Reactive brown dye as well as preparation method and application thereof
By introducing active brown dyes with dual active groups and spray drying technology, the problems of poor lifting power and insufficient blackness of active black KN-B dyes are solved, and high solubility, uniform dyeing and high color fixation rate are achieved, reducing production costs and reducing environmental pollution.
Patent Information
- Application Number
- CN202510326384.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-19
- Publication Date
- 2025-07-08
AI Technical Summary
The existing active black KN-B dyes have defects such as poor lifting power and insufficient blackness, which limits their widespread use, and direct dyes and sulfurized dyes are restricted due to environmental protection issues.
A reactive brown dye is used to improve the reactive activity and solubility of the dye by introducing bireactive groups and hydrophilic groups. Spray drying technology is used to replace salting drying, reducing environmental pollution, and achieving high color fixation rate and dyeing fastness.
It improves the solubility, uniformity and color fixation rate of dyes, improves the dyeing effect, reduces production costs, and reduces environmental pollution.
Smart Images
Figure CN120272029A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of fine chemicals, and particularly relates to an active brown dye, a preparation method thereof, and applications in dyeing and printing of wool, nylon, and cotton fibers. Background Art
[0002] With the increasing application rate of reactive dyes, the market demand is growing, and the market requirements for reactive dyes are also increasing. In cotton fiber dyeing, black dyeing accounts for almost 40%-50%. Direct dyes and sulfur dyes, which are used more frequently, have been prohibited and restricted due to environmental protection issues. Reactive Black KN-B (C.I. Reactive Black 5) has a large consumption because of its low price, good fastness, high fixation rate, and easy washability, and there are no environmental protection issues including AOX. However, Reactive Black KN-B has defects such as poor build-up property and insufficient blackness, which limit its wide use.
[0003] In recent years, compounded reactive dyes have received increasing attention. Dyes with different reactive groups are mixed (including different dye matrices), which play a complementary role, and reactive dyes with similar structures are mixed, which play a synergistic effect. Summary of the Invention
[0004] Based on the existing technology, the purpose of the present invention is to provide an active brown dye with high solubility, fixation rate, color fastness, high stability after dyeing, bright color shade, which can be widely applied to the dip dyeing, pad dyeing, and inkjet printing of cotton, linen, and rayon fiber fabrics, can solve the defects such as poor build-up property and insufficient blackness, and has low production cost and can be widely promoted and applied.
[0005] Another purpose of the present invention is to provide a preparation method of the above-mentioned active brown dye.
[0006] The third purpose of the present invention is to provide the application of the above-mentioned active brown dye in the printing and dyeing of fiber fabrics.
[0007] The technical solution of the present invention is as follows:
[0008] An active brown dye represented by formula (I),
[0009]
[0010] Wherein,
[0011] A represents H or
[0012] A1 represents phenyl or naphthyl; R1 or R2 each independently represents H, -SO3M, -NHCH2SO3M, SO2C2H4OSO3M or SO2C2H4OH;
[0013] B represents H or
[0014] B2 represents phenyl or naphthyl; R3 and R4 each independently represent H, -COOH, OH, C1-C4 alkyl, C1-C4 alkoxy, -SO3M, -NHCH2SO3M, SO2C2H4OSO3M, SO2C2H4OH, -NHC2H4OC2H4OH or -NHCONH2;
[0015] C represents H or
[0016] C3 represents phenyl or naphthyl; R5 or R6 each independently represent H, C1-C4 alkyl, C1-C4 alkoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH;
[0017] and at most one of A, B and C represents H;
[0018] M is H or an alkali metal ion.
[0019] In a preferred embodiment, R1 represents H, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0020] In a preferred embodiment, R2 represents H, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0021] In a preferred embodiment, R3 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0022] In a more preferred embodiment, R3 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0023] In a preferred embodiment, R4 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0024] In a more preferred embodiment, R4 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M.
[0025] In a preferred embodiment, R5 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0026] In a more preferred embodiment, R5 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0027] In a preferred embodiment, R6 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH
[0028] In a more preferred embodiment, R6 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
[0029] In a preferred embodiment, M is H, Na or K, preferably, M is Na.
[0030] For the present invention, the reactive brown dye represented by Formula I can be selected from the following compounds:
[0031]
[0032]
[0033]
[0034]
[0035] The present invention also provides a method for preparing the reactive brown dye represented by Formula (I). When A, B and C do not all represent H, the synthetic route is as follows:
[0036]
[0037] Adopting the technical solution of the present invention, the advantages are as follows:
[0038] (1) Due to the presence of its water-soluble groups, the reactive brown dye of the present invention has high solubility, which can reach 250 g / L.
