Active disperse dye and dyeing process

Abstract

The invention belongs to the technical field of textile production, and relates to an active disperse dye and a dyeing process. The reactive disperse dye comprises a dye matrix and a bis-aziridine chain segment grafted on the dye matrix, and-OCH2-is introduced to an aromatic ring para-position of the bis-aziridine chain segment as an electron-donating group. A dyeing process: after active disperse dye is dissolved, dyeing the textile; the textile consists of more than one of natural fibers and synthetic fibers; the dyeing temperature is 85-100 DEG C, and the dyeing temperature is higher than Tg of the synthetic fibers. According to the invention, a '-OCH2-' electron-donating group is introduced in the para-position of an aromatic ring of a diaziridine chain segment, and the conjugation effect and the induction effect of the group reduce the activation energy of C-N bond breakage, so that carbene can be efficiently generated without depending on a high-temperature or acid-base environment; the problems that in the prior art, the condition for generating carbene through a diaziridine chain segment is harsh, and the color fastness of the dyed textile is low when supercritical CO2 fluid is adopted for dyeing are solved.

Description

Technical Field

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

[0002] Reactive disperse dyes containing diazirine chain segments are a type of special disperse dyes that introduce diazirine groups into the molecular structure. Under certain conditions, diazirine groups can generate carbene groups, which can form covalent bonds with functional groups such as alkyl, amino and hydroxyl groups in fiber molecules. This type of dye not only has excellent absorption spectrum characteristics and thermal stability, but also effectively solves the problem of thermal migration caused by weak interaction between disperse dyes and fibers. By enhancing the binding force between dyes and fibers, reactive disperse dyes containing diazirine chain segments significantly improve the dyeing properties of synthetic fibers such as polypropylene (polypropylene) and aramid, and improve dyeing depth and color fastness, which makes it have excellent application potential in the textile industry, especially in the dyeing process of clothing, household textiles and industrial fabrics that have strict requirements on high wash resistance and high color fastness.

[0003] Reference 1 (Dyes and Pigments, 2025, 233: 112517.), Reference 2 (Dyes and Pigments, 2024, 221: 111784.), Reference 3 (Coloration Technology, 2022, 138(5): 551-564.), and Reference 4 (Dyes and Pigments, 2021, 194: 109555.) disclose active disperse dyes containing diazirine segments, whose fixation temperatures are usually between 120-140°C. These dyes require higher temperatures to achieve the reaction between carbene and cellulose alkyl, which is not conducive to energy conservation and emission reduction, and may have a negative impact on the low glass transition temperature (T g ) synthetic fibers, such as polylactic acid (PLA), acetate fiber, polyamide, polyurethane, etc., which cause strong damage and poor feel.

[0004] Therefore, it is necessary to design a reactive disperse dye with simple conditions for generating carbene from a diaziridine chain segment and use it for dyeing textiles.

[0005] In recent years, supercritical CO2 fluid dyeing technology has attracted widespread attention due to its energy-saving, emission-reduction and waterless dyeing environmentally friendly characteristics. However, the dye system and process of the existing technology still have significant deficiencies, mainly manifested in the low color fastness of dyed textiles. For synthetic fiber dyeing, some existing disperse dyes have good solubility, but the color fastness of fibers or fabrics after polyester fiber dyeing is poor. For cellulose fibers (such as cotton, linen, viscose and other regenerated cellulose fibers), the color fixation reaction of the color fixing groups of traditional reactive dyes (such as halogenated triazines and vinyl sulfone structures) usually requires alkaline conditions, while the supercritical CO2 fluid system requires a small amount of water to swell the fiber, and after reacting with CO2 to generate carbonic acid, the surface of the fiber or fabric becomes acidic, resulting in a significant decrease in the color fixation rate and color fastness.

[0006] Therefore, it is also necessary to design a reactive disperse dye and use it for supercritical CO2 fluid dyeing to solve the above problems. Summary of the invention

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

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

[0009] A reactive disperse dye comprises a dye matrix and a diaziridine chain segment grafted thereon, wherein the structural formula of the diaziridine chain segment is as follows:

[0010] ;

[0011] Wherein, X is -(CH2) n -, n is an integer, n≥2;

[0012] Reactive disperse dyes do not contain water-soluble groups.

[0013] One of the purposes of the present invention is to solve the problem of harsh conditions (high temperature of 120-140°C) for generating carbene from diazirine segments in the prior art. The diazirine segments (specifically trifluoromethylphenyl diazirine segments) of the present application can generate carbene under ultraviolet light (365nm) or low temperature (85-100°C), thanks to the unique chemical properties and optimized design of the diazirine segments. The CN bonds of the three-membered rings in the diazirine molecules have high tension, and this internal stress makes it easy to break under specific conditions to generate carbene (R1-:C-R2). The present invention introduces "-OCH2-" as an electron-donating group at the para position of the aromatic ring of diazirine. This group adjusts the electron density distribution in the molecule through conjugation effect and induction effect, reduces the activation energy required for breaking the CN bond, and thus significantly reduces the energy barrier for carbene generation.

[0014] The photon energy of ultraviolet light (365nm) is about 3.4eV, which can efficiently excite the π→π or n→π transition of the diaziridine molecule, causing the molecule to enter an excited state; in the excited state, the strength of the CN bond is further weakened, and the three-membered ring decomposes into carbene and stable nitrogen (N2). Nitrogen, as a highly stable leaving group, greatly promotes the reaction in the direction of carbene formation.

