CN106468026A - Cotton fiber dye and its dyeing method for supercritical CO2 fluid dyeing - Google Patents

Abstract

The invention provides a method for supercritical CO₂A fluid dyed cotton fiber dye and a method of dyeing the same, the method of dyeing comprising the steps of: step S1, providing a dyeing system, wherein the dyeing system comprises a dye kettle and a dyeing kettle, and the dye kettle and the dyeing kettle are communicated with each other; s2, dissolving cotton fiber dye in a fluid modifier, putting the cotton fiber dye and the fluid modifier into a dye kettle together, and closing the dye kettle; putting the fabric into a dyeing kettle, and then closing the dyeing kettle; step S3, injecting liquid carbon dioxide into the dyeing system, and heating and pressurizing the dyeing system to convert the liquid carbon dioxide into supercritical CO₂Fluid and subjecting the supercritical CO₂Dissolving cotton fiber dye by using a fluid; then the supercritical CO is enabled₂The fluid circulates in the dye kettle and the dyeing kettle, thereby completing dyeing. The cotton fiber dye has excellent adsorption dyeing property, and the synthetic method of the cotton fiber dye is simple in process.

Description

Cotton fiber dye and its dyeing method for supercritical CO2 fluid dyeing

technical field

The invention relates to the field of dyes, in particular to a cotton fiber dye used for supercritical _CO2 fluid dyeing and a dyeing method thereof.

Background technique

Supercritical CO ₂ fluid is a kind of green and environment-friendly fluid medium. It replaces the traditional water bath for dyeing and processing fiber textiles. It has the characteristics of environmental protection and clean production, as well as outstanding energy saving and consumption reduction effects. The status quo of high resource consumption, large amount of sewage discharge, and serious environmental pollution is of great significance.

At present, most studies on dyeing polyester and other synthetic fibers with disperse dyes have been carried out, and some of them have been industrialized. However, the direct use of disperse dyes in supercritical CO ₂ fluid to dye hydrophilic natural fibers such as cotton, wool and silk cannot meet the commercial requirements. Among them, cotton fiber has a market share of up to 37% in the global textile industry, is the most important natural fiber, and is also one of the most difficult natural fibers to dye in supercritical _CO2 fluid. At present, cotton fibers are mainly dyed in three ways: one is to change the polarity of the fluid, but the dyeing effect is not ideal; the other is to modify and dye natural fibers, but the original superior performance of natural fibers is reduced; the third is to use soluble The introduction of active groups into the matrix structure of dyes in supercritical CO ₂ fluids allows dyes to react with fibers and fix them, but there are few related reports.

In addition, compared with the traditional water-bath dyeing system, supercritical CO ₂ fluid is a hydrophobic medium; thus, (natural) fiber expansion, dye diffusion and the use of alkaline agents to promote color fixation reactions, etc. Difficult to achieve in CO ₂ fluid. Therefore, in the supercritical _CO2 fluid dyeing process, how to open the hydrogen bond between the fiber macromolecular chains, and how to improve the reaction of the dye active group and the functional group on the fiber, is to use reactive disperse dyes to make natural cotton fibers in supercritical _CO2 fluid. The key to medium dyeing to obtain satisfactory dyeing results. Therefore, in actual production, it is often necessary to use a large amount of various solvents (generally 30% to 50% or more of the weight of the dyed textiles) or other wetting bulking agents, fiber modifiers, etc. to treat hydrophilic natural fiber textiles. Pretreatment to help fiber bulking, improve dye uptake, or ammonify fiber to improve the fixation rate of dye on fiber, which increases the complexity of the dyeing process and increases the production cost.

Contents of the invention

The present invention aims at fiber expansion, dye diffusion and the use of alkaline agents to promote color fixation reactions, which are easy to achieve in conventional water baths, but are difficult to achieve in supercritical _CO2 fluids. At the same time, in actual production, it is often necessary to use a large number of various solvents or Other wetting and bulking agents, fiber modifiers, etc. pretreat hydrophilic natural fiber textiles to help the fibers expand and improve the dyeing of dyes, or ammonify the fibers to improve the fixation rate of the dyes on the fibers , which increases the complexity of the dyeing process and increases the production cost, a cotton fiber dye and its dyeing method for supercritical CO ₂ fluid dyeing with a simple dyeing process are proposed.