[0039] (2) Due to the high solubility and high levelness of the reactive brown dye of the present invention, the dyed color is full, and the build-up and depth of dyeing are further improved.
[0040] (3) The present invention introduces a double reactive group into the structure of the reactive brown dye, improving the reaction activity of the dye. Further, more hydrophilic groups are introduced to improve the levelness and fixation rate of the reactive dye. When dyeing fiber materials, less amount is used, and the unfixed dye is easier to wash off.
[0041] (4) The drying method is optimized. Direct spray drying is used to replace the original salting-out and filter cake drying methods. There is no sewage discharge, and the dried product obtained by drying can be directly packaged, avoiding environmental pollution and saving production costs.
[0042] (5) The reactive brown dye provided by the present invention reacts with wool, nylon, and cotton fibers by covalent bonding. The covalent bond is quite strong, making the dye have high dyeing fastness. Detailed implementation mode
[0043] The present invention can be better understood according to the following embodiments. However, those skilled in the art can easily understand that the content described in the embodiments is only used to illustrate the present invention and should not and will not limit the present invention described in detail in the claims.
[0044] Example 1
[0045] (1) Dissolution of m-phenylenediamine: In a 150 ml beaker, add 10 parts of water and 11 parts of m-phenylenediamine and make a slurry for 20 min. Under the condition of heating to 20 - 25°C, slowly add 3 parts of 30% hydrochloric acid by mass concentration, and while stirring, make m-phenylenediamine dissolve clearly. Adjust its pH = 4 - 7 and wait for coupling.
[0046] (2) First diazotization reaction: In a 1000 ml beaker, add 300 parts of ice water and 101 parts of compound A1, and make a slurry by ice grinding for 1 hour. Add 10 parts of 30% hydrochloric acid by mass concentration, stir for 10 min, and then slowly add 14 parts of sodium nitrite to form a diazonium salt. During the diazotization process, use Congo red test paper to measure the acidity and show dark blue. If it does not show dark blue, add hydrochloric acid. Use starch potassium iodide test paper to measure sodium nitrite and show slightly blue. Under the condition of 0 - 20°C, continue to react for 1 h, and then use sulfamic acid to eliminate the slightly excessive sodium nitrite.
[0047] (3) First coupling reaction: Under the condition of 5 - 10°C, quickly add the m-phenylenediamine solution obtained in step (1) to the first diazonium salt solution obtained in step (2), react for 2 - 4 hours, and use alkaline H acid solution to detect whether the diazonium salt has completely reacted, while maintaining the temperature at 5 - 15°C throughout the reaction process. After the diazonium salt disappears, adjust the pH to 5 - 8 using sodium bicarbonate.
[0048] (4) Second diazotization reaction: In a 250 ml beaker, add 100 parts of ice water and 20.7 parts of compound C1, and make a slurry by ice grinding for 1 hour. Add 13 parts of 30% hydrochloric acid by mass concentration, stir for 10 min, and then slowly add 7 parts of sodium nitrite to form a diazonium salt. During the diazotization process, use Congo red test paper to measure the acidity and show dark blue. If it does not show dark blue, add hydrochloric acid. Use starch potassium iodide test paper to measure sodium nitrite and show slightly blue. Under the condition of 0 - 10°C, continue to react for 1 h, and then use sulfamic acid to eliminate the slightly excessive sodium nitrite.
[0049] (5) Secondary coupling reaction: Under the condition of 5 - 20 °C, quickly add the secondary diazonium salt solution obtained in step (4) to the primary coupling product obtained in step (3), adjust the pH value to 5 - 8 with sodium bicarbonate, react for 2 - 4 hours, and use an alkaline H-acid solution to detect whether the diazonium salt has completely reacted, while maintaining the temperature at 5 - 15 °C throughout the reaction process. When the diazonium salt disappears, spray dry to obtain the dye product shown in formula 1. The structural formulas of related compounds are as follows:
[0050]
[0051] Among them, the mass spectrometry data of compound 1 are as follows: MS(EI, m / z): 1175.94 [M - H] - 。
[0052] Example 2
[0053] Referring to Example 1, 11 parts of m-phenylenediamine as the coupling component remain unchanged, 20.7 parts of compound C1 are used as the primary diazo component for the primary coupling, and the reaction conditions are the same as those in Example 1 for the primary coupling; 101 parts of compound A1 are used as the secondary diazo component for the secondary coupling, and the reaction conditions remain unchanged. When the diazonium salt disappears, spray dry to obtain the dye product shown in formula 2. The structural formulas of related compounds are as follows:
[0054]
[0055] Among them, the mass spectrometry data of compound 2 are as follows: MS(EI, m / z): 1175.91 [M - H] - 。
[0056] Example 3
[0057] Referring to Example 1, 11 parts of m-phenylenediamine as the coupling component remain unchanged, 58.6 parts of compound A1 are used as the primary diazo component for the primary coupling, and the reaction conditions are the same as those in Example 1 for the primary coupling; the secondary diazo component remains unchanged, and 20.7 parts of compound C1 are used as the secondary diazo component for the secondary coupling. The coupling reaction conditions remain unchanged. When the diazonium salt disappears, spray dry to obtain the dye product shown in formula 3. The structural formulas of related compounds are as follows:
[0058]
[0059] Among them, the mass spectrometry data of compound 3 are as follows: MS(EI, m / z): 971.86 [M - H] - 。
[0060] Example 4
[0061] Referring to Example 1, 11 parts of m-phenylenediamine as the coupling component remain unchanged.
