CN115162033A - Low-resource-consumption salt-free low-alkali dyeing method for reactive dye - Google Patents
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/445—Use of auxiliary substances before, during or after dyeing or printing
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5242—Polymers of unsaturated N-containing compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
- D06P1/67358—Halides or oxyhalides
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Abstract
The invention relates to a salt-free low-alkali dyeing method of a reactive dye with low resource consumption. The method comprises the following steps: soaking cotton fabric in TEMPO oxidation system solution for oxidation, cleaning and drying to obtain oxidized cotton fabric, soaking in cationic modifier solution for modification, washing and drying to obtain pretreated cotton fabric, soaking in reactive dye solution for primary dyeing, adding soda ash for fixation, soaping, washing and drying. The method has the advantages of simple technology, easy industrialization, wide dye application range, high dye uptake and fixation rate, good level-dyeing property, high color fastness, avoidance of use of chemical substances with high price and high toxicity and the like.
Description
Technical Field
The invention belongs to the field of reactive dye dyeing, and particularly relates to a salt-free low-alkali reactive dye dyeing method with low resource consumption.
Background
The reactive dye has bright color, complete chromatogram and excellent wet treatment fastness, is the most important dye for dyeing cellulose fibers, and a large amount of inorganic salt is often used for improving the affinity of the dye to cotton fabrics and the dye uptake and fixation rate of the dye in the dyeing process. The addition of inorganic salt has increased manufacturing cost on the one hand, and on the other hand still can cause the passageway to block up in dyeing equipment caking, and after the dyeing, high concentration's neutral salt remains and is difficult to get rid of in the dyeing waste water moreover, can cause rivers and soil salinization after the emission, causes irreversible destruction to the environment. The desalting treatment of the saline dyeing wastewater by the traditional physical method or biochemical method has low efficiency and high cost. Therefore, the development of a novel low-salt or salt-free dyeing method and process of the reactive dye has important significance for realizing the industrial development targets of energy conservation, emission reduction and ecological environmental protection.
At present, cationic modification of the fabric surface by introducing cationic groups with positive charges into cotton fibers is an effective way for realizing salt-free dyeing of reactive dyes. The electrostatic attraction between the cationic cotton fiber and the anionic dye increases the adsorption of the dye, and greatly reduces the demand on electrolyte in the dyeing process of the cotton fiber. The most common cationization method is to graft a reactive amine compound on cellulose fibers or to pretreat cotton fabrics with a quaternary ammonium compound under alkaline conditions. The cellulose fiber shows greater attraction to anionic dye after being modified by cations, the bonding force between the fiber and the dye is enhanced, and the dye uptake can even reach more than 85-98 percent, so that the reactive dye can dye fabrics under the condition of neutrality or no salt.
However, the binding force between the cationic agent and the cotton fiber is usually weak, most of the high molecular weight polymer cationic agent can only be adsorbed on the outer surface of the cotton fiber, is difficult to diffuse into the multi-scale micropores of the cotton fiber and is stabilized in the fiber, the dye-uptake rate is low, the leveling property and the permeability of dyed fabrics are poor easily caused in the dyeing process, and the low molecular weight cationizing agent has the problems of low substantivity, high concentration, large dosage and the like, so the practical utilization rate of the cationic agent is low [1] 。([1]Correia J,Oliveira F R,Rita D,et al.Preparation of cationic cotton through reaction with different polyelectrolytes[J].Cellulose,2021,28(18):11679-11700.)
Disclosure of Invention
The invention aims to solve the technical problem of providing a salt-free low-alkali dyeing method of a reactive dye with low resource consumption, so as to overcome the defects of low dye-uptake rate, large cationic agent dosage and the like caused by weak binding force between a cationic agent and fibers in the salt-free dyeing process of a cotton fiber reactive dye in the prior art.