The technical scheme that the present invention proposes to solve the above-mentioned technical problem is as follows:

The present invention proposes a kind of dyeing method that is used for the cotton fiber dyestuff of supercritical _CO2fluid dyeing, comprises the following steps:

Step S1, providing a dyeing system, the dyeing system includes a dye kettle and a dye kettle, and the dye kettle and the dye kettle are connected to each other;

Step S2, dissolving the cotton fiber dye in the fluid modifier, putting them into the dye kettle together, and then closing the dye kettle; putting the fabric into the dye kettle, and then closing the dye kettle;

Step S3, inject liquid carbon dioxide into the dyeing system, then heat up and pressurize the dyeing system, convert the liquid carbon dioxide into a supercritical _CO2 fluid, and make the supercritical _CO2 fluid dissolve the cotton fiber dye; The CO ₂ fluid circulates in the dye kettle and the dyeing kettle, so that the supercritical CO ₂ fluid carries the cotton fiber dye and diffuses to the surface and inside of the cotton fiber of the fabric, and then the dyeing is completed;

Step S4, after the dyeing is completed, the floating color is cleaned; then the dyeing system is cooled and decompressed, and finally, the dyeing kettle is opened to take out the dyed fabric.

In the above-mentioned dyeing method of the present invention, the dyeing system also includes a preheater for preheating liquid carbon dioxide, a booster pump for injecting liquid carbon dioxide, and a supercritical _CO2 fluid in the dye kettle and the dye kettle Circulation pump for circulation.

In the above-mentioned dyeing method of the present invention, the dyeing kettle has a hollow dyeing shaft whose wall is covered with through holes; the step S2 further includes: winding the fabric on the dyeing shaft.

In the above-mentioned dyeing method of the present invention, the step S3 also includes: when the temperature and pressure in the dyeing system reach the temperature and pressure required by the dyeing process, turn off the booster pump; wherein, the temperature required by the dyeing process is 80°C- 100℃, the required pressure is 20MPa-30MPa;

Then turn on the circulation pump to circulate the supercritical _CO2 fluid in the dye kettle and the dye kettle.

In the above-mentioned dyeing method of the present invention, the circulation of the supercritical _CO2 fluid in the dye kettle and the dye kettle is forward circulation and reverse circulation alternately.

The present invention also proposes a cotton fiber dye dyed by the above-mentioned dyeing method, which has a s-triazine type active group.

Because of the s-triazine active group, the cotton fiber dye of the invention can react with the cotton fiber, so that the dye can be fixed on the cotton fiber to achieve the effect of dyeing. The cotton fiber dye of the invention has excellent adsorption and dyeing properties. In addition, the synthesis method of the cotton fiber dye of the present invention has a simple process; therefore, the cotton fiber dye for supercritical carbon dioxide fluid dyeing and its synthesis method of the present invention have very broad application prospects.

Description of drawings

The present invention will be further described below in conjunction with accompanying drawing and embodiment, in the accompanying drawing:

Fig. 1 is the synthetic roadmap of yellow cotton fiber dye;

Fig. 2 is the process flow diagram of the yellow cotton fiber dye shown in Fig. 1;

Fig. 3 is the supercritical _CO of the yellow cotton fiber dyestuff of the first embodiment of the present invention The process roadmap of fluid dyeing;

Fig. 4 adopts SCF-Y1 dyestuff to carry out the first schematic diagram of the cotton fabric of supercritical _CO2fluid dyeing;

Fig. 5 adopts SCF-Y1 dyestuff to carry out the second schematic diagram of the cotton fabric of supercritical _CO2fluid dyeing;

Fig. 6 adopts SCF-Y1 dyestuff to carry out the 3rd schematic diagram of the cotton fabric of supercritical _CO2fluid dyeing;

Fig. 7 is the 4th schematic diagram of the cotton fabric that adopts SCF-Y1 dyestuff to carry out supercritical CO ₂ fluid dyeing;

Fig. 8 is the synthetic roadmap of blue cotton fiber dyestuff;

Fig. 9 is the process flow diagram of the blue cotton fiber dye shown in Fig. 8;

