichloromethane each time), combine the organic phases, wash (with a saturated sodium chloride aqueous solution at 25 °C), dry (using anhydrous sodium sulfate), and concentrate to obtain the crude product K. Then, purify the crude product K through a silica gel column (the eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3) to obtain the reactive disperse dye (denoted as heterocyclic dye A4).

[0123] Comparative Example A1

[0124] A preparation method of a reactive disperse dye, the overall process is as Figure 6 shown, and the specific steps are as follows:

[0125] (1) Synthesis of Intermediate 1-3 (the synthesis process is the same as in Example A1);

[0126] (2) Synthesis of Intermediate 6-4;

[0127] (2.1) Dissolve 5.9 mmol of 1,5-dihydroxyanthraquinone in 30 mL of pyridine to obtain a 1,5-dihydroxyanthraquinone solution. Then add 13.4 mmol of acetic anhydride to the 1,5-dihydroxyanthraquinone solution and stir at room temperature for 12 h. Monitor the reaction progress by thin-layer chromatography (silica gel TLC, eluent is a mixture of chloroform and methanol with a volume ratio of 9:1). After the reaction is completed, acidify the reaction system with 25°C saturated hydrochloric acid aqueous solution to precipitate the product. Collect the precipitate by filtration and wash it with ice water until neutral. Then purify the precipitate through a silica gel column (eluent is a mixture of chloroform and n-hexane with a volume ratio of 1:2) to obtain Intermediate 6-1;

[0128] (2.2) At 0°C, dissolve 3.4 mmol of Intermediate 6-1 in 30 mL of dichloromethane to obtain an Intermediate 6-1 solution. Slowly add 8 mmol of chlorosulfonic acid dropwise to the Intermediate 6-1 solution. After the addition is complete, stir the reaction for 3 h. Monitor the reaction progress by thin-layer chromatography (silica gel TLC, eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:1). After the reaction is completed, remove dichloromethane by vacuum distillation. Then adjust the pH value of the system to neutral and purify it by column chromatography (eluent is a mixture of chloroform and n-hexane with a volume ratio of 1:2) to obtain Intermediate 6-2;

[0129] (2.3) Dissolve 2.2 mmol of Intermediate 6-2 in 20 mL of methanol to obtain an Intermediate 6-2 solution. Add 10 mL of sodium hydroxide aqueous solution (concentration 2.5 mol / L) to the Intermediate 6-2 solution and stir at room temperature for 12 h (for deacetylation reaction). Monitor the reaction progress by thin-layer chromatography (silica gel TLC, eluent is a mixture of chloroform and methanol with a volume ratio of 9:1). After the reaction is completed, adjust the pH value of the reaction system to neutral with 1 mol / L hydrochloric acid aqueous solution, precipitate the solid product, collect the precipitate by filtration and wash it with ice water until neutral, and dry it to obtain the crude product L. Then purify the crude product L by silica gel column chromatography (eluent is a mixture of chloroform and methanol with a volume ratio of 9:1) to obtain Intermediate 6-3;

[0130] (2.4) Dissolve 3.77 mmol of Intermediate 6-3 in 15 mL of DMF to obtain an Intermediate 6-3 solution. Add 11.31 mmol of anhydrous potassium carbonate to the Intermediate 6-3 solution and stir for 30 min;

[0131] (2.5) Under argon protection, 5.66 mmol of diethylene glycol-2-bromoethyl methyl ether was added to the system of step (2.4). After stirring at 60 °C for 8 h, the reaction progress was monitored by thin-layer chromatography (silica gel TLC, eluent was a mixture of chloroform and methanol with a volume ratio of 9:1). After the reaction was completed, the reaction system was cooled to room temperature, and the reaction was terminated with 50 mL of ice water;

[0132] (2.6) The aqueous phase generated in step (2.5) was successively subjected to liquid-liquid extraction (3 times, 50 mL of ethyl acetate was used each time), the organic phases were combined, washed (with saturated sodium chloride aqueous solution at 25 °C), dried (with anhydrous sodium sulfate), and concentrated to obtain the crude product M. Then the crude product M was purified by silica gel column (eluent was a mixture of chloroform and methanol with a volume ratio of 9:1) to obtain the intermediate 6-4;

[0133] (3) Synthesis of reactive disperse dyes;

[0134] (3.1) 2.1 mmol of intermediate 6-4 was dissolved in 10 mL of DMF to obtain an intermediate 6-4 solution. 6.3 mmol of anhydrous potassium carbonate was added to the intermediate 6-4 solution and stirred for 30 min;