[0015] The three-membered CN bond in the diaziridine molecule has high internal stress. When heated, the thermal motion of atoms intensifies. The internal stress can cause the CN bond to break, generating carbene intermediates and nitrogen. By introducing the "-OCH2-" electron-donating group at the para position of the aromatic ring of the diaziridine chain segment, the conjugation effect and induction effect of this group reduce the activation energy of the CN bond breakage, allowing carbene to be generated at low temperatures.

[0016] As the preferred technical solution:

[0017] As mentioned above, the reactive disperse dye contains two or more amino groups or hydroxyl groups in the dye matrix, so as to facilitate the connection between the dye matrix and the diaziridine chain segment; the reactive disperse dye is anthraquinone dye, azo dye, phthalocyanine dye or heterocyclic dye.

[0018] The above-mentioned active disperse dye further comprises a polyether segment grafted onto the dye matrix, wherein the number of repeating units of the polyether segment is 2-5, i.e. -(CH2-CH2-O) m -, m = 2-5, the terminal group is methyl (-CH3).

[0019] The present invention also provides a dyeing process, wherein the textile is dyed after dissolving the dye, wherein the dye is a reactive disperse dye, and the reactive disperse dye comprises a dye matrix and a diaziridine chain segment grafted thereon, and the structural formula of the diaziridine chain segment is as follows:

[0020] ;

[0021] Wherein, X is -(CH2) n -, n is an integer, n≥2;

[0022] Reactive disperse dyes do not contain water-soluble groups. The structure design without water-soluble groups avoids the risk of reactive disperse dyes fading due to hydrolysis on the surface of hydrophilic fibers, fundamentally improving the problem of poor color fastness to washing and wet rubbing.

[0023] Textiles are composed of one or more of natural fibers (such as natural cellulose fibers such as cotton and linen, regenerated cellulose fibers such as viscose and lyocell, protein fibers such as wool and silk) and synthetic fibers (such as polyester, iterated polyester, polyamide, polyacrylonitrile, polylactic acid, polypropylene, polyurethane, etc.);

[0024] The dyeing temperature is 85-100°C, which is higher than the T of synthetic fibers. g The dyeing temperature must be within the T of the synthetic fiber. g The molecular chains in the amorphous region of the fiber can begin to thermally migrate. Thermal migration creates a free volume inside the amorphous region of the fiber for dye adsorption and diffusion. The dyeing temperature is preferably higher than the T of the synthetic fiber. g 20~30°C higher, the free volume is larger, and a higher dyeing rate and satisfactory dyeing effect can be obtained after dyeing.

[0025] As the preferred technical solution:

[0026] In the dyeing process as described above, the dye matrix contains more than two amino groups or hydroxyl groups; the active disperse dye is anthraquinone dye, azo dye, phthalocyanine dye or heterocyclic dye.

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

[0028] The temperature limit during dyeing may not be sufficient to generate carbene efficiently, especially under low temperature conditions, where the carbene generation efficiency may be low. During low temperature dyeing, ultraviolet light (365 nm) is introduced to excite the diaziridine chain segment, and the photon energy (about 3.4 eV) triggers π→π or n→π transitions to enhance the generation efficiency of carbene. This can achieve efficient generation of carbene under low temperature conditions, improve the fixation rate of the dye, and reduce the dependence on low T g Thermal damage to fibers.

[0029] In the dyeing process as described above, a color fixing treatment is also performed after dyeing is completed. The process of the color fixing treatment is: the dyed textile is irradiated under ultraviolet light (365nm).

[0030] After 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 diaziridine segments in the dye to generate carbene, which reacts covalently with the fiber to strengthen the color fixation effect, improve the color fixation rate, and further improve the color fastness of the dyed fabric (including washing, wet friction, and sublimation fastness).

[0031] After dyeing or fixing, the textile is also washed to remove unfixed active disperse dyes; when the textile is composed of natural fibers, the above washing is soap washing, hot water washing, and cold water washing in sequence; when the textile is composed of synthetic fibers, the above washing is reduction washing.

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

[0033] When there are multiple fibers or complex fabric structures in the dyeing process, it is necessary to preferentially complete the fixation reaction in a specific area. The present invention uses local ultraviolet light irradiation to accurately control the carbene generation area of ​​the diazirine chain segment to achieve preferential fixation or fancy dyeing in a specific area, thereby improving the flexibility of the dyeing process and can be used for the functional dyeing design of patterned fabrics or composite fabrics.

[0034] A dyeing process as described in any of the above items, wherein supercritical CO2 fluid is used to dissolve the dye.

[0035] The second purpose of the present invention is to solve the problem of low color fastness of dyed textiles when dyeing with supercritical CO2 fluid in the prior art. The diaziridine chain segment in the active disperse dye used in 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 CO2, the carbene generation efficiency and reaction activity are not affected, and 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 a 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 dyeing steps are as follows:

[0037] (a) placing a textile having 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 a reactive disperse dye in a supercritical CO2 fluid dyeing device, and closing the device;

[0038] (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;

[0039] (c) After controlling the supercritical CO2 fluid to circulate in the device for 30-120 minutes (during the circulation process, the supercritical CO2 fluid continuously dissolves the active disperse dye and brings the dissolved active disperse dye to the fiber surface and interior for dyeing), the temperature and pressure are lowered to separate and recover the CO2 and the unreacted active disperse dye.

[0040] A dyeing process as described in any of the above items, wherein the reactive disperse dye further comprises a polyether segment grafted onto the dye matrix, the number of repeating units of the polyether segment is 2-5, and the terminal group is a methyl group; and the textile is composed of hydrophilic fibers.