The invention provides a salt-free low-alkali dyeing method of reactive dyes, which comprises the following steps:
(1) Immersing the cotton fabric into a TEMPO oxidation system solution for oxidation, cleaning and drying to obtain an oxidized cotton fabric, immersing the oxidized cotton fabric into a cationic modifier solution for modification, washing and drying to obtain a pretreated cotton fabric;
(2) And (2) immersing the cotton fabric pretreated in the step (1) into a reactive dye liquor for primary dyeing, adding soda ash for fixation, and soaping, washing and drying to obtain a cotton fabric dyeing finished product.
Preferably, the TEMPO oxidation system solution in the step (1) is a solution containing 2,2,6,6-tetramethylpiperidine oxide, sodium bromide and an oxidizing agent.
Preferably, the mass ratio of the cotton fabric, 2,2,6,6-tetramethylpiperidine oxide, sodium bromide and the oxidizing agent is 10:0.05 to 0.1:0.5 to 1:1 to 5.
Preferably, the oxidant comprises one or more of sodium hypochlorite, sodium chlorite, sodium bromite and sodium dichloroisocyanurate.
Preferably, the step (1) of immersing the cotton fabric in the TEMPO oxidation system solution is performed at room temperature.
Preferably, the process parameters of the oxidation in the step (1) are as follows: the oxidation bath ratio is 1:5 to 1:50, the pH value of the solution is 7 to 12, and the solution is oxidized for 15 to 30min at room temperature.
More preferably, the solution has a pH of 10 to 11.
Preferably, the concentration of the cation modifier solution in the step (1) is 1-5 g/L.
Preferably, the cation modifier in step (1) comprises one or more of polyethyleneimine, poly dimethyl diallyl ammonium chloride, chitosan and poly N, N-dimethylaminoethyl methacrylate.
Preferably, the molecular weight of the cationic modifier in the step (1) is 3 000 to 100 000.
Preferably, the process parameters modified in the step (1) are as follows: the modification bath ratio is 1:5 to 1:20, heating to 40-75 ℃, and carrying out heat preservation modification for 1-4 h.
Preferably, the concentration of the reactive dye liquor in the step (2) is 1-3 g/L.
Preferably, the reactive dye in step (2) includes one or more of monochlorotriazine reactive dye, dichloros-triazine reactive dye, vinyl sulfone reactive dye, bis-monochlorotriazine reactive dye, and monochlorotriazine/vinyl sulfone double reactive group reactive dye.
Preferably, the reactive dye includes one or more of c.i. reactive red 24, c.i. reactive red 111, c.i. reactive red 120, c.i. reactive red 141, c.i. reactive red 195, c.i. reactive red 198, c.i. reactive red 222, c.i. reactive red 239, c.i. reactive blue 4, c.i. reactive blue 19, c.i. reactive blue 21, c.i. reactive blue 41, c.i. reactive blue 194, c.i. reactive blue 198, c.i. reactive blue 222, c.i. reactive blue 231, c.i. reactive yellow 44, c.i. reactive yellow 176, c.i. reactive orange 7, c.i. reactive orange 122, c.i. reactive black 5, c.i. reactive violet 5.
Preferably, the step (2) of immersing the cotton fabric pretreated in the step (1) into a reactive dye solution is carried out at room temperature.
Preferably, the process parameters of the primary dyeing in the step (2) are as follows: the dyeing bath ratio is 1:5 to 1:20, heating to 40-100 ℃ at the heating rate of 1-3 ℃/min, and keeping the temperature for 10-20 min.
Preferably, the process parameters for fixing in the step (2) are as follows: heating to 60-100 ℃ at the heating rate of 1-3 ℃/min, keeping the temperature for 10-20 min, and adding 1-10 g/L of soda ash.
Advantageous effects
(1) According to the invention, selective oxidation of cotton fibers can be realized through a 2,2,6,6-tetramethylpiperidine oxide (TEMPO) mediated catalytic oxidation system, and negative charges can be effectively introduced into cotton fabrics, so that more cationic modifiers are attracted, the utilization rate of the modifiers is improved, and the aim of salt-free low-alkali dyeing of the active dye under low cationic concentration is fulfilled. The method has the advantages of little damage to the fabric, saving the dosage of the cationic modifier, improving the utilization rate of the cationic modifier and reducing the consumption of chemicals.