Fig. 10 is the supercritical CO of the blue cotton fiber dyestuff of the _second embodiment of the present invention The process roadmap of fluid dyeing;

Fig. 11 is the schematic diagram of the cotton fabric that adopts SCF-B1 dyestuff to carry out supercritical _CO Fluid dyeing and through ironing and soaping process;

Figure 12 is a schematic diagram of a cotton fabric dyed with SCF-B1 dye by supercritical _CO fluid, ironed and treated with acetone;

Fig. 13 is the schematic diagram that adopts SCF-B1 dyestuff to carry out supercritical _CO Fluid dyeing and process cotton fabric through soaping process;

Fig. 14 is the schematic diagram of adopting SCF-B1 dyestuff to carry out supercritical _CO Fluid dyeing and the cotton fabric that is processed through ironing and fixation process;

Fig. 15 is the synthetic route figure of red cotton fiber dyestuff;

Fig. 16 shows the process flow diagram of the red cotton fiber dye shown in Fig. 15;

Fig. 17 is the supercritical _CO of the red cotton fiber dyestuff of the third embodiment of the present invention The process roadmap of fluid dyeing;

Fig. 18 is a schematic diagram of cotton fabric dyed by supercritical _CO2 fluid using SCF-R1 dye.

detailed description

The technical problem to be solved in the present invention is: supercritical CO _The fluid belongs to the hydrophobic medium; ₂ It is difficult to realize in fluid; at the same time, in actual production, it is often necessary to use a large amount of various solvents (generally 30% to 50% or more of the weight of the dyed textile) or other wetting bulking agents, fiber modifiers, etc. Water-based natural fiber textiles are pretreated to help fiber bulking, improve dye uptake, or ammonify fibers to improve the fixation rate of dyes on fibers, which increases the complexity of the dyeing process and improves the dyeing process. production cost. The technical thinking of the present invention to solve this technical problem is: adopt the reactive disperse dye that has s-triazine type active group to dye cotton fiber in supercritical CO ₂ fluid. Since the reactive disperse dye has a s-triazine active group, when dyeing in a supercritical _CO2 fluid, the s-triazine active group will react with the fiber, so that the reactive disperse dye can be fixed on the cotton fiber.

In the present invention, the cotton fiber dyes used for supercritical _CO2 fluid dyeing have s-triazine type active groups.

The synthetic method of this cotton fiber dyestuff comprises the following steps:

Step 1, using cyanuric chloride (TCT) as the active group, and putting the dye matrix and the active group into a single or mixed solvent to completely dissolve it, thereby obtaining a reaction system;

Step 2, placing the reaction system in an ice bath at 0°C to 5°C, and then adding cyanuric chloride solution and an acid scavenger dropwise to the reaction system until the condensation reaction of the reaction system ends;

Step 3, diluting the reaction system after the condensation reaction, washing, filtering and drying to obtain the cotton fiber dye.

In the above synthesis method, the dye matrix can be 1,4-diaminoanthraquinone, disperse orange 3 or disperse blue 35. When the dye parent is 1,4-diaminoanthraquinone, the cotton fiber dye is red, which is recorded as reactive disperse red SCF-R1; when the dye parent is disperse orange 3, the cotton fiber dye is yellow, which is recorded as reactive disperse yellow SCF -Y1; when the dye matrix is disperse blue 35, the cotton fiber dye is blue, which is recorded as reactive disperse blue SCF-B1; according to the principle of color matching of three primary colors, cotton fiber dyes of red, yellow and blue can be formulated. Cotton fiber dyes in various other colors.

In the present invention, the dyeing method of above-mentioned cotton fiber dyestuff comprises the following steps:

Step S1, providing a dyeing system, the dyeing system includes a dye kettle and a dye kettle, and the dye kettle and the dye kettle are connected to each other;

In this embodiment, the dyeing system also includes a preheater for preheating liquid carbon dioxide, a booster pump for injecting liquid carbon dioxide, and a circulation pump for circulating supercritical _CO fluid in the dye kettle and the dye kettle .