[0135] (3.2) Under argon protection, 2.5 mmol of intermediate 1-3 was added to the system of step (3.1). After stirring at 50 °C for 10 h, the reaction progress was monitored by thin-layer chromatography (silica gel TLC, eluent was a mixture of chloroform and methanol with a volume ratio of 9:1). After the reaction was completed, the reaction system was cooled to room temperature and diluted with 30 mL of water;

[0136] (3.3) The aqueous phase generated in step (3.2) was successively subjected to liquid-liquid extraction (3 times, 20 mL of dichloromethane was used each time), the organic phases were combined, washed (with saturated sodium chloride aqueous solution at 25 °C), dried, and concentrated to obtain the crude product N. Then the crude product N was purified by silica gel column (eluent was a mixture of chloroform and methanol with a volume ratio of 9:1) to obtain the reactive disperse dye (denoted as anthraquinone dye A5).

[0137] Example A5

[0138] A preparation method of a reactive disperse dye, the overall process is as Figure 7 shown, and the specific steps are as follows:

[0139] (1) Synthesis of intermediate 1-3 (the synthesis process is the same as that of Example A2);

[0140] (2) Synthesis of reactive disperse dyes;

[0141] (2.1) Dissolve 2.5 mmol of 4-amino-4'-hydroxyazobenzene in 15 mL of DMF to obtain a 4-amino-4'-hydroxyazobenzene solution, add 7.5 mmol of anhydrous potassium carbonate thereto, and stir for 30 min;

[0142] (2.2) Under argon protection, add 3.0 mmol of intermediate 1-3 to the system of step (2.1), stir at 50 °C for 8 h, then monitor the reaction progress by thin-layer chromatography (silica gel TLC, eluent is a mixture of chloroform and methanol with a volume ratio of 9:1). After the reaction is completed, cool the reaction system to room temperature and dilute it with 30 mL of water;

[0143] (2.3) The aqueous phase generated in step (2.2) is successively subjected to liquid-liquid extraction (3 times, 20 mL of dichloromethane each time), combine the organic phases, wash (with saturated sodium chloride aqueous solution at 25 °C), dry, and concentrate to obtain crude product O. Then, purify the crude product O through a silica gel column (eluent is a mixture of dichloromethane and methanol with a volume ratio of 95:5) to obtain the reactive disperse dye (denoted as azo dye A6).

[0144] Example A6

[0145] A preparation method of a reactive disperse dye, the overall process is as Figure 8 shown, and the specific steps are as follows:

[0146] (1) Synthesis of intermediate 1-3 (the synthesis process is the same as that of Example A4);

[0147] (2) Synthesis of the reactive disperse dye;

[0148] (2.1) Dissolve 2.4 mmol of intermediate 5-2 in 10 mL of dichloromethane to obtain an intermediate 5-2 solution, add 18 mmol of anhydrous potassium carbonate thereto, and stir for 30 min;

[0149] (2.2) Dissolve 2.9 mmol of intermediate 1-3 in 10 mL of dichloromethane to obtain an intermediate 1-3 solution. Slowly add the intermediate 1-3 solution to the system of step (2.1), then stir and react at 50 °C for 24 h under argon protection. Subsequently, monitor the reaction progress by thin-layer chromatography (silica gel TLC, eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3). After the reaction is completed, cool the reaction system to room temperature and terminate the reaction with 50 mL of ice water;

[0150] (2.3) The aqueous phase generated in step (2.2) is successively subjected to liquid-liquid extraction (3 times, each time using 30 mL of dichloromethane), combining the organic phases, washing (using a saturated sodium chloride aqueous solution at 25 °C), drying, and concentration to obtain the crude product P. Then, the crude product P is purified by a silica gel column (the eluent is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:3) to obtain the reactive disperse dye (denoted as heterocyclic dye A7).

[0151] Example B1

[0152] A dyeing process, the specific steps are as follows:

[0153] (1) Preparation of raw materials;

[0154] Textile: Composed of cotton fibers, with a moisture content of 50 wt%;

[0155] Reactive disperse dye: Anthraquinone dye A1;

[0156] (2) Dyeing;

[0157] (2.1) Place the textile and the reactive disperse dye in a supercritical CO 2 fluid dyeing device and seal the device; among them, the mass ratio of the textile to the reactive disperse dye is 100:5;

[0158] (2.2) Introduce CO 2 into the device, raise the temperature to 85 °C, and at the same time raise the pressure to 25 MPa to mix the reactive disperse dye with the supercritical CO 2 fluid; among them, the volume-mass ratio of CO 2 to the textile is 1 L:60 g;

[0159] (2.3) Control the supercritical CO 2 fluid to circulate in the device for 60 min, then cool down and reduce the pressure to separate and recover CO 2 and the unreacted reactive disperse dye.

