Preparation and application of a multi-azo reactive dye for printing and dyeing cotton fabric

Abstract

The application discloses a kind of multi-azo cotton fabric printing and dyeing active dye preparation and its application, belong to dye preparation technical field.The application provides a kind of active dye for cotton fabric dyeing as shown in the following general structure, the active dye can solve the soaping and rubbing of real cotton fabric and other color fastness problems, while the active dye has the advantages of bright color, complete color spectrum, good wet fastness, low synthesis cost and strong applicability.

Description

TECHNICAL FIELD

[0001] The application relates to preparation of a multi-azo reactive dye for cotton fabric printing and dyeing and application thereof, and belongs to the technical field of dye preparation. BACKGROUND

[0002] Reactive dyes are bright in color and complete in color spectrum, and are often used in cotton fabric printing and dyeing. Meanwhile, the reactive dyes are good in wet treatment and rubbing color fastness, and do not contain carcinogenic aromatic amines and heavy metal ions, so that the application of the reactive dyes is more and more extensive. However, in order to meet the needs of consumers for other color lights, the three primary colors are often mixed in different proportions in production, however, due to the great difference in fiber directness of reactive dyes with different structures, there is a great difference in dyeing rate and dissolution rate, thereby causing a series of problems such as great difference in dyeing cylinder, serious color difference, poor level dyeing and the like, and when printing, printing defects of inconsistent color before and after printing are formed. Therefore, it is often necessary to repair, thereby increasing enterprise cost and increasing wastewater discharge. SUMMARY

[0003] The application provides preparation of a multi-azo reactive dye and application thereof, three-chloro-s-triazine is used as a bridge group, a double-azo dye based on H acid / K acid and a double-azo dye based on 2,4-diaminobenzene sulfonic acid are synthesized into one dye molecular structure through molecular structure design, and through adjustment of structure change of a diazo component, new reactive dyes with multiple different color lights are obtained while intramolecular color mixing is realized. Meanwhile, the reactive dyes contain three or more reactive groups, and are suitable for cotton fabric dyeing or printing.

[0004] The application aims to provide a multi-azo reactive dye for cotton fabric printing and dyeing, and the structural general formula of the dye is as follows:

[0005]

[0006] in the formula, R1 and R2 are the following structures:

[0007] ①R1 and R2 are independently selected from:

[0008]

[0009] ②R1 is R2 is selected from:

[0010]

[0011] ③R1 is selected from:

[0012]

[0013] R2 is selected from:

[0014]

[0015] wherein n, m are independently selected from 1, 2 or 3.

[0016] In one embodiment of the present application, the dye structure is specifically as follows:

[0017]

[0018] In one embodiment of the present application, the preparation method of the polyazo cotton fabric printing and dyeing reactive dye with the structure shown in formula (1) comprises the following steps:

[0019] (1) uniformly beating the 4-ethyl sulfate sulfonyl aniline aqueous solution at 0-5℃, then adding concentrated hydrochloric acid, and slowly adding sodium nitrite aqueous solution to perform diazotization reaction; after the reaction is completed, adding a small amount of sulfamic acid to eliminate excess sodium nitrite, to obtain a diazonium salt;

[0020] (2) adding the diazotization salt in step (1) into a portion of H acid aqueous solution to perform coupling reaction, to obtain a coupling product system;

[0021] (3) adding the coupling product system obtained in step (2) into a uniformly beaten cyanuric chloride suspension to perform condensation reaction, to obtain a condensation liquid;

[0022] (4) adding 2,4-diamino benzene sulfonic acid into the condensation liquid obtained in step (3) to perform condensation reaction, to obtain a di-condensation liquid;

[0023] (5) preparing a diazonium salt according to the process of step (1);

[0024] (6) adding the diazonium salt obtained in step (5) into the di-condensation liquid obtained in step (4) to perform coupling reaction, salting out, filtering, and drying, to obtain a polyazo H acid-based cotton fabric printing and dyeing reactive dye.

[0025] As a preferred technical scheme:

[0026] In one embodiment of the present application, the mass fraction of the 4-ethyl sulfate sulfonyl aniline aqueous solution in step (1) is 20%-25%.

[0027] In one embodiment of the present application, the mass fraction of the sodium nitrite aqueous solution in step (1) is 30%.

[0028] In one embodiment of the present application, the diazotization reaction temperature in step (1) is 0-5℃, and the diazotization reaction time is 1-2h.

[0029] In one embodiment of the present application, the molar ratio of H acid in step (2) to step (1) is 0.97-0.99:1.

[0030] In one embodiment of the present application, the mass fraction of the aqueous solution of H acid in step (2) is 20-25%.

[0031] In one embodiment of the present application, the molar ratio of cyanuric chloride to H acid in step (3) is 1:1-1.02.

[0032] In one embodiment of the present application, the mass fraction of cyanuric chloride in the cyanuric chloride suspension in step (3) is 20-25%.

[0033] In one embodiment of the present application, the pH value of the condensed solution in step (3) is 4.0-4.5, which is adjusted by using 15% sodium carbonate.

[0034] In one embodiment of the present application, the condensation reaction temperature in step (3) is 0-5°C, the condensation reaction time is 4h, and the condensation reaction pH value is 4.0-4.5.

[0035] In one embodiment of the present application, the uniformly beaten cyanuric chloride suspension in step (3) is obtained by beating the cyanuric chloride suspension at 0-5°C for 0.5-0.7h.

[0036] In one embodiment of the present application, the molar ratio of 2,4-diaminobenzenesulfonic acid to H acid in step (4) is 1:1-1.02.

[0037] In one embodiment of the present application, the pH value of the di-condensed solution in step (4) is 4.0-4.5, which is adjusted by using 15% sodium carbonate.

[0038] In one embodiment of the present application, the condensation reaction temperature in step (4) is 30-35°C, the condensation reaction time is 2-3h, and the condensation reaction pH value is 4-4.5.

[0039] In one embodiment of the present application, the molar ratio of diazonium salt to H acid in step (6) is 1:1-1.02.

[0040] In one embodiment of the present application, the coupling reaction pH value in step (6) is adjusted to 4.5-5.0 by using 10% sodium hydroxide.