[0041] The existing dye system and process also have the problem that the dye is not easy to separate from the fluid after being dissolved in the supercritical CO2 fluid and is adsorbed onto the hydrophilic fiber, resulting in low dyeing 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 segment, which can reduce the melting point and inter-crystal force of the reactive disperse dye, increase the solubility of the reactive disperse dye in supercritical CO2, and reduce the dissolution energy consumption of the reactive disperse dye. More importantly, when the reactive disperse dye contacts the hydrophilic fiber containing a small amount of water, the polyether segment can form a hydrogen bond to help the reactive disperse dye to separate from the supercritical CO2 fluid and adsorb onto the hydrophilic fiber. This characteristic significantly improves the affinity of the non-water-soluble reactive disperse dye to the hydrophilic fiber, effectively improves the dyeing rate and realizes dark dyeing.

[0043] The chain length of the polyether segment in the reactive disperse dye of the present invention is suitable, which can avoid the problem that the polyether segment due to too short chain length improves the solubility of the reactive disperse dye in supercritical CO2 fluid is not good and the affinity of the reactive disperse dye with hydrophilic fiber is too weak, and the problem that the reactive disperse dye has weak diffusion ability inside the fiber due to too long chain length, and the polyether segment can wrap the reactive group, affecting its reaction with the fiber. In this way, the dye can not only be more effectively dissolved in the supercritical CO2 fluid, which is convenient for transmission in the dyeing process, but also can keep good contact with the fiber, ensuring that the dye molecules can evenly and quickly penetrate into the fiber interior, and achieve ideal dyeing depth and uniformity.

[0044] The terminal group of the polyether chain segment designed in the present invention is a methyl group, which is relatively inert and not easy to participate in the reaction, thus helping to improve the stability and diffusion capacity of the active disperse dye molecules.

[0045] Beneficial effects:

[0046] (1) The present invention introduces an electron-donating group "-OCH2-" at the para position of the aromatic ring of the diazirine chain segment. The conjugation effect and induction effect of this group reduce the activation energy of the CN bond breakage, so that carbene can be efficiently generated without relying on high temperature or acidic or alkaline environment, thereby solving the problems of harsh conditions for the generation of carbene from diazirine chain segments in the prior art and low color fastness of dyed textiles when dyeing with supercritical CO2 fluid.

[0047] (2) The reactive disperse dyes of the present invention contain polyether segments, which can reduce the melting point and inter-crystal force of the reactive disperse dyes, increase the solubility of the reactive disperse dyes in supercritical CO2, and reduce the dissolution energy consumption of the reactive disperse dyes. More importantly, when the reactive disperse dyes come into contact with hydrophilic fibers containing a small amount of water, the polyether segments can form hydrogen bonds to help the reactive disperse dyes escape from the supercritical CO2 fluid and adsorb onto the hydrophilic fibers. This characteristic significantly improves the affinity of the non-water-soluble reactive disperse dyes for the hydrophilic fibers, effectively improving the dyeing rate and achieving dark dyeing.

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

[0049] Figure 1 and Figure 2 The reactive disperse dye synthesis process of Example A1;

[0050] Figure 3 The reactive disperse dye synthesis process of Example A2;

[0051] Figure 4 The reactive disperse dye synthesis process of Example A3;

[0052] Figure 5 The reactive disperse dye synthesis process of Example A4;

[0053] Figure 6 This is the reactive disperse dye synthesis process of Comparative Example A1;

[0054] Figure 7 The reactive disperse dye synthesis process of Example A5;

[0055] Figure 8 This is the reactive disperse dye synthesis process of Example A6. DETAILED DESCRIPTION

[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 are not intended 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 fall within the scope limited by the appended claims of the application equally.

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

[0058] Color fastness to soap washing: measured in accordance with GB / T 3921-2008 standard;

[0059] Color fastness to dry / wet rubbing: measured in accordance with GB / T 3920-2008;

[0060] Color fastness to light: measured in accordance with GB / T 8426-1998;

[0061] Color fastness to dry heat: measured in accordance with GB / T 5718-1997;

[0062] Dye uptake: measured in accordance with GB / T 23976.1-2009 standard;

[0063] Color depth Integ value: measured in accordance with GB / T 21875-2016 standard.

[0064] Example A1

[0065] A method for preparing a reactive disperse dye, the overall process is as follows Figure 1 to Figure 2 As shown, the specific steps are as follows:

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

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

[0068] (1.2) Slowly add solution B (consisting of 1032 mmol of H2SO4, 45 mL of trifluoroacetic acid and 15 mL of acetonitrile) dropwise into solution A, slowly raise the temperature of the system to 25°C, stir the reaction 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) is sequentially subjected to liquid-liquid extraction (3 times, each time using 150 mL of ether), the organic phases are combined, washed (2 times, each time using 150 mL of a 25°C saturated sodium thiosulfate aqueous solution), dried (using anhydrous sodium sulfate), and concentrated to obtain a crude product A, which is then purified by a silica gel column (the eluent is pentane) to obtain an intermediate 1-1 (a light 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·H2O into a flask, heat to 40 °C, and then bubble with argon for 15 min to remove oxygen.

[0071] (1.5) After adding bis(2,4-pentanedione)copper(II) in three batches to the system of step (1.4), the NMR fluorine spectrum ( 19F-NMR) was used to monitor the reaction progress. After the reaction was completed, 500 mL of water was added to terminate the reaction. The amount of the first batch of bis(2,4-pentanedionate) copper (II) added was 80 mmol. The second batch of bis(2,4-pentanedionate) copper (II) was added 20 h after the first batch of bis(2,4-pentanedionate) copper (II) was added, and the amount added was 40 mmol. The third batch of bis(2,4-pentanedionate) copper (II) was added 4 h after the second batch of bis(2,4-pentanedionate) copper (II) was added, and the amount added was 40 mmol.