[0160] Tests show that the soaping color fastness of the dyed textile is 4-5 levels, the dry rubbing color fastness is 5 levels, the wet rubbing color fastness is 4-5 levels, the light color fastness is 5 levels, the dry heat color fastness is 5 levels, the dye uptake rate is 92%, and the color depth Integ value is 93.4.

[0161] Comparative Example B1

[0162] A dyeing process, which is only different from Example B1 in that: Anthraquinone dye A1 is replaced with an equal mass of Anthraquinone dye A5.

[0163] Tests show that the soaping color fastness of the dyed textile is grade 4, the wet rubbing color fastness is grade 3 - 4, the dye uptake rate is 36%, and the color depth Integ value is 46.8.

[0164] Compared with Comparative Example B1, the soaping color fastness, wet rubbing color fastness, dye uptake rate, and color depth Integ value of the dyed textile in Example B1 are significantly reduced. This is because the anthraquinone dye A5 used in Comparative Example B1 contains a water - soluble group (sulfonate group), and the sulfonate group can form strong hydrogen - bond interactions with oxygen and nitrogen atoms on the dye molecule, resulting in enhanced intermolecular interactions within the dye solid. It is difficult for supercritical CO 2 fluid to effectively disassemble these strongly interacting dye molecules. Therefore, the solubility of anthraquinone dye A5 in supercritical CO 2 fluid is relatively low, which directly leads to a decrease in the dye uptake rate and a reduction in the color depth Integ value. At the same time, because anthraquinone dye A5 contains a water - soluble group, the dye that is not fully fixed on the fiber is easily dissolved in water and falls off from the fiber surface, resulting in a decrease in the soaping color fastness and wet rubbing color fastness.

[0165] Example B2

[0166] A dyeing process, the specific steps are as follows:

[0167] (1) Preparation of raw materials;

[0168] Textile: Composed of ramie fibers, with a moisture content of 70 wt%;

[0169] Reactive disperse dye: Azo dye A2;

[0170] (2) Dyeing;

[0171] (2.1) Place the textile and the reactive disperse dye in a supercritical CO 2 fluid dyeing device and seal the device; among them, the mass ratio of the textile to the reactive disperse dye is 100:6;

[0172] (2.2) Introduce CO 2 , raise the temperature to 90 °C, and at the same time raise the pressure to 15 MPa to mix the reactive disperse dye with supercritical CO 2 fluid; among them, the volume - mass ratio of CO 2 to the textile is 1 L:50 g;

[0173] (2.3) Under ultraviolet light irradiation, control the supercritical CO 2 fluid to circulate in the device for 30 min, then cool down and reduce the pressure, and separate and recover CO 2 and the unreacted reactive disperse dye.

[0174] Tests show that the soaping color fastness of the dyed textile is 4-5 grades, the dry rubbing color fastness is 5 grades, the wet rubbing color fastness is 4-5 grades, the light color fastness is 4-5 grades, the dry heat color fastness is 5 grades, the dye uptake rate is 95%, and the color depth Integ value is 96.2.

[0175] Example B3

[0176] A dyeing process, which is only different from Example B2 in that: the azo dye A2 is replaced with an equal mass of azo dye A6.

[0177] Tests show that the soaping color fastness of the dyed textile is 4-5 grades, the dry rubbing color fastness is 5 grades, the wet rubbing color fastness is 4-5 grades, the light color fastness is 4-5 grades, the dry heat color fastness is 5 grades, the dye uptake rate is 28%, and the color depth Integ value is 38.5.

[0178] Compared with Example B2, the dye uptake rate and color depth Integ value of the dyed textile in Example B3 are significantly reduced. This is because the azo dye A6 used in Example B3 does not contain a polyether chain segment and has a relatively strong molecular rigidity. It is easy for dye molecules to form strong π-π stacking interactions among themselves, and supercritical CO 2 fluids are difficult to effectively disperse these strongly interacting dye molecules. Therefore, the solubility of azo dye A6 in supercritical CO 2 fluids is relatively low, which directly leads to a decrease in the dye uptake rate and a decrease in the color depth Integ value.