Step S2, dissolving the cotton fiber dye in the fluid modifier, putting them into the dye kettle together, and then closing the dye kettle; putting the fabric into the dye kettle, and then closing the dye kettle;

In this step, the dyeing kettle has a hollow dyeing shaft whose wall is covered with through holes. Generally, the dyeing shaft is a stainless steel shaft. It can be understood that the dyeing shaft can also be made of other materials. The fabric is wound on the dyeing shaft.

Step S3, inject liquid carbon dioxide into the dyeing system, then heat up and pressurize the dyeing system, convert the liquid carbon dioxide into a supercritical _CO2 fluid, and make the supercritical _CO2 fluid dissolve the cotton fiber dye; The CO ₂ fluid circulates in the dye kettle and the dyeing kettle, so that the supercritical CO ₂ fluid carries the cotton fiber dye and diffuses to the surface and inside of the cotton fiber of the fabric, and then the dyeing is completed;

In this step, when the temperature and pressure in the dyeing system reach the temperature and pressure required by the dyeing process, the booster pump can be turned off. Here, the required temperature for the dyeing process is 80°C-100°C, and the required pressure is 20MPa -30MPa; Then turn on the circulating pump to circulate the supercritical _CO2 fluid in the dye kettle and dyeing kettle. Here, the circulation of the supercritical _CO2 fluid in the dye kettle and the dyeing kettle is forward circulation and reverse circulation alternately, so as to promote the dyeing effect of the supercritical _CO2 fluid to be more uniform.

Step S4, after the dyeing is completed, the floating color is cleaned; then the dyeing system is cooled and decompressed, and finally, the dyeing kettle is opened to take out the dyed fabric.

In this step, the supercritical _CO fluid can be separated and recovered by cooling down and depressurizing the dyeing system.

In order to make the technical purpose, technical solution and technical effect of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

first embodiment

This embodiment provides a kind of synthetic method of yellow cotton fiber dye.

Specifically, with reference to Fig. 1, Fig. 1 is the synthetic route of yellow cotton fiber dye, can see, present embodiment adopts disperse orange 3 and cyanuric chloride as raw material, makes a Cl on cyanuric chloride replace disperse orange 3 One H on the amino group, thus synthesizing yellow cotton fiber dye.

With reference to Fig. 2, Fig. 2 has shown the process flowchart of the yellow cotton fiber dye shown in Fig. 1.

The synthetic method of yellow cotton fiber dyestuff comprises:

Step 1, using disperse orange 3 as the dye matrix, and putting the dye matrix into a mixed solvent of dioxane and water to completely dissolve it, thereby obtaining a reaction system;

In the mixed solvent of dioxane and water, the mass ratio of 1,4-dioxane to distilled water is 2:1 or 1:(1～3);

Further, Disperse Orange 3 adopts 0.001mol; here, the mass ratio of Disperse Orange 3 and mixed solvent determines the reaction speed, which can be determined according to specific test conditions;

Step 2. Place the reaction system in an ice bath at 0°C to 5°C, use cyanuric chloride (TCT) as the active group, and then add cyanuric chloride solution and acid scavenger dropwise to the reaction system until the reaction system The condensation reaction ends;

In this embodiment, 0.1M sodium hydroxide is used as the acid scavenger. The molar ratio of cyanuric chloride to disperse orange 3 is 2:1.

This step also includes: during the process of adding the cyanuric chloride solution and the acid scavenger dropwise to the reaction system, magnetic stirring is performed on the reaction system; in this embodiment, the magnetic stirring time is 3 hours.

Step 3, diluting the reaction system after the condensation reaction, washing, filtering and drying to obtain the yellow cotton fiber dye.

Here, for the convenience of recording the dyeing effect later, the yellow cotton fiber dye is recorded as SCF-Y1 dye.

With reference to Fig. 3, Fig. 3 is the process roadmap of the supercritical _CO2 fluid dyeing of the yellow cotton fiber dyestuff of the first embodiment of the present invention.

As shown in Figure 3, the supercritical _CO fluid dyeing method of yellow cotton fiber dye includes the following steps:

Step S1, provide a dyeing system, the dyeing system includes a dye kettle and a dyeing kettle, the dye kettle and the dyeing kettle are connected to each other; in this embodiment, the dyeing system also includes a preheater for preheating liquid carbon dioxide, for injecting liquid Booster pump for carbon dioxide, circulation pump for circulating supercritical _CO2 fluid in dye kettle and dyeing kettle.