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

[0073] (1.7) 365.58 mmol of intermediate 1-2 was dissolved in 600 mL of dichloromethane and cooled at 0°C to obtain an intermediate 1-2 solution, 548.37 mmol of triphenylphosphine was dissolved in 200 mL of dichloromethane to obtain a triphenylphosphine solution, and the triphenylphosphine solution was added to the intermediate 1-2 solution to obtain a mixed solution;

[0074] (1.8) Dissolve 438.70 mmol of carbon tetrabromide in 300 mL of dichloromethane and degas to obtain a carbon tetrabromide solution. Slowly add the carbon tetrabromide solution dropwise to the mixed solution, stir the reaction at 0°C for 2 h, then stir the reaction at 25°C for 24 h, and then dilute the reaction system with water;

[0075] (1.9) The aqueous phase generated in step (1.8) was subjected to liquid-liquid extraction (3 times, each time using 50 mL of dichloromethane), the organic phases were combined, dried (using anhydrous magnesium sulfate), filtered, and concentrated to obtain a crude product C, which was then purified by a silica gel column (the eluent was pentane) to obtain intermediate 1-3 (as a yellow oil);

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

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

[0078] (2.2) Under argon protection, add 5.66 mmol of diethylene glycol-2-bromoethyl methyl ether to the system of step (2.1), stir at 60°C for 6 h, and monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of ethyl acetate and n-hexane in 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;

[0079] (2.3) The aqueous phase generated in step (2.2) was sequentially subjected to liquid-liquid extraction (3 times, each time using 50 mL of ethyl acetate), the organic phases were combined, washed (using a 25°C saturated sodium chloride aqueous solution), dried (using anhydrous sodium sulfate), and concentrated to obtain a crude product D, which was then purified by a silica gel column (the eluent was a mixture of ethyl acetate and n-hexane in a volume ratio of 1:3) to obtain an intermediate 2-1;

[0080] (3) Synthesis of reactive disperse dyes;

[0081] (3.1) Dissolve 2.1 mmol of intermediate 2-1 in 10 mL of acetonitrile to obtain an intermediate 2-1 solution. Add 6.3 mmol of anhydrous potassium carbonate to the intermediate 2-1 solution and stir for 30 min.

[0082] (3.2) Under argon protection, add 2.5 mmol of intermediate 1-3 to the system of step (3.1), stir and react at 50°C for 8 h, and monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of dichloromethane and methanol in a volume ratio of 9:1). After the reaction is completed, cool the reaction system to room temperature and dilute with 30 mL of water;

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

[0084] Example A2

[0085] A method for preparing a reactive disperse dye, the overall process is as follows Figure 3 As shown, the specific steps are as follows:

[0086] (1) Intermediates 1-3 ( ) synthesis;

[0087] The synthesis process is basically the same as that of Example A1, except that: Step (1.4) is as follows: 320 mmol of intermediate 1-1, 320 mL of dimethyl sulfoxide, 961.4 mmol of propylene glycol and 801 mmol of CsOH·H2O are added to a flask, heated to 42°C, and then bubbled with argon for 15 min to remove oxygen;

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

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

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

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

[0092] (3) Synthesis of reactive disperse dyes;

[0093] (3.1) Dissolve 2.5 mmol of intermediate 3-1 in 15 mL of DMF to obtain an 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 intermediate 1-3 to the system of step (3.1), stir evenly, and then stir at 50°C for 8 h. Monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of dichloromethane and methanol in a volume ratio of 9:1). After the reaction is completed, cool the reaction system to room temperature and dilute with 30 mL of water;

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

[0096] Example A3

[0097] A method for preparing a reactive disperse dye, the overall process is as follows Figure 4 As shown, the specific steps are as follows:

[0098] (1) Intermediates 1-3 ( ) synthesis;

[0099] The synthesis process is basically the same as that of Example A1, except that: Step (1.4) is as follows: 320 mmol of intermediate 1-1, 320 mL of dimethyl sulfoxide, 961.4 mmol of 1,5-pentanediol and 801 mmol of CsOH·H2O are added to a flask, heated to 50°C, and then bubbled with argon for 15 min to remove oxygen;

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

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

[0102] (2.2) Under argon protection, slowly add 3.75 mmol of methyl-pentaethylene glycol-bromide to the system of 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, the developing solvent is a mixture of ethyl acetate and n-hexane in 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) was sequentially subjected to liquid-liquid extraction (3 times, each time using 30 mL of ethyl acetate), the organic phases were combined, washed (using a 25°C saturated sodium chloride aqueous solution), dried (using anhydrous sodium sulfate), and concentrated to obtain a crude product H, which was then purified by a silica gel column (the eluent was a mixture of dichloromethane and methanol in a volume ratio of 95:5) to obtain an intermediate 4-1;

[0104] (3) Synthesis of reactive disperse dyes;

[0105] (3.1) Dissolve 1.7 mmol of intermediate 4-1 in 20 mL of dichloromethane to obtain an intermediate 4-1 solution. Add 2.2 mmol of 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, the system of step (3.1) was stirred at 50°C for 12 h, and the reaction progress was monitored by thin layer chromatography (silica gel TLC, the developing solvent was a mixture of ethyl acetate and n-hexane in a volume ratio of 1:1). After the reaction was completed, the reaction system was cooled to room temperature and terminated with 50 mL of ice water;

[0107] (3.3) The aqueous phase generated in step (3.2) was sequentially subjected to liquid-liquid extraction (3 times, each time using 30 mL of ethyl acetate), the organic phases were combined, washed (using a saturated sodium chloride aqueous solution at 25°C), dried (using anhydrous sodium sulfate), and concentrated to obtain a crude product I. The crude product I was then purified by a silica gel column (the eluent was a mixture of ethyl acetate and n-hexane in a volume ratio of 1:3) to obtain a reactive disperse dye (referred to as phthalocyanine dye A3).