[0041] In one embodiment of the present application, in step (6), sodium hydroxide is added to adjust the pH value to 4.0-4.5, and the reaction is carried out at 15-25°C for 5-6h.

[0042] In one embodiment of the present application, in step (6), the salting-out is carried out by weighing potassium chloride at 10% of the total mass at the end of the reaction; the filtration is carried out by suction filtration; and the drying temperature is 55-60°C.

[0043] In one embodiment of the present application, the dye structure is specifically as follows:

[0044]

[0045] In one embodiment of the present application, the preparation method of the polyazo cotton fabric printing and dyeing reactive dye with the structure shown in formula (2) comprises the following steps:

[0046] (1) diazotization reaction: uniformly beat the K acid aqueous solution at 0-5℃, slowly drop the NaNO2 aqueous solution to perform diazotization, and obtain the diazotized K acid solution C;

[0047] (2) coupling reaction: uniformly beat the H acid aqueous solution at 0-5℃, and adjust the pH value to 5.5-6.0; then mix with the diazotized K acid solution C obtained in step (1), after the mixing is completed, adjust the solution pH value to about 4.0, and keep the temperature at 0-5.0℃ to perform coupling reaction; obtain the product system after the coupling of H acid and diazotized K acid;

[0048] (3) first condensation reaction: beat the trichloroisocyanuric acid aqueous solution at 0-5℃, add the pull-off powder to uniformly beat the trichloroisocyanuric acid; add the uniformly beaten trichloroisocyanuric acid solution to the product system after the coupling of H acid and diazotized K acid obtained in step (2), adjust the pH value to about 4.0, and keep the temperature at 0-5.0℃ to perform first condensation reaction, and obtain the first condensate;

[0049] (4) second condensation reaction: after the first condensate obtained in step (3) is warmed to 30-35℃, add 2,4-diamino benzene sulfonic acid, keep the temperature unchanged, and react for a period of time to obtain the second condensate;

[0050] (5) diazotization reaction: uniformly beat the 4-ethyl sulfate sulfonyl aniline aqueous solution at 0-5℃, add concentrated hydrochloric acid, and then slowly drop the NaNO2 aqueous solution to perform diazotization, and obtain the diazotized p-ester acid solution D;

[0051] (6) coupling reaction: after the second condensate obtained in step (4) is cooled to 0-5.0℃, add the diazotized p-ester aqueous solution D obtained in step (5) to the second condensate, adjust the solution pH value to about 5.0, and keep the temperature at 0-5.0℃ to perform coupling reaction;

[0052] (7) after the reaction is completed, add KCl to perform salting-out, filter and dry to obtain the crude reactive dye; finally, dissolve in 100 mL of ethanol, drop water, filter and dry to obtain the pure reactive dye.

[0053] In one embodiment of the present application, the dye structure is specifically as follows:

[0054]

[0055] In one embodiment of the present application, the preparation method of the polyazo cotton fabric printing and dyeing reactive dye shown in the structure of formula (3) comprises the following steps:

[0056] (1) diazotization reaction: uniformly pulp the p-ester aqueous solution at 0-5°C, add concentrated hydrochloric acid, and slowly drop NaNO2 aqueous solution for diazotization to obtain the diazotized p-ester solution E;

[0057] (2) coupling reaction: uniformly pulp the H acid aqueous solution at 0-5°C, and adjust the pH value to 5.5-6.0; then mix with the diazotized p-ester solution E obtained in step (1), after the mixing is completed, adjust the solution pH value to about 4.0 and keep the temperature at 0-5.0°C for coupling reaction to obtain the product system after coupling of H acid and diazotized p-ester;

[0058] (3) first condensation reaction: uniformly pulp the cyanuric chloride aqueous solution at 0-5°C, add pull-apart powder to make the cyanuric chloride pulp uniformly; add the uniformly pulped cyanuric chloride solution to the product system after coupling of H acid and diazotized p-ester obtained in step (2), adjust the pH value to about 4.0, and keep the temperature at 0-5.0°C for first condensation reaction, and obtain the monosubstituted product after the reaction is completed;

[0059] (4) second condensation reaction: after the monosubstituted product obtained in step (3) is warmed to 30-35°C, 2,4-diamino benzene sulfonic acid is added, the temperature is kept unchanged, and the reaction is carried out for a period of time to obtain the disubstituted product;

[0060] (5) diazotization reaction: uniformly pulp the 2-amino-1,4-benzenedisulfonic acid aqueous solution at 0-5°C, add concentrated hydrochloric acid, and then slowly drop NaNO2 aqueous solution for diazotization to obtain the diazotized 2-amino-1,4-benzenedisulfonic acid solution F;

[0061] (6) coupling reaction: after the disubstituted product obtained in step (4) is cooled to 0-5.0°C, the diazotized K acid aqueous solution F obtained in step (5) is added to the disubstituted product, the solution pH value is adjusted to about 5.0, and the temperature is kept at 0-5.0°C for coupling reaction;

[0062] (7) after the reaction is completed, KCl is added for salting-out, filtration and drying to obtain the crude reactive dye; finally, the crude reactive dye is dissolved in 100 mL of ethanol, water is added dropwise, and filtration and drying are carried out to obtain the pure reactive dye.

[0063] The present application also provides a printing paste formula, which comprises the above-mentioned polyazo cotton fabric printing and dyeing reactive dye.

[0064] In one embodiment of the present application, the printing paste formula comprises 1-8% of the above-mentioned multi-azo cotton fabric printing and dyeing reactive dye, 5% urea, 1-3% sodium carbonate, 40-53% water, and 40% sodium alginate paste, in terms of mass fraction.

[0065] The present application also provides the use of the above-mentioned multi-azo cotton fabric printing and dyeing reactive dye in fabric dyeing.

[0066] The present application also provides the use of the above-mentioned multi-azo cotton fabric printing and dyeing reactive dye in silk dyeing.