[0062] (1) Dissolution of m-phenylenediamine: In a 150 ml beaker, add 10 parts of water and 11 parts of m-phenylenediamine, and slurry for 20 min. Under the condition of heating to 20 - 25 °C, slowly add 3 parts of 30% hydrochloric acid by mass concentration. While stirring, dissolve m-phenylenediamine until clear, adjust its pH = 4 - 7, and wait for coupling.
[0063] (2) First diazotization reaction: Use 19 parts of compound A4 as the first diazo component, add 100 parts of ice water, slurry with ice grinding for 1 hour, add 13 parts of 30% hydrochloric acid by mass concentration, stir for 10 min, slowly add 7 parts of sodium nitrite to form a diazonium salt. During the diazotization process, use Congo red test paper to measure the acidity and show dark blue. If it does not show dark blue, add hydrochloric acid. Use starch potassium iodide test paper to measure sodium nitrite and show slightly blue. Under the condition of 0 - 10 °C, continue the reaction for 1 h, and then use sulfamic acid to eliminate the slightly excessive sodium nitrite.
[0064] (3) First coupling reaction: Under the condition of 5 - 10 °C, quickly add the m-phenylenediamine solution obtained in step (1) to the first diazonium salt solution obtained in step (2), react for 2 - 4 hours, use an alkaline H-acid solution to detect whether the diazonium salt has completely reacted, and at the same time keep the temperature at 5 - 15 °C throughout the reaction process. After the diazonium salt disappears, obtain the first coupling product.
[0065] (4) Second diazotization reaction: In a 1000 ml beaker, add 300 parts of ice water and 29.3 parts of compound A3, slurry with ice grinding for 1 hour, add 10 parts of 30% hydrochloric acid by mass concentration, stir for 10 min, then slowly add 14 parts of sodium nitrite to form a diazonium salt. During the diazotization process, use Congo red test paper to measure the acidity and show dark blue. If it does not show dark blue, add hydrochloric acid. Use starch potassium iodide test paper to measure sodium nitrite and show slightly blue. Under the condition of 0 - 20 °C, continue the reaction for 1 h, and then use sulfamic acid to eliminate the slightly excessive sodium nitrite.
[0066] (5) Second coupling reaction: Under the condition of 5 - 20 °C, quickly add the second diazonium salt solution obtained in step (4) to the first coupling product obtained in step (3), adjust the pH value to 5 - 8 with sodium bicarbonate, react for 2 - 4 hours, use an alkaline H-acid solution to detect whether the diazonium salt has completely reacted, and at the same time keep the temperature at 5 - 15 °C throughout the reaction process. After the diazonium salt disappears, obtain the second coupling product.
[0067] (6) Third diazotization reaction: Use 50.5 parts of compound A1 as the third diazo component, add 150 parts of ice water, slurry with ice grinding for 1 hour, add 10 parts of 30% hydrochloric acid by mass concentration, stir for 10 min, slowly add 7 parts of sodium nitrite to form a diazonium salt. During the diazotization process, use Congo red test paper to measure the acidity and show dark blue. If it does not show dark blue, add hydrochloric acid. Use starch potassium iodide test paper to measure sodium nitrite and show slightly blue. Under the condition of 0 - 20 °C, continue the reaction for 1 h, and then use sulfamic acid to eliminate the slightly excessive sodium nitrite.