[0179] Example B4

[0180] A dyeing process, which is only different from Example B2 in that: in step (2), step (2.3) is not carried out.

[0181] Tests show that the soaping color fastness of the dyed textile is 4 grades, the dry rubbing color fastness is 4-5 grades, the wet rubbing color fastness is 4 grades, the light color fastness is 4 grades, the dry heat color fastness is 4-5 grades, the dye uptake rate is 89%, and the color depth Integ value is 91.3.

[0182] Example B5

[0183] A dyeing process, the specific steps are as follows:

[0184] (1) Preparation of raw materials;

[0185] Textile: composed of wool fibers, with a moisture content of 100 wt%;

[0186] Reactive disperse dye: phthalocyanine dye A3;

[0187] (2) Dyeing;

[0188] (2.1) Place the textile and the reactive disperse dye in a supercritical CO 2 fluid dyeing device and seal the device; wherein, the mass ratio of the textile to the reactive disperse dye is 100:4;

[0189] (2.2) Introduce CO 2 into the device, raise the temperature to 100 °C, and at the same time raise the pressure to 30 MPa to mix the reactive disperse dye with the supercritical CO 2 fluid; wherein, the volume-mass ratio of CO 2 to the textile is 1 L:45 g;

[0190] (2.3) Control the supercritical CO 2 fluid to circulate in the device for 90 min, then cool down and reduce the pressure to separate and recover CO 2 and the unreacted reactive disperse dye;

[0191] (3) Fixing treatment;

[0192] Irradiate the dyed textile under ultraviolet light for 30 min.

[0193] Tests show that after the fixing treatment, the soaping color fastness of the textile is grade 5, the dry rubbing color fastness is grade 5, the wet rubbing color fastness is grade 4 - 5, the light color fastness is grade 6, the dry heat color fastness is grade 5, the dye uptake rate is 91%, and the color depth Integ value is 91.2.

[0194] Example B6

[0195] A dyeing process, the specific steps are as follows:

[0196] (1) Preparation of raw materials;

[0197] Textile: Composed of silk fibers, with a moisture content of 60 wt%;

[0198] Reactive disperse dye: Heterocyclic dye A4;

[0199] (2) Dyeing;

[0200] (2.1) Place the textile, the reactive disperse dye and decamethylcyclopentasiloxane (D5) in the dyeing tank of an infrared dyeing machine and seal the dyeing tank; wherein, the mass ratio of the textile to the reactive disperse dye is 100:5, and the volume-mass ratio of D5 to the textile is 1 L:33 g;

[0201] (2.2) Control the dyeing temperature at 90 °C, dye the textile in the dyeing tank for 70 min, then open the dyeing tank and take out the textile;

[0202] (3) Fixing treatment;

[0203] Cover a part of the dyed textile, and expose the other part to ultraviolet light for 20 minutes.

[0204] The test shows that the soaping color fastness of the fixed-color treated part of the textile (i.e., the area exposed to ultraviolet light) is grade 5, the dry rubbing color fastness is grade 5, the wet rubbing color fastness is grade 5, the light color fastness is grade 5, the dry heat color fastness is grade 5, the dye uptake rate is 91.5%, and the color depth Integ value is 92.1; the soaping color fastness of the part of the textile without fixed-color treatment (i.e., the covered area) is grade 4-5, the dry rubbing color fastness is grade 5, the wet rubbing color fastness is grade 4-5, the light color fastness is grade 5, the dry heat color fastness is grade 5, the dye uptake rate is 90.3%, and the color depth Integ value is 91.1.

[0205] Example B7

[0206] A dyeing process, the specific steps are as follows:

[0207] (1) Preparation of raw materials;

[0208] Textile: composed of polylactic acid fiber, moisture content is 0 wt%;

[0209] Reactive disperse dye: heterocyclic dye A4;

[0210] (2) Dyeing;

[0211] (2.1) Place the textile and the reactive disperse dye in a supercritical CO 2 fluid dyeing device and close the device; among them, the mass ratio of the textile to the reactive disperse dye is 100:4;

[0212] (2.2) Introduce CO 2 into the device, raise the temperature to 92 °C, and at the same time raise the pressure to 24 MPa to make the reactive disperse dye mix with the supercritical CO 2 fluid; among them, the volume-mass ratio of CO 2 to the textile is 1 L:55 g;

[0213] (2.3) Control the supercritical CO 2 fluid to circulate in the device for 45 minutes, then cool down and depressurize to separate and recover CO 2 and the unreacted reactive disperse dye.