(2) Compared with the traditional reactive dye dyeing method, the method can realize salt-free low-alkali dyeing. The reactive dye used in dyeing has no selectivity on the structure of the dye, the dye has wide application range, high dye uptake and fixation rate, good level dyeing property and high dyeing fastness, and has the advantages of reducing production cost and reducing environmental pollution.
(3) Compared with the existing low-salt and salt-free dyeing technology of the reactive dye, the method has the advantages of small dosage and high utilization rate of the cationic modifier, simple production process, easy operation, strong practicability, no need of special equipment, and easy implementation of industrial popularization.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The main reagents are as follows: 2,2,6,6-Tetramethylpiperidine oxide (Shanghai Aladdin Biotechnology GmbH), sodium bromide, sodium carbonate, sodium sulfate, sodium hydroxide, sodium dichloroisocyanurate (national group chemical Co., ltd.), polyethyleneimine (Mw 5000g/mol, basff China GmbH), polydimethyldiallylammonium chloride (Mw 100,000g/mol, shanghai Meclin Biotechnology GmbH), C.I. reactive Red 195, C.I. reactive Red 24 (Zhejiang Longsheng group GmbH).
Example 1
(1) Pretreatment of cotton fabric: 0.1562g of 2, 6-tetramethylpiperidine oxide and 1.029g of sodium bromide were dissolved in 1000mL of deionized water, and 0.11g of sodium dichloroisocyanurate was added to 50mL of the solution to prepare a TEMPO oxidation system solution. Soaking 1g of cotton fabric into the solution at room temperature, oxidizing the cotton fabric for 30min at room temperature, slowly dropwise adding 1mol/L sodium hydroxide in the reaction process to maintain the pH value of the solution at about 10, and cleaning and drying the oxidized cotton fabric after the reaction is finished; then soaking the oxidized cotton fabric into 20mL of 3g/L polyethyleneimine (Mw 5000 g/mol) solution, heating to 40 ℃, preserving heat for modification for 4h, taking out the fabric, washing and drying.
(2) The cotton fiber dyeing process comprises the following steps: immersing the pretreated cotton fabric into C.I. reactive red 195 dye solution at room temperature, wherein the dye concentration is 2% (o.w.f), the bath ratio is 1:20, heating to 70 ℃ at the speed of 3 ℃/min, preserving heat for 10min, adding 0.01g of soda ash, heating to 70 ℃ at the speed of 3 ℃/min, preserving heat for 20min, taking out the fabric, washing with soaping water, and drying to obtain a finished cotton fabric dyeing product.
Example 2
(1) The cotton fiber modification treatment process comprises the following steps: same as in example 1.
(2) The cotton fiber dyeing process comprises the following steps: the same as in example 1, except that the reactive dye was c.i. reactive red 24, the fixing temperature after soda ash addition was 90 ℃.
Example 3
(1) The cotton fiber modification treatment process comprises the following steps: the same as in example 1, except that the cationic modifier in step (1) was poly (dimethyldiallylammonium chloride) (Mw 100,000g/mol), and the cationic modification was: the reaction is carried out for 1h by water bath oscillation at 75 ℃.
(2) The cotton fiber dyeing process comprises the following steps: same as in example 2.
Comparative example 1
The present comparative example is a c.i. reactive red 24 traditional dyeing of cotton fabric: a c.i. reactive red 24 dye liquor and a raw cotton fabric were added to a conical flask at a dye concentration of 2% (o.w.f), bath ratio 1: and 20, heating to 60 ℃, keeping the temperature for 10min, adding half 100g/L of sodium sulfate, heating to 90 ℃ at the speed of 3 ℃/min, keeping the temperature for 20min, adding the rest sodium sulfate, keeping the temperature for 30min, adding 15g/L of soda ash, keeping the temperature for 30min, taking out the fabric, and washing with water, soaping and water to obtain a cotton fabric dyeing finished product.