Step S2, dissolving the yellow cotton fiber dye in the fluid modifier, putting them into the dye kettle together, and then closing the dye kettle; putting the fabric into the dye kettle, and then closing the dye kettle;

In this step, the yellow cotton fiber dyestuff is reactive disperse yellow SCF-Y1, and its admixture is 3% omf; the fluid modifier is methyl alcohol, and its admixture is 10wt% of the supercritical _CO fluid.

In this step, the dyeing kettle has a hollow dyeing shaft whose wall is covered with through holes. Generally, the dyeing shaft is a stainless steel shaft. It can be understood that the dyeing shaft can also be made of other materials. The fabric is wound on the dyeing shaft.

Step S3, inject liquid carbon dioxide into the dyeing system, then heat up and pressurize the dyeing system, convert the liquid carbon dioxide into a supercritical _CO2 fluid, and make the supercritical _CO2 fluid dissolve the yellow cotton fiber dye; then make the supercritical CO2 fluid dissolve the yellow cotton fiber dye; The critical CO ₂ fluid circulates in the dye kettle and the dyeing kettle, so that the supercritical CO ₂ fluid carries the yellow cotton fiber dye and diffuses to the surface and interior of the cotton fiber of the fabric, and then the dyeing is completed;

In this step, when the temperature and pressure in the dyeing system reach the temperature and pressure required by the dyeing process, the booster pump can be turned off. Here, the required temperature for the dyeing process is 100°C and the required pressure is 28MPa; then open Circulation pump to circulate the supercritical _CO2 fluid in the dye kettle and dyeing kettle. Here, the circulation of the supercritical _CO2 fluid in the dye kettle and the dyeing kettle is forward circulation and reverse circulation alternately, to promote the dyeing effect of the supercritical _CO2 fluid to be more uniform; wherein, the supercritical _CO2 fluid is in the dye kettle and The cycle time of the cycle in the dyeing kettle is 90min.

Step S4, after the dyeing is completed, the floating color is cleaned; then the dyeing system is cooled and decompressed, and finally, the dyeing kettle is opened to take out the dyed fabric.

As shown in Figures 4-7, Figures 4-7 are schematic diagrams of cotton fabrics dyed with supercritical _CO2 fluid using different SCF-Y1 dyes.

Here, in the synthetic method of the SCF-Y1 dye that Fig. 4 adopts, the mass ratio of 1,4-dioxane and distilled water is 1:1; In the synthetic method of the SCF-Y1 dye that Fig. 5 adopts, 1, The mass ratio of 4-dioxane and distilled water is 1:2; in the synthetic method of SCF-Y1 dye adopted in Fig. 6, the mass ratio of 1,4-dioxane and distilled water is 1:3; Fig. 7 In the synthetic method of the SCF-Y1 dye used, the mass ratio of 1,4-dioxane to distilled water is 3:1.

second embodiment

This embodiment provides a kind of synthetic method of blue cotton fiber dye.

Specifically, referring to Fig. 8, Fig. 8 is a synthetic route of blue cotton fiber dye, as can be seen, the present embodiment adopts disperse blue 35 and cyanuric chloride as raw materials, so that a Cl on cyanuric chloride replaces disperse blue One H on the hydroxyl group of 35, thereby synthesizing the blue cotton fiber dye.

Referring to FIG. 9, FIG. 9 shows a process flow diagram of the blue cotton fiber dye shown in FIG. 8.

The synthetic method of blue cotton fiber dyestuff comprises:

Step 1. Use disperse blue 35 as the dye matrix, and put the dye matrix into a mixed solvent of tetrahydrofuran and water to completely dissolve it, thereby obtaining a reaction system;

In the mixed solvent of tetrahydrofuran and water, the mass ratio of tetrahydrofuran and distilled water is 3:1;

Further, disperse blue 35 adopts 0.001mol; here, the ratio of disperse blue 35 and mixed solvent determines the reaction speed, which can be determined according to specific test conditions;

Step 2. Place the reaction system in an ice bath at 0°C to 5°C, use cyanuric chloride (TCT) as the active group, and then add cyanuric chloride solution and acid scavenger dropwise to the reaction system until the reaction system The condensation reaction ends;

In this embodiment, 0.1M sodium hydroxide is used as the acid scavenger. The molar ratio of cyanuric chloride to disperse blue 35 is 2:1.