[0108] Example A4

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

[0110] (1) Intermediates 1-3 ( ) synthesis;

[0111] The synthesis process is basically the same as that of Example A1, except that: Step (1.4) is as follows: 320 mmol of intermediate 1-1, 320 mL of dimethyl sulfoxide, 961.4 mmol of 1,4-butanediol and 801 mmol of CsOH·H2O are added to a flask, heated to 45°C, and then bubbled with argon for 15 min to remove oxygen;

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

[0113] (2.1) Dissolve 3.4 mmol of 2-amino-4,6-dibromobenzothiazole in 10 mL of water to obtain a 2-amino-4,6-dibromobenzothiazole solution, add 5 mL of a 37% by volume aqueous solution of hydrochloric acid, and cool in an ice-water bath to 0-5°C;

[0114] (2.2) Dissolve 7.2 mmol of NaNO2 in 5 mL of water, stir at 0-5°C for 15 min, and monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of dichloromethane and methanol in a volume ratio of 9:1). After the reaction is completed, intermediate 5-1 is obtained;

[0115] (2.3) Dissolve 4.8 mmol of N,N-diethyl-p-phenylenediamine 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, slowly drop 3.4 mmol of intermediate 5-1 into the solution. After stirring at 0-5°C for 1 hour, monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of ethyl acetate and n-hexane in a volume ratio of 1:1). After the reaction is completed, filter the reaction product, collect the solid product, wash it with cold ethanol in turn, vacuum dry it, and purify it by silica gel column chromatography (the eluent is a mixture of ethyl acetate and n-hexane in a volume ratio of 1:2) to obtain intermediate 5-2;

[0116] (2.4) Dissolve 2.8 mmol of intermediate 5-2 in 10 mL of dichloromethane to obtain an intermediate 5-2 solution. Add 21.56 mmol of anhydrous potassium carbonate to the intermediate 5-2 solution and stir 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 of step (2.4), then continue to add 0.2 mmol of palladium chloride and 0.4 mmol of triphenylphosphine, and stir the reaction at 50°C for 24 hours. Monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of ethyl acetate and n-hexane in 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) was sequentially subjected to liquid-liquid extraction (3 times, each time using 30 mL of dichloromethane), the organic phases were combined, washed (using a 25°C saturated sodium chloride aqueous solution), dried (using anhydrous sodium sulfate), and concentrated to obtain a crude product J, which was then purified by a silica gel column (the eluent was a mixture of ethyl acetate and n-hexane in a volume ratio of 1:3) to obtain an intermediate 5-3;

[0119] (3) Synthesis of reactive disperse dyes;

[0120] (3.1) Dissolve 2.4 mmol of 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 intermediate 1-3 in 10 mL of dichloromethane, slowly dropwise add the mixture to the system of step (3.1), stir for 30 min, and then stir and react at 50°C for 24 h under argon protection. Monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of ethyl acetate and n-hexane in 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) was subjected to liquid-liquid extraction (3 times, each time using 30 mL of dichloromethane), the organic phases were combined, washed (using a saturated sodium chloride aqueous solution at 25°C), dried (using anhydrous sodium sulfate), and concentrated to obtain a crude product K. The crude product K was then purified by a silica gel column (the eluent was a mixture of ethyl acetate and n-hexane in a volume ratio of 1:3) to obtain a reactive disperse dye (referred to as heterocyclic dye A4).

[0123] Comparative Example A1

[0124] A method for preparing a reactive disperse dye, the overall process is as follows Figure 6 As shown, the specific steps are as follows:

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

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

[0127] (2.1) 5.9 mmol of 1,5-dihydroxyanthraquinone was dissolved in 30 mL of pyridine to obtain a 1,5-dihydroxyanthraquinone solution. 13.4 mol of acetic anhydride was then added to the 1,5-dihydroxyanthraquinone solution. After stirring at room temperature for 12 h, the reaction progress was monitored by thin layer chromatography (silica gel TLC, the developing solvent was a mixture of chloroform and methanol in a volume ratio of 9:1). After the reaction was completed, the reaction system was acidified with a 25°C saturated hydrochloric acid aqueous solution to precipitate the product. The precipitate was collected by filtration and washed with ice water until neutral. The precipitate was purified by a silica gel column (the eluent was a mixture of chloroform and n-hexane in a volume ratio of 1:2) to obtain intermediate 6-1;

[0128] (2.2) At 0°C, 3.4 mol of intermediate 6-1 was dissolved in 30 mL of dichloromethane to obtain an intermediate 6-1 solution. 8 mol of chlorosulfonic acid was slowly added dropwise to the intermediate 6-1 solution. After the addition was complete, the reaction was stirred for 3 h. The reaction progress was monitored by thin layer chromatography (silica gel TLC, the developing solvent was a mixture of ethyl acetate and n-hexane in a volume ratio of 1:1). After the reaction was completed, the dichloromethane was removed by vacuum distillation. The pH value of the system was adjusted to neutral, and then purified by column chromatography (the eluent was a mixture of chloroform and n-hexane in a volume ratio of 1:2) to obtain intermediate 6-2;