[0068] (7) Primary coupling reaction: Under the condition of 5 - 20 °C, quickly add the tertiary diazonium salt solution obtained in step (6) to the secondary coupling product obtained in step (5), adjust the pH value to 5 - 8 with sodium bicarbonate, react for 2 - 4 hours, and use an alkaline H-acid solution to detect whether the diazonium salt has completely reacted, while maintaining the temperature at 5 - 15 °C throughout the reaction process. When the diazonium salt disappears, spray drying gives the dye product shown in Formula 4. The structural formulas of the related compounds are as follows:
[0069]
[0070] Among them, the mass spectrometry data of Compound 4 are as follows: MS(EI, m / z): 1056.97[M - H] - 。
[0071] Example 5
[0072] Same as Example 4, 11 parts of m-phenylenediamine as the coupling component remain unchanged, 19 parts of Compound A4 are used as the primary diazo component, 50.5 parts of Compound A1 are used as the secondary diazo component, 29.3 parts of Compound A3 are used as the tertiary diazo component, the reaction conditions remain unchanged, the diazonium salt disappears, and after standardization processing, spray drying gives the dye product shown in Formula 5. The structural formulas of the related compounds are as follows:
[0073]
[0074] Among them, the mass spectrometry data of Compound 5 are as follows: MS(EI, m / z): 1056.97[M - H] - 。
[0075] Example 6
[0076] Same as Example 1, 11 parts of m-phenylenediamine as the coupling component remain unchanged, 19 parts of Compound A4 are used as the primary diazo component, 101 parts of Compound A1 are used as the secondary diazo component, the reaction conditions remain unchanged, the diazonium salt disappears, and spray drying gives
[0077] the dye product shown in Formula 6. The structural formulas of the related compounds are as follows:
[0078]
[0079] Among them, the mass spectrometry data of Compound 6 are as follows: MS(EI, m / z): 1158.86[M - H] - 。
[0080] Example 7
[0081] Same as Example 4, 11 parts of m-phenylenediamine as the coupling component remain unchanged. 50.5 parts of Compound A1 are used as the primary diazo component, 29.3 parts of Compound A3 are used as the secondary diazo component, and 19 parts of Compound A4 are used as the tertiary diazo component. The reaction conditions remain unchanged. The diazonium salt disappears, and the dye product shown in Formula 7 is obtained by spray drying. The structural formulas of the related compounds are as follows:
[0082]
[0083] Among them, the mass spectrometry data of Compound 7 are as follows: MS(EI, m / z): 1056.95[M-H] - 。
[0084] Example 8
[0085] Same as Example 1, 11 parts of m-phenylenediamine as the coupling component remain unchanged. 101 parts of Compound A1 are used as the primary diazo component, and 19 parts of Compound A4 are used as the secondary diazo component. The reaction conditions remain unchanged. The diazonium salt disappears, and the dye product shown in Formula 7 is obtained by spray drying. The structural formulas of the related compounds are as follows:
[0086]
[0087] Among them, the mass spectrometry data of Compound 8 are as follows: MS(EI, m / z): 1157.85[M-H] - 。
[0088] Example 9
[0089] Same as Example 1, 11 parts of m-phenylenediamine as the coupling component remain unchanged. 38 parts of Compound A5 are used as the primary diazo component, and hydrochloric acid is not added during diazotization. Other reaction conditions remain unchanged. 101 parts of Compound A1 are used as the secondary diazo component. The reaction conditions remain unchanged. The diazonium salt disappears, and the dye product shown in Formula 9 is obtained by spray drying. The structural formulas of the related compounds are as follows:
[0090]
[0091] Among them, the mass spectrometry data of Compound 9 are as follows: MS(EI, m / z): 1296.83[M-H] - 。
[0092] Example 10
[0093] Same as Example 9, 11 parts of m-phenylenediamine as the coupling component remain unchanged. 101 parts of Compound A1 are used as the primary diazo component. The reaction conditions remain unchanged. 38 parts of Compound A5 are used as the secondary diazo component, and hydrochloric acid is not added during diazotization. Other reaction conditions remain unchanged. The diazonium salt disappears, and the dye product shown in Formula 10 is obtained by spray drying. The structural formulas of the related compounds are as follows:
[0094]
[0095]
[0096] Among them, the mass spectrometry data of compound 10 are as follows: MS (EI, m / z): 1296.85 [M-H] - .
[0097] Example 11
[0098] Referring to Example 1, 11 parts of m-phenylenediamine as the coupling component remained unchanged, and 101 parts of compound A1 were used as the primary diazo component. The first coupling was carried out under the same reaction conditions as in Example 1. The reaction was carried out until the diazonium salt disappeared, and the resulting dye product of formula 11 was obtained by spray drying. The structural formulas of the related compounds are as follows:
[0099]
[0100] Among them, the mass spectrometry data of compound 11 are as follows: MS (EI, m / z): 939.672 [M-H] - .