[0067] Advantages:

[0068] The dye of the present application belongs to multi-active group azo dye, and is more firmly combined with fabric due to multiple active groups on one dye molecule, has a high color fixation rate, and has a good dyeing building-up power on fabric. The dye has multiple active groups on one molecule, can be well combined with fabric even if the relative molecular mass is large, and successfully presents green color through intramolecular color matching, avoiding the problems of poor reproducibility and color difference caused by color matching of different dyes. BRIEF DESCRIPTION OF DRAWINGS

[0069] Figure 1 is a dyeing process flow chart using the dye prepared in Example 1;

[0070] Figure 2 is an infrared spectrum of the reactive dye in Example 1;

[0071] Figure 3 is an ultraviolet absorption spectrum of the reactive dye in Example 1;

[0072] Figure 4 is the building-up power of the reactive dye in Example 1;

[0073] Figure 5 is the printing building-up power of the reactive dye in Example 2;

[0074] Figure 6 is an ultraviolet absorption spectrum of the reactive dye in Example 2;

[0075] Figure 7 is an infrared spectrum of the reactive dye in Example 2;

[0076] Figure 8 is the printing building-up power of the reactive dye in Example 3;

[0077] Figure 9 is an ultraviolet absorption spectrum of the reactive dye in Example 3;

[0078] Figure 10is the infrared spectrum of the reactive dye in Example 3;

[0079] Figure 11 is the printing build-up of the reactive dye in Comparative Example 1;

[0080] Figure 12 is the UV absorption spectrum of the reactive dye in Comparative Example 1;

[0081] Figure 13 is the infrared spectrum of the reactive dye in Comparative Example 1.

[0082] Figure 14 is the printing build-up of the reactive dye in Comparative Example 2;

[0083] Figure 15 is the UV absorption spectrum of the reactive dye in Comparative Example 2;

[0084] Figure 16 is the infrared spectrum of the reactive dye in Comparative Example 2 DETAILED DESCRIPTION

[0085] The application will be further described with reference to the following specific examples. It should be understood that these examples are intended to illustrate the application and are not intended to limit the scope of the application. Furthermore, it should be understood that various modifications and changes can be made to the application by those skilled in the art upon reading the contents of this disclosure, which are intended to be within the scope of the application.

[0086] The p-ester involved in the following examples of the present application refers to 4-sulfatoethylsulfone aniline, and the corresponding structure is as follows:

[0087]

[0088] The H acid refers to 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid, and the corresponding structure is as follows:

[0089] The m-diamine refers to 2,4-diaminobenzenesulfonic acid, and the corresponding structure is as follows:

[0090] Example 1

[0091] Synthesis process and spectral data of the reactive dye with the following structure:

[0092]

[0093] (i.e. )

[0094] The corresponding synthesis route of the present example is as follows:

[0095] (1)

[0096] (2)

[0097]

[0098] (3)

[0099] (4)

[0100] (5)

[0101] (1) Diazotization reaction: 5.82 g of p-ester was weighed and made into a 20% aqueous solution, which was uniformly pulped at 0-5°C, then 3.5 mL of concentrated hydrochloric acid was added, and 4.73 g of 30% NaNO2 aqueous solution was slowly added dropwise. After the dropwise addition was completed, the diazotization was carried out for 1.5 h, and the potassium iodide test paper was kept slightly blue. After the reaction was completed, a small amount of sulfamic acid was added to eliminate excess nitrous acid. The diazotized p-ester solution A was obtained.

[0102] (2) Coupling reaction: 3.91 g of H acid was weighed and made into a 20% aqueous solution, which was uniformly pulped at 0-5°C for 30 min, then the pH value was adjusted to 5.5-6.0 with 20% sodium bicarbonate aqueous solution. The above solution was mixed with the diazotized p-ester solution A obtained in step (1), and after the mixing was completed, the pH value of the solution was adjusted to about 4.0 with 10% sodium hydroxide solution, the temperature was kept at 0-5.0°C, and the reaction end point was detected by TLC. The coupling product of H acid and diazotized p-ester was obtained.

[0103] (3) First condensation reaction: 1.86 g of cyanuric chloride was weighed and made into a 20% aqueous solution, which was pulped at 0-5°C for 30 min, then 2 drops of 5% Raney powder aqueous solution were added to make the cyanuric chloride pulping uniform. The uniformly pulped cyanuric chloride solution was added to the coupling product of H acid and diazotized p-ester, the pH value was adjusted to about 4.0 with 20% sodium bicarbonate aqueous solution, the temperature was kept at 0-5.0°C, and whether the reaction reached the end point was detected by amino reagent. The monosubstituted product was obtained after the reaction was completed.

[0104] (4) Second condensation reaction: the monosubstituted product was warmed to 30-35°C, then 2.23 g of m-dian was weighed and added to the monosubstituted product, the temperature was kept unchanged, the reaction was carried out for a period of time, and the end point of the reaction was detected by TLC. The disubstituted product was obtained.

[0105] (5) diazotization: 5.82 g of p-ester was dissolved in water to form a 20% solution, and then was uniformly beaten at 0-5°C. 3.5 mL of concentrated hydrochloric acid was added, and then 4.73 g of 30% NaNO2 solution was slowly added dropwise. After the addition was completed, diazotization was carried out for 1.5 h, and the potassium iodide test paper was kept slightly blue. After the reaction was completed, a small amount of sulfamic acid was added to eliminate excess nitrous acid. A diazotized p-ester solution B was obtained.

[0106] (6) coupling reaction: the diester obtained in step (4) was cooled to 0-5.0°C, and then the diazotized p-ester solution B obtained in step (5) was added. The pH value of the solution was adjusted to about 5.0 by using 10% sodium hydroxide solution, and the temperature was kept at 0-5.0°C. The reaction end point was detected by TLC;

[0107] (7) salting-out: KCl was weighed according to 10% of the total liquid amount at the end of the reaction, and then was used for salting-out. The crude reactive dye was obtained by filtration and drying, and the yield was 78.91%.

[0108] (8) the crude reactive dye obtained above was dissolved in 100 mL of ethanol, and then 5 mL of water was added dropwise. The pure reactive dye was obtained by filtration and drying.