[0129] (2.3) 2.2 mmol of intermediate 6-2 was dissolved in 20 mL of methanol to obtain an intermediate 6-2 solution. 10 mL of sodium hydroxide aqueous solution (concentration of 2.5 mol / L) was added to the intermediate 6-2 solution. After stirring at room temperature for 12 h (for deacetylation reaction), the reaction progress was monitored by thin layer chromatography (silica gel TLC, the developing solvent was a mixture of chloroform and methanol in a volume ratio of 9:1). After the reaction was completed, the pH value of the reaction system was adjusted to neutral with 1 mol / L hydrochloric acid aqueous solution to precipitate a solid product. The precipitate was collected by filtration and washed with ice water until neutral, and dried to obtain a crude product L. The crude product L was purified by silica gel column chromatography (the eluent was a mixture of chloroform and methanol in a volume ratio of 9:1) to obtain an 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, add 5.66 mmol of diethylene glycol-2-bromoethyl methyl ether to the system of step (2.4), stir at 60°C for 8 h, and monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of chloroform and methanol in a volume ratio of 9:1). After the reaction is completed, cool the reaction system to room temperature and terminate the reaction with 50 mL of ice water;

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

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

[0134] (3.1) Dissolve 2.1 mmol of intermediate 6-4 in 10 mL of DMF to obtain an intermediate 6-4 solution. Add 6.3 mmol of anhydrous potassium carbonate to the intermediate 6-4 solution and stir for 30 min.

[0135] (3.2) Under argon protection, add 2.5 mmol of intermediate 1-3 to the system of step (3.1), stir at 50°C for 10 h, and monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of chloroform and methanol in a volume ratio of 9:1). After the reaction is completed, cool the reaction system to room temperature and dilute with 30 mL of water;

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

[0137] Example A5

[0138] A method for preparing a reactive disperse dye, the overall process is as follows Figure 7 As shown, the specific steps are as follows:

[0139] (1) Synthesis of intermediate 1-3 (synthesis process is the same as 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, 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, and monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of chloroform and methanol in a volume ratio of 9:1). After the reaction is completed, cool the reaction system to room temperature and dilute with 30 mL of water;

[0143] (2.3) The aqueous phase generated in step (2.2) was subjected to liquid-liquid extraction (3 times, each time using 20 mL of dichloromethane), the organic phases were combined, washed (using a saturated sodium chloride aqueous solution at 25°C), dried, and concentrated to obtain a crude product O. The crude product O was then purified by a silica gel column (the eluent was a mixture of dichloromethane and methanol in a volume ratio of 95:5) to obtain a reactive disperse dye (denoted as azo dye A6).

[0144] Example A6

[0145] A method for preparing a reactive disperse dye, the overall process is as follows Figure 8 As shown, the specific steps are as follows:

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

[0147] (2) Synthesis of reactive disperse dyes;

[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, 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), and stir the reaction at 50°C for 24 h under argon protection. Then, monitor the reaction progress by thin layer chromatography (silica gel TLC, the developing solvent is a mixture of ethyl acetate and n-hexane in 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) was subjected to liquid-liquid extraction (3 times, each time using 30 mL of dichloromethane), the organic phases were combined, washed (using a saturated sodium chloride aqueous solution at 25°C), dried, and concentrated to obtain a crude product P. The crude product P was then purified by a silica gel column (the eluent was a mixture of ethyl acetate and n-hexane in a volume ratio of 1:3) to obtain a reactive disperse dye (referred to as heterocyclic dye A7).

[0151] Example B1

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

[0153] (1) Preparation of raw materials;

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

[0155] Reactive disperse dyes: anthraquinone dye A1;

[0156] (2) Staining;

[0157] (2.1) placing textiles and reactive disperse dyes in a supercritical CO2 fluid dyeing device, and sealing the device; wherein the mass ratio of the textiles to the reactive disperse dyes is 100:5;

[0158] (2.2) CO2 is introduced into the device, the temperature is raised to 85°C, and the pressure is raised to 25 MPa, so that the reactive disperse dye is mixed with the supercritical CO2 fluid; wherein the volume mass ratio of CO2 to textile is 1 L:60 g;

[0159] (2.3) After the supercritical CO2 fluid is controlled to circulate in the device for 60 minutes, the temperature and pressure are lowered to separate and recover the CO2 and unreacted active disperse dye.

[0160] Tests show that the color fastness of the dyed textiles to soaping is level 4-5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 4-5, the color fastness to light is level 5, the color fastness to dry heat is level 5, the dyeing rate is 92%, and the color depth Integ value is 93.4.

[0161] Comparative Example B1

[0162] A dyeing process, which is different from Example B1 only in that the anthraquinone dye A1 is replaced by anthraquinone dye A5 of equal mass.

[0163] Tests show that the color fastness to soaping of the dyed textiles is level 4, the color fastness to wet rubbing is level 3-4, the dyeing rate is 36%, and the color depth Integ value is 46.8.

[0164] Compared with Example B1, the color fastness to soaping, color fastness to wet rubbing, dyeing rate and color depth Integ value of the dyed textiles in Comparative 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 a strong hydrogen bond interaction with the oxygen atoms and nitrogen atoms on the dye molecule, resulting in enhanced interaction between molecules inside the dye solid. It is difficult for the supercritical CO2 fluid to effectively break up these strongly interacting dye molecules. Therefore, the solubility of the anthraquinone dye A5 in the supercritical CO2 fluid is low, which directly leads to a decrease in the dyeing rate and a decrease in the color depth Integ value. At the same time, since the 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 reduced color fastness to soaping and color fastness to wet rubbing.