Comparative example 2
The comparative example is the traditional cationization modification and dyeing of cotton fabric: (1) cationization modification: according to the bath ratio of 1:20 preparing 30 g/L3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, then adding 0.0638g sodium hydroxide, immersing 1g cotton fiber into the treatment solution after the preparation of the treatment solution, and treating for 1 hour at 70 ℃. And after the reaction is finished, taking out the fabric, washing and drying. (2) cotton fiber dyeing process: the same as in example 2, except that the amount of soda added was 0.30g.
Comparative example 3
This comparative example is a comparison of example 2 without selective oxidation. (1) a cotton fiber modification treatment process: 1g of cotton fabric is immersed in 20mL of 3g/L polyethyleneimine (Mw 5000 g/mol) solution prepared, the temperature is raised to 40 ℃, the temperature is kept for modification for 4 hours, and the fabric is taken out, washed and dried.
(2) The cotton fiber dyeing process comprises the following steps: same as in example 2.
Comparative example 4
This comparative example is a comparison of example 3 without selective oxidation. (1) a cotton fiber modification treatment process: 1g of cotton fabric is immersed in 20mL of poly dimethyl diallyl ammonium chloride (Mw 100, 000g/mol) with the concentration of 3g/L, the water bath oscillation reaction is carried out for 1h at the temperature of 75 ℃, and the fabric is taken out, washed and dried.
(2) The cotton fiber dyeing process comprises the following steps: same as in example 2.
The K/S value was determined by a color measuring and matching instrument (Datacolor SF650, datacolor, USA). Wash and soaping fastnesses the dyed samples were tested according to the standard GB/T3921-2008 using a Wash fastness tester (Ningbo textile Instrument works, SW-24).
The method for measuring the dye-uptake rate comprises the following steps: respectively diluting the standard dye liquor and the dyeing residual liquor by corresponding times N with deionized water 0 And N 1 The absorbance of the solution at the maximum absorption wavelength was measured with an ultraviolet-visible spectrophotometer (Shanghai Mei spectral instruments Co., ltd., UV-1800 PC), and the dye uptake on the fiber was calculated according to the formula (1).
In the formula: a. The 0 -absorbance of the standard dye liquor after dilution; n is a radical of 0 -fold after dilution of standard dye liquor; a. The 1 -absorbance of the dye raffinate after dilution; n is a radical of 1 Fold dilution of the dye raffinate.
The method for measuring the color fixing rate comprises the following steps: collecting residual liquid of fabric washing and soaping after color fixation, and respectively using deionized water to fix volume to V 2 mL、V 3 mL, respectively diluting the corresponding times N according to the absorbance 2 、N 3 . And (3) calculating the fixation rate of the dye on the fiber according to the formula (2).
In the formula: a. The 0 -absorbance of the standard dye liquor after dilution; n is a radical of 0 -fold after dilution of standard dye liquor; a. The 1 -absorbance of the stain after dilution; n is a radical of hydrogen 1 -the dilution factor of the dyebath and the centrifuged raffinate; a. The 2 -absorbance of the rinse solution after dilution; n is a radical of 2 -the dilution factor of the rinsing liquid; a. The 3 -absorbance of the soap wash after dilution; n is a radical of 3 -dilution of the soaping solution; v 0 -a constant volume of staining standard solution; v 2 -a constant volume of flushing liquid; v 3 -volumetric volume of soap wash.
The dyeing results of the examples and comparative examples are shown in table 1, and the chemical agent amounts of the examples and comparative examples are shown in table 2.
TABLE 1 comparison of dyeing results of examples and comparative examples
TABLE 2 comparison of the amounts of chemicals used in the examples and comparative examples (based on the mass of 1g of cotton fabric)
As can be seen from tables 1 and 2, the consumption amount of the chemical reagents for cotton fiber modification of examples 1, 2 and 3 of the present invention is less than that of the chemical reagents of the schemes of comparative examples 1 and 2, but the dye yield, the dye uptake and the fixation ratio are equivalent to or even higher than those of the three schemes, which shows that the chemical reagents consumed by the modified dyeing of the cationic absorbing agent after TEMPO oxidation are less than those consumed by the traditional salt-adding dyeing and the traditional cationic modified dyeing, and the dyeing effect is equivalent to or even better than that of the traditional cationic modified dyeing. Although the reagent amount of the catalytic oxidation system is consumed more than the reagent amount of the catalytic oxidation system in the comparison ratios 3 and 4 in the embodiments 2 and 3, the dye yield, the dye uptake and the fixation rate are obviously superior to those of the latter two, and the advantage of the selective oxidation of the cotton fiber is illustrated. The color fastness performance of the embodiment of the invention is excellent.