This step also includes: during the process of adding the cyanuric chloride solution and the acid scavenger dropwise to the reaction system, magnetic stirring is performed on the reaction system; in this embodiment, the magnetic stirring time is 3 hours.

Step 3, diluting the reaction system after the condensation reaction, washing, filtering and drying to obtain the blue cotton fiber dye.

Here, in order to facilitate the recording of the dyeing effect later, the blue cotton fiber dye is recorded as SCF-B1 dye.

Referring to FIG. 10 , FIG. 10 is a process roadmap of supercritical CO ₂ fluid dyeing of blue cotton fiber dyes according to the second embodiment of the present invention.

As shown in Figure 10, the supercritical _CO2 fluid dyeing method of blue cotton fiber dye includes the following steps:

Step S1, provide a dyeing system, the dyeing system includes a dye kettle and a dyeing kettle, the dye kettle and the dyeing kettle are connected to each other; in this embodiment, the dyeing system also includes a preheater for preheating liquid carbon dioxide, for injecting liquid Booster pump for carbon dioxide, circulation pump for circulating supercritical _CO2 fluid in dye kettle and dyeing kettle.

Step S2, dissolving the blue cotton fiber dye in the fluid modifier, putting them into the dye kettle together, and then closing the dye kettle; putting the fabric into the dye kettle, and then closing the dye kettle;

In this step, the blue cotton fiber dye is reactive disperse blue SCF-B1, and its admixture is 2% omf; the fluid modifier is methyl alcohol, and its admixture is 10wt% of the supercritical _CO fluid.

In this step, the dyeing kettle has a hollow dyeing shaft whose wall is covered with through holes. Generally, the dyeing shaft is a stainless steel shaft. It can be understood that the dyeing shaft can also be made of other materials. The fabric is wound on the dyeing shaft.

Step S3, injecting liquid carbon dioxide into the dyeing system, then heating and pressurizing the dyeing system, converting the liquid carbon dioxide into a supercritical _CO2 fluid, and making the supercritical _CO2 fluid dissolve the blue cotton fiber dye; and then using The supercritical CO ₂ fluid circulates in the dye kettle and the dyeing kettle, so that the supercritical CO ₂ fluid carries the blue cotton fiber dye and diffuses to the surface and inside of the cotton fiber of the fabric, and then the dyeing is completed;

In this step, when the temperature and pressure in the dyeing system reach the temperature and pressure required by the dyeing process, the booster pump can be turned off. Here, the required temperature for the dyeing process is 100°C and the required pressure is 30MPa; then open Circulation pump to circulate the supercritical _CO2 fluid in the dye kettle and dyeing kettle. Here, the circulation of the supercritical _CO2 fluid in the dye kettle and the dyeing kettle is forward circulation and reverse circulation alternately, to promote the dyeing effect of the supercritical _CO2 fluid to be more uniform; wherein, the supercritical _CO2 fluid is in the dye kettle and The cycle time of the cycle in the dyeing kettle is 120min.

Step S4, after the dyeing is completed, the floating color is cleaned; then the dyeing system is cooled and decompressed, and finally, the dyeing kettle is opened to take out the dyed fabric.

As shown in Figures 11-14, Figures 11-14 are schematic diagrams of cotton fabrics dyed with SCF-B1 dyes in supercritical CO ₂ fluid and washed and floated.

Here, the cotton fabric shown in Figure 11 was treated with ironing and soaping, the cotton fabric shown in Figure 12 was ironed and treated with acetone; the cotton fabric shown in Figure 13 was only treated with soaping, and the cotton fabric shown in Figure 13 was only treated with soaping. The cotton fabric shown in 14 has been treated with iron drying and color fixing;

third embodiment

This embodiment provides a kind of synthetic method of red cotton fiber dye.