[0109] The nuclear magnetic resonance hydrogen spectrum data are as follows: 1H NMR (400 MHz, DMSO-d6) δ 15.41 (s, 1H, -SO3H), 15.38 (s, 1H, -SO3H), 11.53 (s, 1H, -SO3H), 10.63 (s, 1H, -SO3H), 10.39 (s, 1H, -SO3H), 9.47 (s, 1H, -NH), 9.20 (s, 1H, -NH), 8.25 (s, 2H, -NH2), 8.22 (s, 1H, Ar-H), 8.20 (s, 1H, Ar-H), 8.17 (s, 1H, Ar-H), 7.96 (s, 1H, Ar-H), 7.94 (s, 2H, -CH2), 7.92 (s, 2H, -CH2), 7.91 (s, 1H, Ar-H), 7.89 (s, 1H, Ar-H), 7.52 (s, 2H, -CH2), 7.48 (s, 1H, Ar-H), 7.46 (s, 1H, Ar-H), 7.35 (s, 1H, Ar-H), 7.23 (s, 1H, Ar-H), 7.20 (s, 1H, Ar-H), 7.18 (d, 2H, -CH2), 7.16 (d, 2H, -CH2), 7.14 (s, 1H, Ar-H), 7.11 (s, 1H, Ar-H), 7.10 (s, 2H), 6.98 (s, 1H, Ar-H), 6.67 (s, 1H, Ar-H), 6.65 (s, 1H, Ar-H), 6.42 (s, 1H, Ar-H), 6.39 (s, 1H, Ar-H), 6.37 (s, 1H, Ar-H), 6.36 (d 2H, -CH2), 6.32 (s, 1H,), 6.26 (d, 2H, -CH2), 6.20 (d, 2H, -CH2), 1.22 (s, 1H, -OH).

[0110] Its infrared spectrum is shown in Figure 1 , and the specific data are as follows: 3418, 2776, 1718, 1592, 1488, 1408, 1340, 1212, 1125, 1043, 997, 841, 736 cm -1 .

[0111] Application performance:

[0112] The dye obtained in Example 1 was dispersed in deionized water to prepare a dye solution with a concentration of 0.01 g / L. The UV absorption spectrum of the dye solution was measured, and the results are shown in Figure 3 The dye solution has absorption at 400 nm and 592 nm, indicating that there are yellow and blue light emitters in the molecule. The dye solution is theoretically green, and the solution color is consistent with the observation by the naked eye.

[0113] Determination of dyeing build-up of the dyes on cotton fabric: The dyes obtained in Example 1 were dispersed in deionized water to prepare dyeing solutions with dye concentrations of 0.5%, 1%, 2%, 3%, and 5% (o.w.f (on weight of fabric)) respectively, and cotton fabric was dyed according to the dyeing procedure shown in Figure 1 The KS values of the dyed fabric were determined after the test dyeing, and the results are shown in Figure 4

[0114] Determination of dyeing characteristic values of the dyes: The dyes obtained in Example 1 were dispersed in deionized water to prepare dyeing solutions with dye concentrations of 0.5%, and cotton fabric was dyed, and the directness (S), reactivity (R), exhaustion (E), and fixation (F) of the dyes on silk fabric were calculated according to Formulas (1) to (4):

[0115]

[0116]

[0117]

[0118]

[0119] In the formulas, A0 is the absorbance value of the dyeing solution before dyeing; A1 is the absorbance value of the dyeing residue 30 minutes before fixation; A2 and A3 are the absorbance values of the dyeing residue 5 minutes and 45 minutes after fixation, respectively; and A4 is the absorbance value of the soaping residue after dyeing.

[0120] The test results are as follows

[0121]

[0122] Determination of the dyeing fastness performance of the dyes: The dyes obtained in Example 1 were dispersed in deionized water to prepare dyeing solutions with dye concentrations of 0.5 g / L, and cotton fabric was dyed, and the color fastness of the dyed fabric was tested. The color fastness to rubbing was tested according to ISO 105-X12:2001 Textiles-Color fastness tests-Rubbing fastness, and the color fastness to washing was tested according to ISO 105-C03:2010 Textiles-Color fastness tests-Washing fastness. The test results are as follows.

[0123]

[0124] Example 2

[0125] Synthesis process and spectral data of the reactive dyes with the following structure:

[0126]

[0127] (i.e. )

[0128] ​The corresponding synthetic route of this example is:

[0129] (1)

[0130] (2)

[0131] (3)

[0132] (4)

[0133] (5)

[0134] (6)

[0135] Preparation process:

[0136] (1) diazotization reaction: take K acid 10.99g, make into 20% aqueous solution, uniformly beat at 0-5℃, then slowly add 4.73g of 30% NaNO2 aqueous solution, after dropwise addition, diazotization for 1.5h, keep potassium iodide test paper slightly blue. After the reaction is completed, in order to eliminate excess nitrous acid, add a small amount of sulfamic acid; obtain diazotized K acid solution C. (K acid refers to 2-naphthylamine-3,6,8-trisulfonic acid, the corresponding structure is: ).

[0137] (2) coupling reaction: take H acid 3.91g, make into 20% aqueous solution, uniformly beat at 0-5℃ for 30min, then adjust pH value to 5.5-6.0 with 20% sodium bicarbonate aqueous solution. Mix the above solution with diazotized K acid solution C obtained in step (1), after mixing, adjust the solution pH value to about 4.0 with 10% sodium hydroxide solution, keep the temperature at 0-5.0℃, use TLC to detect the reaction end point; obtain the product system after coupling of H acid and diazotized K acid.

[0138] (3) first condensation reaction: take cyanuric chloride 1.86g, make into 20% aqueous solution, beat at 0-5℃ for 30min, then add 2 drops of 5% Raney nickel aqueous solution to make the cyanuric chloride solution uniform. Add the uniform cyanuric chloride solution to the product system after coupling of H acid and diazotized K acid, adjust the pH value to about 4.0 with 20% sodium bicarbonate aqueous solution, keep the temperature at 0-5.0℃, use amino reagent to detect whether the reaction reaches the end point; after the reaction is completed, obtain the first condensate.