[0165] Example B2

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

[0167] (1) Preparation of raw materials;

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

[0169] Reactive disperse dyes: azo dye A2;

[0170] (2) Staining;

[0171] (2.1) placing textiles and reactive disperse dyes in a supercritical CO2 fluid dyeing device, and sealing the device; wherein the mass ratio of the textiles to the reactive disperse dyes is 100:6;

[0172] (2.2) CO2 is introduced into the device, the temperature is raised to 90°C, and the pressure is raised to 15 MPa, so that the reactive disperse dye is mixed with the supercritical CO2 fluid; wherein the volume mass ratio of CO2 to textile is 1 L:50 g;

[0173] (2.3) Under ultraviolet light irradiation, the supercritical CO2 fluid is controlled to circulate in the device for 30 minutes, and then the temperature and pressure are reduced to separate and recover the CO2 and unreacted active disperse dye.

[0174] Tests show that the color fastness of the dyed textiles to soaping is level 4-5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 4-5, the color fastness to light is level 4-5, the color fastness to dry heat is level 5, the dyeing rate is 95%, and the color depth Integ value is 96.2.

[0175] Example B3

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

[0177] Tests show that the color fastness of the dyed textiles to soaping is level 4-5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 4-5, the color fastness to light is level 4-5, the color fastness to dry heat is level 5, the dyeing rate is 28%, and the color depth Integ value is 38.5.

[0178] Compared with Example B2, the dyeing rate and color depth Integ value of the dyed textiles in Example B3 are significantly reduced. This is because the azo dye A6 used in Example B3 does not contain a polyether segment, the molecular rigidity is relatively strong, and strong π-π stacking interactions are easily formed between the dye molecules. It is difficult for the supercritical CO2 fluid to effectively break up these strongly interacting dye molecules. Therefore, the solubility of the azo dye A6 in the supercritical CO2 fluid is relatively low, which directly leads to a decrease in the dyeing rate and a decrease in the color depth Integ value.

[0179] Example B4

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

[0181] Tests show that the color fastness to soaping of the dyed textiles is level 4, the color fastness to dry rubbing is level 4-5, the color fastness to wet rubbing is level 4, the color fastness to light is level 4, the color fastness to dry heat is level 4-5, the dyeing 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] Textiles: composed of wool fibers, with a moisture content of 100wt%;

[0186] Reactive disperse dyes: Phthalocyanine dye A3;

[0187] (2) Staining;

[0188] (2.1) placing textiles and reactive disperse dyes in a supercritical CO2 fluid dyeing device, and sealing the device; wherein the mass ratio of the textiles to the reactive disperse dyes is 100:4;

[0189] (2.2) CO2 is introduced into the device, the temperature is raised to 100°C, and the pressure is raised to 30 MPa, so that the reactive disperse dye is mixed with the supercritical CO2 fluid; wherein the volume mass ratio of CO2 to textile is 1 L:45 g;

[0190] (2.3) After the supercritical CO2 fluid is controlled to circulate in the device for 90 minutes, the temperature and pressure are lowered to separate and recover the CO2 and unreacted active disperse dye;

[0191] (3) Color fixing treatment;

[0192] The dyed textiles were irradiated under UV light for 30 min.

[0193] Tests show that after color fixation treatment, the color fastness to soap washing is level 5, the color fastness to dry friction is level 5, the color fastness to wet friction is level 4-5, the color fastness to light is level 6, the color fastness to dry heat is level 5, the dyeing 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] Textiles: composed of silk fibers, with a moisture content of 60wt%;

[0198] Reactive disperse dyes: heterocyclic dye A4;

[0199] (2) Staining;

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

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

[0202] (3) Color fixing treatment;

[0203] A portion of the dyed textile is covered and the other portion is exposed to ultraviolet light for 20 minutes.

[0204] Tests show that the color fastness to washing with soap of the part of the textile that has been treated with color fixing (i.e. the area exposed to ultraviolet light) is level 5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 5, the color fastness to light is level 5, the color fastness to dry heat is level 5, the dyeing rate is 91.5%, and the color depth Integ value is 92.1; the color fastness to washing with soap of the part of the textile that has not been treated with color fixing (i.e. the covered area) is level 4-5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 4-5, the color fastness to light is level 5, the color fastness to dry heat is level 5, the dyeing 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] Textiles: composed of polylactic acid fibers, with a moisture content of 0wt%;

[0209] Reactive disperse dyes: heterocyclic dye A4;

[0210] (2) Staining;

[0211] (2.1) placing textiles and reactive disperse dyes in a supercritical CO2 fluid dyeing device, and sealing the device; wherein the mass ratio of the textiles to the reactive disperse dyes is 100:4;

[0212] (2.2) CO2 is introduced into the device, the temperature is raised to 92°C, and the pressure is raised to 24 MPa, so that the reactive disperse dye is mixed with the supercritical CO2 fluid; wherein the volume mass ratio of CO2 to textile is 1 L:55 g;

[0213] (2.3) After the supercritical CO2 fluid is controlled to circulate in the device for 45 minutes, the temperature and pressure are lowered to separate and recover the CO2 and unreacted active disperse dye.

[0214] Tests show that the color fastness of the dyed textiles to soaping is level 4-5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 4-5, the color fastness to light is level 5, the color fastness to dry heat is level 5, the dyeing rate is 92.4%, and the color depth Integ value is 88.9.

[0215] Example B8

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

[0217] Tests show that the color fastness of the dyed textiles to soaping is level 4-5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 4-5, the color fastness to light is level 5, the color fastness to dry heat is level 5, the dyeing rate is 56.3%, and the color depth Integ value is 54.6.