Claims (10)
1. A salt-free low-alkali dyeing method of reactive dyes comprises the following steps:
(1) Soaking cotton fabric into TEMPO oxidation system solution for oxidation, cleaning and drying to obtain oxidized cotton fabric, soaking the oxidized cotton fabric into cation modifier solution for modification, washing and drying to obtain pretreated cotton fabric;
(2) And (2) immersing the cotton fabric pretreated in the step (1) into reactive dye liquor for primary dyeing, adding soda ash for fixation, and performing soaping, washing and drying to obtain a cotton fabric dyeing finished product.
2. The method of claim 1, wherein the TEMPO oxidation system solution of step (1) is a solution containing 2,2,6,6-tetramethylpiperidine oxide, sodium bromide and an oxidizing agent; the mass ratio of the cotton fabric, 2,2,6,6-tetramethylpiperidine oxide, sodium bromide and oxidant is 10:0.05 to 0.1:0.5 to 1:1 to 5.
3. The method of claim 2, wherein the oxidizing agent comprises one or more of sodium hypochlorite, sodium chlorite, sodium bromite, and sodium dichloroisocyanurate.
4. The method according to claim 1, wherein the oxidation in step (1) has the following process parameters: the oxidation bath ratio is 1:5 to 1:50, the pH value of the solution is 7 to 12, and the solution is oxidized for 15 to 30min at room temperature.
5. The method according to claim 1, wherein the concentration of the cationic modifier solution in the step (1) is 1 to 5g/L; the cation modifier comprises one or more of polyethyleneimine, poly dimethyl diallyl ammonium chloride, chitosan and poly N, N-dimethylaminoethyl methacrylate; the molecular weight of the cationic modifier is 3 000-100 000.
6. The method according to claim 1, wherein the process parameters modified in step (1) are: the modification bath ratio is 1:5 to 1:20, heating to 40-75 ℃, and carrying out heat preservation modification for 1-4 h.
7. The method as claimed in claim 1, wherein the concentration of the reactive dye liquor in the step (2) is 1-3 g/L; the reactive dye comprises one or more of monochlorotriazine reactive dye, dichloros-triazine reactive dye, vinyl sulfone reactive dye, bis-monochlorotriazine reactive dye and monochlorotriazine/vinyl sulfone double-reactive group reactive dye.
8. The method of claim 7, wherein the reactive dye comprises one or more of C.I. reactive red 24, C.I. reactive red 111, C.I. reactive red 120, C.I. reactive red 141, C.I. reactive red 195, C.I. reactive red 198, C.I. reactive red 222, C.I. reactive red 239, C.I. reactive blue 4, C.I. reactive blue 19, C.I. reactive blue 21, C.I. reactive blue 41, C.I. reactive blue 194, C.I. reactive blue 198, C.I. reactive blue 222, C.I. reactive blue 231, C.I. reactive yellow 44, C.I. reactive yellow 176, C.I. reactive orange 7, C.I. reactive orange 122, C.I. reactive black 5, and C.I. reactive violet 5.
9. The method as claimed in claim 1, wherein the process parameters of the primary dyeing in the step (2) are as follows: the dyeing bath ratio is 1:5 to 1:20, heating to 40-100 ℃ at the heating rate of 1-3 ℃/min, and preserving the heat for 10-20 min.
10. The method according to claim 1, wherein the process parameters for fixing in step (2) are: heating to 60-100 ℃ at the heating rate of 1-3 ℃/min, keeping the temperature for 10-20 min, and adding 1-10 g/L of soda ash.
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