[0139] (4) Secondary condensation reaction: after the mono-condensate is warmed to 30-35°C, 2.23 g of m-diamine is weighed and added to the mono-condensate, the temperature is kept constant, the reaction is carried out for a period of time, and the end point of the reaction is detected by TLC to obtain the di-condensate.

[0140] (5) Diazotization reaction: 5.24 g of p-ester is weighed to form a 20% aqueous solution, which is uniformly beaten at 0-5°C, 3.5 mL of concentrated hydrochloric acid is added, and then 4.13 g of 30% NaNO2 aqueous solution is slowly added dropwise. After the dropwise addition is completed, the diazotization is carried out for 1.5 h, and the potassium iodide test paper is kept slightly blue. After the reaction is completed, a small amount of sulfamic acid is added to eliminate excess nitrous acid; the diazotized p-ester acid solution D is obtained.

[0141] (6) Coupling reaction: the di-condensate obtained in step (4) is cooled to 0-5.0°C, and the diazotized p-ester aqueous solution D obtained in step (5) is added to the di-condensate. The pH value of the solution is adjusted to about 5.0 by using 10% sodium hydroxide aqueous solution, the temperature is kept at 0-5.0°C, and the end point of the reaction is detected by TLC.

[0142] (7) Salting-out: KCl is weighed according to 10% of the total liquid amount at the end of the reaction for salting-out, and the crude reactive dye is obtained by suction filtration and drying, with a yield of 78.91%.

[0143] (8) The crude reactive dye obtained above is dissolved in 100 mL of ethanol, and 5 mL of water is added dropwise, and the pure reactive dye is obtained by suction filtration and drying.

[0144] The infrared spectrum thereof is shown in Figure 7 , and the specific data are as follows: 3439.80, 3194.29, 1552.22, 1419.69, 1181.54, 1137.61, 1039.86, 736.11 cm -1 .

[0145] Application performance:

[0146] The dyeing and printing lifting power of the dye is determined: printing paste is prepared by using the dye with a concentration of 1 wt%, 2 wt%, 4 wt%, 6 wt%, and 8 wt% (with respect to the weight of the printing paste), and the printing paste formula is shown in Table 1. The cotton fabric is printed, and after the printing is completed, the printed fabric is pre-dried at 80°C for 5 min, and then steamed for 8 min, and finally, soaping, washing, and drying are carried out to obtain the printed fabric, and the KS value of the printed fabric is tested, and the results are shown in Figure 5 .

[0147] Table 1 Printing paste formula (mass fraction)

[0148]

[0149] The 4% sodium alginate paste refers to a paste with a mass fraction of 4% sodium alginate. The specific formula is as follows (taking 100 g as an example): 1 g of resist salt S is dissolved in 95 g of deionized water, and then 4 g of sodium alginate is added under stirring, and the 4% sodium alginate paste is obtained after stirring for 30 min. The resist salt S is sodium m-nitrobenzenesulfonate.

[0150] The dye printing fixation rate of the dye is determined by using formula (5) to calculate the dye printing fixation rate F of the dye with a concentration of 1%.

[0151]

[0152] In the formula, A0 is the absorbance of the dye before fixation, A1 is the absorbance of the soaping residual solution after fixation, and A2 is the absorbance of the residual solution after washing.

[0153] The final determination shows that the dye printing fixation rate of the dye is 56.12%.

[0154] The ultraviolet absorption spectrum is determined by referring to the method in Example 1, and the result is shown in Figure 6 .

[0155] The dye printing fastness performance of the dye is determined: the color fastness of the fabric after printing with a dye concentration of 1% is tested. The color fastness to rubbing is tested according to ISO 105-X12:2001 Textiles-Color Fastness Tests-Rubbing Fastness; and the color fastness to washing is tested according to ISO 105-C03:2010 Textiles-Color Fastness Tests-Washing Fastness. The test results are as follows.

[0156]

[0157] Example 3:

[0158] The synthesis process and spectral data of the reactive dye with the following structure are as follows:

[0159]

[0160] (i.e. )

[0161] The corresponding synthesis route is as follows:

[0162] (1)

[0163] (2)

[0164] (3)

[0165] (4)

[0166] (5)

[0167] (6)

[0168] Preparation process:

[0169] (1) Diazotization reaction: 5.82 g of p-ester was weighed and made into a 20% aqueous solution, which was uniformly pulped at 0-5°C, then 3.5 mL of concentrated hydrochloric acid was added, and 1.42 g of 30% NaNO2 aqueous solution was slowly added dropwise. After the dropwise addition was completed, diazotization was carried out for 1.5 h, and the potassium iodide test paper was slightly blue. After the reaction was completed, a small amount of sulfamic acid was added to eliminate excess nitrous acid; the diazotized p-ester solution E was obtained.

[0170] (2) Coupling reaction: 3.91 g of H acid was weighed and made into a 20% aqueous solution, which was uniformly pulped at 0-5°C for 30 min, then the pH value was adjusted to 5.5-6.0 with 20% sodium bicarbonate aqueous solution. The above solution was mixed with the diazotized p-ester solution E obtained in step (1), and after the mixing was completed, the pH value of the solution was adjusted to about 4.0 with 10% sodium hydroxide solution, the temperature was kept at 0-5.0°C, and TLC was used to detect the end point of the reaction; the product system after coupling of H acid and diazotized p-ester was obtained.

[0171] (3) First condensation reaction: 1.86 g of cyanuric chloride was weighed and made into a 20% aqueous solution, which was pulped at 0-5°C for 30 min, then 2 drops of 5% Raney powder aqueous solution were added to make the cyanuric chloride pulping uniform. The uniformly pulped cyanuric chloride solution was added to the product system after coupling of H acid and diazotized p-ester, the pH value was adjusted to about 4.0 with 20% sodium bicarbonate aqueous solution, the temperature was kept at 0-5.0°C, and the amino reagent was used to detect whether the reaction reached the end point; the monomonomer was obtained after the reaction was completed.

[0172] (4) Second condensation reaction: the monomonomer was warmed to 30-35°C, then 2.23 g of m-bis was weighed and added to the monomonomer, the temperature was kept unchanged, the reaction was carried out for a period of time, and TLC was used to detect the end point of the reaction; the dimonomer was obtained.