[0218] Compared with Example B7, the dyeing rate and color depth Integ value of the dyed textiles in Example B8 are significantly reduced. This is because the heterocyclic dye A7 used in Example B8 does not contain a polyether segment, the molecular rigidity is relatively strong, and strong π-π stacking interactions are easily formed between the dye molecules. It is difficult for the supercritical CO2 fluid to effectively break up these strongly interacting dye molecules. Therefore, the solubility of the heterocyclic dye A7 in the supercritical CO2 fluid is relatively low, which directly leads to a decrease in the dyeing rate and a decrease 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] Textiles: composed of acetate fibers, with a moisture content of 0wt%;

[0223] Reactive disperse dyes: azo dye A2;

[0224] (2) Staining;

[0225] (2.1) placing textiles and reactive disperse dyes in a supercritical CO2 fluid dyeing device, and sealing the device; wherein the mass ratio of the textiles to the reactive disperse dyes is 100:3;

[0226] (2.2) CO2 is introduced into the device, the temperature is raised to 98°C, and the pressure is raised to 20 MPa, so that the reactive disperse dye is mixed with the supercritical CO2 fluid; wherein the volume mass ratio of CO2 to textile is 1 L:48 g;

[0227] (2.3) Under ultraviolet light irradiation, the supercritical CO2 fluid is controlled to circulate in the device for 75 minutes, and then the temperature and pressure are reduced to separate and recover CO2 and unreacted active disperse dye.

[0228] Tests show that the color fastness of the dyed textiles to soaping is level 5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 5, the color fastness to light is level 6, the color fastness to dry heat is level 5, the dyeing 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 fibers with a moisture content of 0wt%;

[0233] Reactive disperse dyes: Phthalocyanine dye A3;

[0234] (2) Staining;

[0235] (2.1) placing textiles and reactive disperse dyes in a supercritical CO2 fluid dyeing device, and sealing the device; wherein the mass ratio of the textiles to the reactive disperse dyes is 100:5;

[0236] (2.2) CO2 is introduced into the device, the temperature is raised to 92°C, and the pressure is raised to 28MPa, so that the reactive disperse dye is mixed with the supercritical CO2 fluid; wherein the volume mass ratio of CO2 to reactive disperse dye is 1L:52g;

[0237] (2.3) After the supercritical CO2 fluid is controlled to circulate in the device for 80 minutes, the temperature and pressure are lowered to separate and recover the CO2 and the unreacted active disperse dye;

[0238] (3) Color fixing treatment;

[0239] The dyed textiles were irradiated under UV light for 20 min.

[0240] Tests show that the color fastness to soaping of textiles after color fixation treatment is level 5, the color fastness to dry friction is level 5, the color fastness to wet friction is level 4-5, the color fastness to light is level 6, the color fastness to dry heat is level 5, the dyeing 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 0wt%;

[0245] Reactive disperse dyes: anthraquinone dye A1;

[0246] (2) Staining;

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

[0248] (2.2) Control the dyeing temperature to 95°C, dye the textile in the dyeing tank for 65 minutes, open the dyeing tank and take out the textile;

[0249] (3) Color fixing treatment;

[0250] A portion of the dyed textile is covered and another portion is exposed to ultraviolet light for 35 minutes.

[0251] Tests show that the color fastness to washing with soap of the part of the textile that has been treated with color fixing (i.e. the area exposed to ultraviolet light) is level 4-5, the color fastness to dry rubbing is level 5, the color fastness to wet rubbing is level 4-5, the color fastness to light is level 5, the color fastness to dry heat is level 5, the dyeing rate is 92.4%, and the color depth Integ value is 93.5; the color fastness to washing with soap of the part of the textile that has not been treated with color fixing (i.e. the covered area) is level 4, the color fastness to dry rubbing is level 4-5, the color fastness to wet rubbing is level 4, the color fastness to light is level 5, the color fastness to dry heat is level 4-5, the dyeing 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 grafted thereon, characterized in that: The structural formula of the diaziridine chain segment is as follows: ； Wherein, X is -(CH2) n -, n is an integer, n≥2; Reactive disperse dyes do not contain water-soluble groups.

2. A reactive disperse dye according to claim 1, characterized in that: It also includes a polyether segment grafted on a dye matrix, wherein the number of repeating units of the polyether segment is 2-5 and the terminal group is a methyl group.

3. 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 chain segment grafted thereon. The structural formula of the diaziridine chain segment is as follows: ； Wherein, X is -(CH2) n -, n is an integer, n≥2; 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°C, which is higher than the T of synthetic fibers. g .

4. A dyeing process according to claim 3, characterized in that: The dye matrix contains two or more amino groups or hydroxyl groups; the reactive disperse dyes are anthraquinone dyes, azo dyes, phthalocyanine dyes or heterocyclic dyes.

5. A dyeing process according to claim 3, characterized in that: During the dyeing process, ultraviolet light is also used to irradiate the dyeing system.

6. A dyeing process according to claim 3, 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.

7. A dyeing process according to claim 6, 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.

8. A dyeing process according to any one of claims 3 to 7, characterized in that: Supercritical CO2 fluid is used to dissolve the dye.

9. A dyeing process according to claim 8, 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 closing 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 reduced to separate and recover CO2 and unreacted active disperse dye.

10. A dyeing process according to claim 3 or 4, characterized in that: The reactive disperse dye also includes a polyether segment grafted onto a dye matrix, the number of repeating units of the polyether segment is 2-5, and the terminal group is a methyl group; the textile is composed of hydrophilic fibers.

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