Specifically, referring to Fig. 15, Fig. 15 is a synthesis route of red cotton fiber dye, it can be seen that this embodiment adopts 1,4-diaminoanthraquinone and cyanuric chloride as raw materials to make one on cyanuric chloride Cl replaces the H on one amino group of 1,4-diaminoanthraquinone, or replaces the H on the two amino groups of 1,4-diaminoanthraquinone with Cl on two cyanuric chlorides, thereby synthesizing red cotton Fiber dye.

Referring to FIG. 16, FIG. 16 shows a process flow diagram of the red cotton fiber dye shown in FIG. 15.

The synthetic method of red cotton fiber dyestuff comprises:

Step 1, using 1,4-diaminoanthraquinone (i.e. disperse violet 1) as the dye matrix, and putting the dye matrix into a mixed solvent of 1,4-dioxane and water to completely dissolve it, thereby obtaining reaction system;

In the mixed solvent of 1,4-dioxane and water, the mass ratio of 1,4-dioxane to distilled water is 4:1;

Further, 0.001mol is used for 1,4-diaminoanthraquinone; here, the ratio of 1,4-diaminoanthraquinone to the mixed solvent determines the reaction speed, which can be determined according to specific test conditions;

Step 2. Place the reaction system in an ice bath at 0°C to 5°C, use cyanuric chloride (TCT) as the active group, and then add cyanuric chloride solution and acid scavenger dropwise to the reaction system until the reaction system The condensation reaction ends;

In this embodiment, 0.1M sodium hydroxide is used as the acid scavenger. The molar ratio of cyanuric chloride to 1,4-diaminoanthraquinone is 1:3.

This step also includes: during the process of adding the cyanuric chloride solution and the acid scavenger dropwise to the reaction system, magnetic stirring is performed on the reaction system; in this embodiment, the magnetic stirring time is 2.5 hours.

Step 3, diluting the reaction system after the condensation reaction, washing, filtering and drying to obtain the red cotton fiber dye.

Here, in order to facilitate the recording of the dyeing effect later, the red cotton fiber dye is recorded as SCF-R1 dye.

Referring to Fig. 17, Fig. 17 is a process roadmap of supercritical CO ₂ fluid dyeing of red cotton fiber dyes according to the third embodiment of the present invention.

As shown in Figure 17, the supercritical _CO2 fluid dyeing method of red cotton fiber dye includes the following steps:

Step S1, provide a dyeing system, the dyeing system includes a dye kettle and a dyeing kettle, the dye kettle and the dyeing kettle are connected to each other; in this embodiment, the dyeing system also includes a preheater for preheating liquid carbon dioxide, for injecting liquid Booster pump for carbon dioxide, circulation pump for circulating supercritical _CO2 fluid in dye kettle and dyeing kettle.

Step S2, dissolving the red cotton fiber dye in the fluid modifier, putting them into the dye kettle together, and then closing the dye kettle; putting the fabric into the dye kettle, and then closing the dye kettle;

In this step, the red cotton fiber dye is reactive disperse red SCF-R1, and its admixture is 3% omf; the fluid modifier is methanol, and its admixture is 10wt% of the supercritical _CO fluid.

In this step, the dyeing kettle has a hollow dyeing shaft whose wall is covered with through holes. Generally, the dyeing shaft is a stainless steel shaft. It can be understood that the dyeing shaft can also be made of other materials. The fabric is wound on the dyeing shaft.

Step S3, inject liquid carbon dioxide into the dyeing system, then heat up and pressurize the dyeing system, convert the liquid carbon dioxide into a supercritical _CO2 fluid, and make the supercritical _CO2 fluid dissolve the red cotton fiber dye; then make the supercritical CO2 fluid dissolve the red cotton fiber dye; The critical CO ₂ fluid circulates in the dye kettle and the dyeing kettle, so that the supercritical CO ₂ fluid carries the red cotton fiber dye and diffuses to the surface and interior of the cotton fiber of the fabric, and then completes the dyeing;

In this step, when the temperature and pressure in the dyeing system reach the temperature and pressure required by the dyeing process, the booster pump can be turned off. Here, the required temperature for the dyeing process is 120°C and the required pressure is 28MPa; then open Circulation pump to circulate the supercritical _CO2 fluid in the dye kettle and dyeing kettle. Here, the circulation of the supercritical _CO2 fluid in the dye kettle and the dyeing kettle is forward circulation and reverse circulation alternately, to promote the dyeing effect of the supercritical _CO2 fluid to be more uniform; wherein, the supercritical _CO2 fluid is in the dye kettle and The cycle time of the cycle in the dyeing kettle is 120min.