[0173] (5) Diazotization reaction: 5.05 g of 2,5 acid was weighed and made into a 20% aqueous solution, which was uniformly pulped at 0-5°C, then 3.5 mL of concentrated hydrochloric acid was added, and 4.13 g of 30% NaNO2 aqueous solution was slowly added dropwise. After the dropwise addition was completed, diazotization was carried out for 1.5 h, and the potassium iodide test paper was slightly blue. After the reaction was completed, a small amount of sulfamic acid was added to eliminate excess nitrous acid; the diazotized 2,5 acid solution F was obtained. (2,5 acid refers to 2-amino-1,4-benzenedisulfonic acid, and the corresponding structure is: ).

[0174] (6) Coupling reaction: the diester obtained in step (4) is cooled to 0-5.0°C, and the diazotized K acid aqueous solution F obtained in step (5) is added to the diester, the pH value of the solution is adjusted to about 5.0 with 10% sodium hydroxide aqueous solution, the temperature is kept at 0-5.0°C, and whether the reaction reaches the end point is detected by TLC;

[0175] (7) Salting-out: KCl is weighed according to 10% of the total liquid amount at the end of the reaction for salting-out, and the crude reactive dye is obtained by suction filtration and drying, with a yield of 78.91%.

[0176] (8) The above obtained reactive dye is dissolved in 100 mL of ethanol, and 5 mL of water is added dropwise, and the pure product of the reactive dye is obtained by suction filtration and drying.

[0177] Its infrared spectrum is shown in Figure 10 , and the specific data are as follows: 2798.37, 1749.55, 1478.06, 1410.99, 1176.04, 1125.77, 1044.14 cm -1 .

[0178] Application performance:

[0179] The printing dyeing build-up of the dye obtained in this example is determined by referring to the method in Example 2, and the results are shown in Figure 8 .

[0180] The printing fixation rate of the dye is determined by using formula (5) to calculate the printing fixation rate F of the dye with a concentration of 1%, and the final determination shows that the printing fixation rate of the dye is 70.71%.

[0181] The ultraviolet absorption spectrum is determined by referring to the method in Example 1, and the results are shown in Figure 9 .

[0182] The printing fastness performance of the dye is determined, and the test results are as follows.

[0183]

[0184] Comparative Example 1:

[0185] Synthesis process and spectral data of the reactive dye with the following structure:

[0186]

[0187] (i.e. )

[0188] The corresponding synthesis route of this comparative example is:

[0189] (1)

[0190] (2)

[0191] (3)

[0192] (4)

[0193] (5)

[0194] (6)

[0195] Preparation process:

[0196] (1) diazotization reaction: 2,5 acid 5.61 g was weighed and prepared into a 20% aqueous solution, which was uniformly pulped at 0-5°C, then 3.5 mL of concentrated hydrochloric acid was added, and 4.73 g of 30% NaNO2 aqueous solution was slowly added dropwise. After the dropwise addition was completed, diazotization was carried out for 1.5 h, and the potassium iodide test paper was slightly blue. After the reaction was completed, a small amount of sulfamic acid was added to eliminate excess nitrous acid; the diazotized 2,5 acid solution G was obtained.

[0197] (2) coupling reaction: H acid 3.91 g was weighed and prepared into a 20% aqueous solution, which was uniformly pulped at 0-5°C for 30 min, then the pH value was adjusted to 5.5-6.0 with 20% sodium bicarbonate aqueous solution. The above solution was mixed with the diazotized 2,5 acid solution G obtained in step (1), and after the mixing was completed, the pH value of the solution was adjusted to about 4.0 with 10% sodium hydroxide solution, the temperature was kept at 0-5.0°C, and TLC was used to detect the end point of the reaction; the product system after the coupling of H acid and diazotized 2,5 acid was obtained.

[0198] (3) first condensation reaction: cyanuric chloride 1.86 g was weighed and prepared into a 20% aqueous solution, which was pulped at 0-5°C for 30 min, then 2 drops of 5% Raney nickel aqueous solution were added to make the cyanuric chloride solution uniform. The uniformly pulped cyanuric chloride solution was added to the product system after the coupling of H acid and diazotized 2,5 acid, the pH value was adjusted to about 4.0 with 20% sodium bicarbonate aqueous solution, the temperature was kept at 0-5.0°C, and amino reagent was used to detect whether the reaction reached the end point; the monomonomer was obtained after the reaction was completed.

[0199] (4) second condensation reaction: the monomonomer was warmed to 30-35°C, then m-bis 2.23 g was weighed and added to the monomonomer, the temperature was kept unchanged, the reaction was carried out for a period of time, and TLC was used to detect the end point of the reaction; the dimonomer was obtained.

[0200] (5) diazotization: 5.24 g of p-position ester was weighed and dissolved in water to form a 20% solution, and then uniformly pulped at 0-5°C. 3.5 mL of concentrated hydrochloric acid was added, and then 4.13 g of 30% NaNO2 solution was slowly added dropwise. After the addition was completed, diazotization was carried out for 1.5 h, and the potassium iodide test paper was kept slightly blue. After the reaction was completed, a small amount of sulfamic acid was added to eliminate excess nitrous acid. The diazotized p-position ester solution H was obtained.

[0201] (6) coupling reaction: the diacetal obtained in step (4) was cooled to 0-5.0°C, and the diazotized p-position ester solution H obtained in step (5) was added to the diacetal. The pH value of the solution was adjusted to about 5.0 by using 10% sodium hydroxide solution, and the temperature was kept at 0-5.0°C. The reaction end point was detected by TLC.

[0202] (7) salting out: KCl was weighed according to 10% of the total liquid volume at the end of the reaction, and the crude reactive dye was obtained by filtration and drying, with a yield of 78.91%.

[0203] (8) The reactive dye obtained above was dissolved in 100 mL of ethanol, and then 5 mL of water was added dropwise. The pure reactive dye was obtained by filtration and drying.

[0204] Its infrared spectrum is shown in Figure 13 , and the specific data are as follows: 3442.30, 2882.86, 1554.31, 1487.24, 1394.45, 1185.29, 1044.78, 740.66 cm -1 .