[0214] The test shows that the soaping color fastness of the dyed textile is grade 4-5, the dry rubbing color fastness is grade 5, the wet rubbing color fastness is grade 4-5, the light color fastness is grade 5, the dry heat color fastness is grade 5, the dye uptake rate is 92.4%, and the color depth Integ value is 88.9.

[0215] Example B8

[0216] A dyeing process, which is only different from Example B7 in that: the heterocyclic dye A4 is replaced with an equal mass of heterocyclic dye A7.

[0217] Tests show that the soaping color fastness of the dyed textile is 4 - 5 levels, the dry rubbing color fastness is 5 levels, the wet rubbing color fastness is 4 - 5 levels, the light color fastness is 5 levels, the dry heat color fastness is 5 levels, the dye uptake rate is 56.3%, and the color depth Integ value is 54.6.

[0218] Compared with Example B7, the dye uptake rate and color depth Integ value of the dyed textile in Example B8 are significantly reduced. This is because the heterocyclic dye A7 used in Example B8 does not contain a polyether chain segment and has a relatively strong molecular rigidity. It is easy for dye molecules to form strong π - π stacking interactions among themselves. Supercritical CO 2 fluids are difficult to effectively disassemble these strongly interacting dye molecules. Therefore, the solubility of the heterocyclic dye A7 in supercritical CO 2 fluids is relatively low, which directly leads to a decrease in the dye uptake rate and a reduction in the color depth Integ value.

[0219] Example B9

[0220] A dyeing process, the specific steps are as follows:

[0221] (1) Preparation of raw materials;

[0222] Textile: Composed of acetate fiber, with a moisture content of 0 wt%;

[0223] Reactive disperse dye: Azo dye A2;

[0224] (2) Dyeing;

[0225] (2.1) Place the textile and the reactive disperse dye in a supercritical CO 2 fluid dyeing device and seal the device; among them, the mass ratio of the textile to the reactive disperse dye is 100:3;

[0226] (2.2) Introduce CO 2 , raise the temperature to 98 °C, and at the same time raise the pressure to 20 MPa to mix the reactive disperse dye with supercritical CO 2 fluid; among them, the volume - mass ratio of CO 2 to the textile is 1 L:48 g;

[0227] (2.3) Under ultraviolet light irradiation, control the supercritical CO 2 fluid to circulate in the device for 75 min, then cool down and reduce the pressure, and separate and recover CO 2 and the unreacted reactive disperse dye.

[0228] The tests show that the soaping color fastness of the dyed textile is grade 5, the dry rubbing color fastness is grade 5, the wet rubbing color fastness is grade 5, the light color fastness is grade 6, the dry heat color fastness is grade 5, the dye uptake rate is 95%, and the color depth Integ value is 88.5.

[0229] Example B10

[0230] A dyeing process, the specific steps are as follows:

[0231] (1) Preparation of raw materials;

[0232] Textile: composed of polyamide 56 fiber, moisture content is 0wt%;

[0233] Reactive disperse dye: phthalocyanine dye A3;

[0234] (2) Dyeing;

[0235] (2.1) Place the textile and the reactive disperse dye in a supercritical CO 2 fluid dyeing device and seal the device; among them, the mass ratio of the textile to the reactive disperse dye is 100:5;

[0236] (2.2) Introduce CO 2 into the device, raise the temperature to 92°C, and at the same time raise the pressure to 28MPa to make the reactive disperse dye mix with the supercritical CO 2 fluid; among them, the volume-mass ratio of CO 2 to the reactive disperse dye is 1L:52g;

[0237] (2.3) Control the supercritical CO 2 fluid to circulate in the device for 80 minutes, then cool down and reduce the pressure, and separate and recover CO 2 and the unreacted reactive disperse dye;

[0238] (3) Fixing treatment;

[0239] Irradiate the dyed textile under ultraviolet light for 20 minutes.

[0240] The tests show that the soaping color fastness of the textile after fixing treatment is grade 5, the dry rubbing color fastness is grade 5, the wet rubbing color fastness is grade 4 - 5, the light color fastness is grade 6, the dry heat color fastness is grade 5, the dye uptake rate is 94.7%, and the color depth Integ value is 93.1.