Step S4, after the dyeing is completed, the floating color is cleaned; then the dyeing system is cooled and decompressed, and finally, the dyeing kettle is opened to take out the dyed fabric.

As shown in Fig. 18, Fig. 18 is a schematic diagram of cotton fabric dyed with SCF-R1 dye by supercritical _CO2 fluid.

As can be seen from Figures 4-7, 11-14, and 18, it is feasible to apply SCF-Y1 dyes, SCF-B1 dyes and SCF-R1 dyes to supercritical _CO2 fluid dyeing; and SCF-Y1 dyes, SCF -B1 dyes and SCF-R1 dyes showed excellent adsorption and dyeing properties on cotton fibers in supercritical CO ₂ fluid, and could achieve dyeing and reactive fixation on cotton fibers at a relatively low temperature of 80°C.

Because of the s-triazine active group, the cotton fiber dye of the invention can react with the cotton fiber, so that the dye can be fixed on the cotton fiber to achieve the effect of dyeing. The cotton fiber dye of the invention has excellent adsorption and dyeing properties. In addition, the synthesis method of the cotton fiber dye of the present invention has a simple process; therefore, the cotton fiber dye for supercritical carbon dioxide fluid dyeing and its synthesis method of the present invention have very broad application prospects.

The invention described and claimed herein is not to be limited in scope by the specific embodiments disclosed therein, since these embodiments serve only as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, those skilled in the art will appreciate from the foregoing description that various modifications and variations of the embodiments shown and described herein are possible. Such modifications are also within the scope of the appended claims.

Claims (6)

1. a kind of dyeing method that is used for supercritical CO _The cotton fiber dyestuff of fluid dyeing, it is characterized in that, may further comprise the steps: Step S1, providing a dyeing system, the dyeing system includes a dye kettle and a dye kettle, and the dye kettle and the dye kettle are connected to each other; Step S2, dissolving the cotton fiber dye in the fluid modifier, putting them into the dye kettle together, and then closing the dye kettle; putting the fabric into the dye kettle, and then closing the dye kettle; Step S3, inject liquid carbon dioxide into the dyeing system, then heat up and pressurize the dyeing system, convert the liquid carbon dioxide into a supercritical _CO2 fluid, and make the supercritical _CO2 fluid dissolve the cotton fiber dye; The CO ₂ fluid circulates in the dye kettle and the dyeing kettle, so that the supercritical CO ₂ fluid carries the cotton fiber dye and diffuses to the surface and inside of the cotton fiber of the fabric, and then the dyeing is completed; Step S4, after the dyeing is completed, the floating color is cleaned; then the dyeing system is cooled and decompressed, and finally, the dyeing kettle is opened to take out the dyed fabric. 2. dyeing method according to claim 1, is characterized in that, described dyeing system also comprises the preheater that is used for preheating liquid carbon dioxide, is used to inject the booster pump of liquid carbon dioxide, is used to make supercritical _CO2 Circulation pump for circulating fluid in dye tank and dye tank. 3 . The dyeing method according to claim 1 , wherein the dyeing kettle has a hollow dyeing shaft whose wall is covered with through holes; the step S2 further comprises: winding the fabric on the dyeing shaft. 4 . 4. The dyeing method according to claim 2, characterized in that, said step S3 also includes: when the temperature and pressure in the dyeing system reach the temperature and pressure required by the dyeing process, closing the booster pump; wherein, the dyeing The temperature required for the process is 80°C-100°C, and the required pressure is 20MPa-30MPa; Then turn on the circulation pump to circulate the supercritical _CO2 fluid in the dye kettle and the dye kettle. 5. dyeing method according to claim 4 is characterized in that, supercritical CO _The circulation of fluid in dye still and dyeing still is that forward circulation and reverse circulation carry out alternately. 6. A cotton fiber dye dyed by the dyeing method according to any one of claims 1-5, characterized in that it has a s-triazine active group.