[0205] Application performance:

[0206] The dyeing build-up of the dye was measured by the method in Example 2, and the results are shown in Figure 11 .

[0207] The dyeing fixation rate of the dye was measured by using formula (5) to calculate the dyeing fixation rate F of the dye with a concentration of 1%, and the final measurement showed that the dyeing fixation rate of the dye was 45.93%.

[0208] The ultraviolet absorption spectrum was measured by the method in Example 1, and the results are shown in Figure 12 .

[0209] The printing fastness performance of the dye was measured, and the results are as follows.

[0210]

[0211] Comparative Example 2

[0212] Structure:

[0213]

[0214] (i.e. ) the corresponding synthetic route is:

[0215] (1)

[0216] (2)

[0217] (3)

[0218] (4)

[0219] (5)

[0220] (6)

[0221] The specific preparation process is:

[0222] (1) diazotization reaction: take 5.82 g of p-ester, prepare a 20% aqueous solution, uniformly pulp at 0-5°C, then add 3.5 mL of concentrated hydrochloric acid, slowly add 1.42 g of 30% NaNO2 aqueous solution, after the addition is completed, diazotize for 1.5 h, keep the potassium iodide test paper slightly blue. After the reaction is completed, in order to eliminate excess nitrous acid, a small amount of sulfamic acid is added; obtain the diazotized p-ester solution I.

[0223] (2) coupling reaction: take 3.91 g of H acid, prepare a 20% aqueous solution, uniformly pulp at 0-5°C for 30 min, then adjust the pH value to 5.5-6.0 with 20% sodium bicarbonate aqueous solution. Mix the above solution with the diazotized p-ester solution I obtained in step (1), after the mixing is completed, adjust the pH value of the solution to about 4.0 with 10% sodium hydroxide solution, keep the temperature at 0-5.0°C, use TLC to detect the reaction end point; obtain the product system after the coupling of H acid and diazotized p-ester.

[0224] (3) first condensation reaction: take 1.86 g of cyanuric chloride, prepare a 20% aqueous solution, pulp at 0-5°C for 30 min, then add 2 drops of 5% Raney powder aqueous solution to make the cyanuric chloride pulp uniformly. Add the uniformly pulped cyanuric chloride solution to the product system after the coupling of H acid and diazotized p-ester, adjust the pH value to about 4.0 with 20% sodium bicarbonate aqueous solution, keep the temperature at 0-5.0°C, use amino reagent to detect whether the reaction reaches the end point; after the reaction is completed, obtain the first condensate.

[0225] (4) Secondary condensation reaction: after the mono-condensate is warmed to 30-35°C, 2.23 g of m-diamine is weighed and added to the mono-condensate, the temperature is kept constant, the reaction is allowed to proceed for a period of time, and the reaction is detected by TLC to determine whether the reaction has reached the end point, to obtain the di-condensate.

[0226] (5) Diazotization reaction: 9.86 g of K acid is weighed and dissolved in water to form a 20% aqueous solution, which is uniformly pulped at 0-5°C, and then 4.13 g of a 30% NaNO2 aqueous solution is slowly added dropwise. After the addition is completed, the diazotization is carried out for 1.5 h, and the potassium iodide test paper is kept slightly blue. After the reaction is completed, a small amount of sulfamic acid is added to eliminate excess nitrous acid, to obtain the diazotized K acid solution J.

[0227] (6) Coupling reaction: the di-condensate obtained in step (4) is cooled to 0-5.0°C, and the diazotized K acid aqueous solution J obtained in step (5) is added to the di-condensate. A 10% NaOH aqueous solution is used to adjust the pH of the solution to about 5.0, the temperature is kept at 0-5.0°C, and the reaction is detected by TLC to determine whether the reaction has reached the end point.

[0228] (7) Salting-out: KCl is weighed at 10% of the total liquid volume at the end of the reaction, and the crude reactive dye is obtained by filtration and drying, with a yield of 78.91%.

[0229] (8) The crude reactive dye obtained above is dissolved in 100 mL of ethanol, and 5 mL of water is added dropwise, and the pure reactive dye is obtained by filtration and drying.

[0230] The infrared spectrum thereof is shown in Figure 16 , and the specific data are as follows: 3057.86, 1553.52, 1416.64, 1108.22, 1037.31, 840.83, 612.37 cm -1 .

[0231] Application performance:

[0232] The dye building-up of the dye obtained in Comparative Example 2 is determined by the method in Reference Example 1, and the results are shown in Figure 14 .

[0233] The UV absorption spectrum of the dye obtained in Comparative Example 2 is determined by the method in Reference Example 1, and the results are shown in Figure 15 .

[0234] The printing fastness performance of the dye is determined, and the test results are as follows.

[0235]

[0236] The dye in Comparative Example 2 is configured to a concentration of 0.5% to dye cotton fabric by the process of Reference Example 1.

[0237] The test results are as follows:

[0238]

[0239]

[0240] The above provided examples are not intended to limit the scope of the present application, nor are the described steps intended to limit the order of their execution. Those skilled in the art will make obvious modifications to the present application in light of the prior art knowledge, which also fall within the protection scope defined by the claims of the present application.

Claims

1. A reactive dye for printing and dyeing polyazo cotton fabrics, characterized in that, The general formula for the dye structure is: In the formula, R1 and R2 have the following structures: ①R1 and R2 are independently selected from: ②R1 is R2 is selected from: ③R1 is selected from: R2 is selected from: Where n and m are independently selected from 1, 2 or 3 respectively.