[0241] Example B11

[0242] A dyeing process, the specific steps are as follows:

[0243] (1) Preparation of raw materials;

[0244] Textiles: Composed of polyurethane fibers, with a moisture content of 0 wt%;

[0245] Reactive disperse dye: Anthraquinone dye A1;

[0246] (2) Dyeing;

[0247] (2.1) Place the textiles, reactive disperse dye, and D5 in the dyeing tank of an infrared dyeing machine and seal the dyeing tank; among them, the mass ratio of textiles to reactive disperse dye is 100:4, and the volume-mass ratio of D5 to textiles is 1 L:30 g;

[0248] (2.2) Control the dyeing temperature at 95 °C. After dyeing the textiles in the dyeing tank for 65 min, open the dyeing tank and take out the textiles;

[0249] (3) Fixing treatment;

[0250] Cover a part of the dyed textiles, and expose the other part to ultraviolet light for 35 min.

[0251] Tests show that for the part of the textiles after the fixing treatment (i.e., the area exposed to ultraviolet light), the soaping color fastness is 4 - 5 grades, the dry rubbing color fastness is 5 grades, the wet rubbing color fastness is 4 - 5 grades, the light color fastness is 5 grades, the dry heat color fastness is 5 grades, the dye uptake rate is 92.4%, and the color depth Integ value is 93.5; for the part of the textiles without the fixing treatment (i.e., the covered area), the soaping color fastness is 4 grades, the dry rubbing color fastness is 4 - 5 grades, the wet rubbing color fastness is 4 grades, the light color fastness is 5 grades, the dry heat color fastness is 4 - 5 grades, the dye uptake rate is 90.3%, and the color depth Integ value is 91.5.

Claims

1. A reactive disperse dye comprising a dye matrix and a diaziridine segment and a polyether segment grafted thereon, characterized in that: The dye matrix contains two or more amino or hydroxyl groups; the structural formula of the diaziridine chain segment is as follows: Wherein, X is -(CH2) n -, n is an integer, n≥2; The number of repeating units of the polyether segment is 2-5, and the terminal group is methyl; Reactive disperse dyes are anthraquinone dyes, azo dyes, phthalocyanine dyes or heterocyclic dyes, and the reactive disperse dyes do not contain water-soluble groups.

2. A dyeing process, after dissolving the dye, dyeing the textile, characterized in that: The dye is a reactive disperse dye, which includes a dye matrix and a diaziridine segment and a polyether segment grafted thereon; the dye matrix contains two or more amino groups or hydroxyl groups; the structural formula of the diaziridine segment is as follows: Wherein, X is -(CH2) n -, n is an integer, n≥2; The number of repeating units of the polyether segment is 2-5, and the terminal group is methyl; Reactive disperse dyes are anthraquinone dyes, azo dyes, phthalocyanine dyes or heterocyclic dyes, and the reactive disperse dyes do not contain water-soluble groups; Textiles are composed of more than one type of natural and synthetic fibers; The dyeing temperature is 85-100℃, which is higher than the T of synthetic fibers. g .

3. A dyeing process according to claim 2, characterized in that: After dyeing, a color fixing treatment is also carried out. The process of the color fixing treatment is: the dyed textiles are irradiated under ultraviolet light.

4. A dyeing process according to claim 3, characterized in that: During the color fixing treatment, the dyed textiles are covered so that only local areas of the dyed textiles are exposed to ultraviolet light.

5. A dyeing process according to any one of claims 2 to 4, characterized in that: Supercritical CO2 fluid is used to dissolve the dye.

6. A dyeing process according to claim 5, characterized in that: The steps for dyeing are as follows: (a) placing a textile having a moisture content of 0-100 wt % and a reactive disperse dye in a supercritical CO2 fluid dyeing device, and sealing the device; (b) introducing CO2 into the device, raising the temperature to 85-100°C, and simultaneously raising the pressure to 15-30MPa, so that the reactive disperse dye is mixed with the supercritical CO2 fluid; (c) After controlling the supercritical CO2 fluid to circulate in the device for 30-120 minutes, the temperature and pressure are lowered to separate and recover CO2 and unreacted active disperse dye.

7. A dyeing process according to claim 6, characterized in that: In step (c), while controlling the supercritical CO2 fluid to circulate in the device, ultraviolet light is also used to irradiate the dyeing system.

8. A dyeing process according to claim 2, characterized in that: Textiles are composed of hydrophilic fibers.

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