[0101] Example 12
[0102] Same as Example 1, 11 parts of m-phenylenediamine as the coupling component remained unchanged. 19 parts of compound A4 were used as the primary diazo component, and 50.5 parts of compound A1 were used as the secondary diazo component. The reaction conditions remained unchanged. After the diazonium salt disappeared, spray drying gave
[0103] the dye product of formula 12. The structural formulas of the related compounds are as follows:
[0104]
[0105] Among them, the mass spectrometry data of compound 12 are as follows: MS (EI, m / z): 743.61 [M-H] - .
[0106] Comparative Example 1
[0107]
[0108] Comparative Example 2
[0109]
[0110] Dyeing test description:
[0111] Weigh 1 g of the dyes prepared in the examples, Comparative Example 1, and Comparative Example 2. First, dissolve them thoroughly with an appropriate amount of water, and then make up the volume to 250 ml in a volumetric flask. Pipette 50 ml of the dye solution and mix it with 50 ml of water. Then add 5 g of cotton cloth and 6 g of sodium sulfate. Then, heat it at a rate of 10 °C / min to 60 °C. After maintaining for 30 minutes, add 2 g of sodium carbonate, and then keep dyeing at 60 °C for 30 minutes. Subsequently, take out the dyed cotton cloth, boil it with a non-ionic detergent at boiling point for 15 minutes, then wash it with water and dry it at about 70 °C. Test the performance of the samples in the examples and comparative examples according to the unified national dye inspection standards respectively. The results are shown in Table 1.
[0112] Table 1 Dyeing test results of the performance of the examples and comparative examples
[0113]
[0114] The performance inspection methods of the examples and comparative examples are carried out in accordance with the unified national dye inspection standards, which are specifically as follows.
[0115]
[0116]
[0117] It can be seen from the printing and dyeing test results in Table 1 that the inkjet printing reactive brown dyes disclosed in the examples of the present invention perform well in terms of rubbing fastness, light fastness, washing fastness, solubility, alkali resistance stability, and fixation rate, especially in terms of solubility and fixation rate.
[0118] Compared with the dyes disclosed in Comparative Example 1 and Comparative Example 2, the inkjet printing reactive brown dyes disclosed in the present invention have better performance in terms of rubbing fastness, light fastness, washing fastness, solubility, alkali resistance stability, and fixation rate.
[0119] The above examples are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that it is still possible to modify the technical solutions described in the foregoing examples, or to equivalently replace some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the examples of the present invention.
Claims
1. An active brown dye represented by the formula (I), wherein, A represents H or A1 represents phenyl or naphthyl; R1 or R2 each independently represents H, -SO3M, -NHCH2SO3M, SO2C2H4OSO3M or SO2C2H4OH; B represents H or B2 represents phenyl or naphthyl; R3 and R4 each independently represents H, -COOH, OH, C1-C4 alkyl, C1-C4 alkoxy, -SO3M, -NHCH2SO3M, SO2C2H4OSO3M, SO2C2H4OH, -NHC2H4OC2H4OH or -NHCONH2; C represents H or C3 represents phenyl or naphthyl; R5 or R6 each independently represents H, C1-C4 alkyl, C1-C4 alkoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH; and at most one of A, B and C represents H; M is H or an alkali metal ion.
2. The reactive brown dye according to claim 1, characterized in that, R1 represents H, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH; R2 represents H, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
3. The reactive brown dye according to claim 1, characterized in that, R3 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH, preferably, R3 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
4. The reactive brown dye according to claim 1, characterized in that, R4 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH; preferably, R4 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
5. The reactive brown dye according to claim 1, characterized in that, R5 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH, preferably, R5 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH.
6. The reactive brown dye according to claim 1, characterized in that, R6 represents H, methyl, methoxy, ethyl, ethoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH; preferably, R6 represents H, methyl, methoxy, -SO3M, -SO2C2H4OSO3M or SO2C2H4OH; M is H, Na or K, preferably, M represents Na.
7. The reactive brown dye according to claim 1, characterized in that, The dye is selected from the following compounds:
8. A method for preparing the reactive brown dye according to claim 1, characterized in that, When none of A, B and C represents H, the synthesis route is as follows:
9. A dye composition, which uses the active brown dye according to any one of claims 1 to 7 as an active component, supplemented with auxiliaries in the dye field, and the auxiliaries are one or more of a dust-proof agent, a filler, and sodium sulfate.
10. The application of the active brown dye according to any one of claims 1 to 7 in the printing and dyeing of fiber fabrics; especially in the dip dyeing, pad dyeing or inkjet printing of cotton, linen or rayon fibers.