2. The reactive dye for printing and dyeing polyazo cotton fabrics according to claim 1, characterized in that, R1 is selected from: R2 is 3. The reactive dye for printing and dyeing polyazo cotton fabrics according to claim 1, characterized in that, The specific structural formula of the dye is as follows:

4. The reactive dye for printing and dyeing polyazo cotton fabrics according to claim 3, characterized in that, Its preparation method includes the following steps: (1) Diazotization reaction: After uniformly slurrying the K acid aqueous solution at 0-5℃, NaNO2 aqueous solution is slowly added dropwise to carry out diazotization, and the diazotized K acid solution C is obtained; (2) Coupling reaction: The H acid aqueous solution is uniformly slurried at 0-5℃ and the pH value is adjusted to 5.5-6.0; then it is mixed with the diazotized K acid solution C obtained in step (1). After the mixing is completed, the pH value of the solution is adjusted to about 4.0 and the temperature is maintained at 0-5.0℃ to carry out the coupling reaction; the product system after coupling of H acid and diazotized K acid is obtained. (3) Primary condensation reaction: The cyanuric chloride aqueous solution is pulped at 0-5℃, and the separating powder is added to make the cyanuric chloride pulp uniform; the uniformly pulped cyanuric chloride solution is added to the product system after coupling H acid and diazotized K acid obtained in step (2), the pH value is adjusted to about 4.0, and the temperature is kept at 0-5.0℃ to carry out a primary condensation reaction to obtain a condensate; (4) Secondary condensation reaction: After heating the primary condensate obtained in step (3) to 30-35°C, add 2,4-diaminobenzenesulfonic acid, keep the temperature constant, and react for a period of time to obtain the secondary condensate; (5) Diazotization reaction: 4-ethyl sulfate sulfone aniline aqueous solution is uniformly slurried at 0-5℃, concentrated hydrochloric acid is added, and then NaNO2 aqueous solution is slowly added dropwise to carry out diazotization, so as to obtain the diazotized para-ester acid solution D. (6) Coupling reaction: After cooling the dicondensate obtained in step (4) to 0-5.0℃, add the diazotized para-ester aqueous solution D obtained in step (5) to the dicondensate, adjust the pH of the solution to about 5.0, and keep the temperature at 0-5.0℃ to carry out the coupling reaction. (7) After the reaction is complete, KCl is added for salting out, filtered and dried to obtain crude reactive dye; finally, it is dissolved in 100 mL of ethanol, water is added dropwise, filtered and dried to obtain pure reactive dye.

5. The reactive dye for printing and dyeing polyazo cotton fabrics according to claim 1, characterized in that, The specific structural formula of the dye is as follows:

6. The reactive dye for printing and dyeing polyazo cotton fabrics according to claim 5, characterized in that, Its preparation method includes the following steps: (1) Diazotization reaction: The para-ester aqueous solution was uniformly slurried at 0-5℃, concentrated hydrochloric acid was added, and NaNO2 aqueous solution was slowly added dropwise to carry out diazotization, resulting in diazotized para-ester solution E. (2) Coupling reaction: H acid aqueous solution is uniformly slurried at 0-5℃ and the pH value is adjusted to 5.5-6.0; then it is mixed with the diazotized para ester solution E obtained in step (1). After mixing, the pH value of the solution is adjusted to about 4.0 and the temperature is kept at 0-5.0℃ to carry out the coupling reaction, so as to obtain the product system after coupling of H acid and diazotized para ester. (3) Primary condensation reaction: The cyanuric chloride aqueous solution is pulped at 0-5℃, and the separating powder is added to make the cyanuric chloride pulp uniform; the uniformly pulped cyanuric chloride solution is added to the product system after coupling of H acid and diazotized para ester obtained in step (2), the pH value is adjusted to about 4.0, and the temperature is kept at 0-5.0℃ to carry out a primary condensation reaction. After the reaction is completed, a primary condensate is obtained. (4) Secondary condensation reaction: After heating the primary condensate obtained in step (3) to 30-35°C, add 2,4-diaminobenzenesulfonic acid, keep the temperature constant, and react for a period of time to obtain the secondary condensate; (5) Diazotization reaction: 2-amino-1,4-benzenedisulfonic acid aqueous solution is uniformly slurried at 0-5℃, concentrated hydrochloric acid is added, and then NaNO2 aqueous solution is slowly added dropwise to carry out diazotization, so as to obtain diazotized 2-amino-1,4-benzenedisulfonic acid solution F. (6) Coupling reaction: After cooling the dicondensate obtained in step (4) to 0-5.0℃, add the diazotized 2-amino-1,4-benzenedisulfonic acid solution F obtained in step (5) to the dicondensate, adjust the pH of the solution to about 5.0, and keep the temperature at 0-5.0℃ to carry out the coupling reaction. (7) After the reaction is complete, KCl is added for salting out, filtered and dried to obtain crude reactive dye; finally, it is dissolved in 100 mL of ethanol, water is added dropwise, filtered and dried to obtain pure reactive dye.

7. A reactive dye for printing and dyeing polyazo cotton fabrics, characterized in that, The specific structural formula of the dye is as follows:

8. The reactive dye for printing and dyeing polyazo cotton fabrics according to claim 7, characterized in that, Its preparation method includes the following steps: (1) After uniformly slurrying the aqueous solution of 4-ethyl sulfone aniline at 0-5℃, concentrated hydrochloric acid was added, and sodium nitrite aqueous solution was slowly added dropwise to carry out the diazotization reaction; after the reaction was completed, a small amount of aminosulfonic acid was added to eliminate excess sodium nitrite to obtain the diazonium salt. (2) Add the diazo salt from step (1) to a portion of an aqueous solution of H acid to carry out a coupling reaction to obtain a coupling product system. (3) The coupling product system obtained in step (2) is added to a uniformly slurried cyanuric chloride suspension for condensation reaction to obtain a condensate. (4) Add 2,4-diaminobenzenesulfonic acid to the first condensate obtained in step (3) to carry out a condensation reaction to obtain the second condensate; (5) Prepare diazonium salt according to the process in step (1); (6) The diazonium salt obtained in step (5) is added to the diazonium solution obtained in step (4) for coupling reaction, salting out, filtering, and drying to obtain a reactive dye for cotton fabric printing and dyeing based on H acid polyazo.

9. A printing paste formula, characterized in that, It contains the reactive dyes for printing and dyeing polyazo cotton fabrics as described in any one of claims 1-8.

10. The application of the reactive dyes for printing and dyeing polyazo cotton fabrics as described in any one of claims 1-8 in fabric dyeing.

11. The application of the reactive dyes for printing and dyeing polyazo cotton fabrics as described in any one of claims 1-8 in the preparation of dyed cotton fabrics.

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