Multipurpose high-performance functional environment-friendly reactive brilliant blue dye and preparation method thereof

Abstract

The invention provides a multipurpose high-performance functional environment-friendly reactive brilliant blue dye and a preparation method thereof, and solves the common use defects of low solubility, poor saline-alkaline resistance, poor leveling property and reproducibility and low fixation rate improvement of the existing reactive brilliant blue dye, and the existing reactive brilliant blue dye is difficult to be suitable for low-salt and small-bath-ratio dyeing and low-urea printing. The dye composition has the advantages that the dye composition can be widely applied to dip dyeing, pad dyeing and ink-jet printing of cotton, hemp, cellulosic fiber, protein fiber or artificial cotton fiber fabrics, the problems of poor color defect, staining, washing fastness and wet treatment fastness and the like after dyeing are easily caused, and the dye composition has higher solubility, good fixation rate, saline-alkaline resistance stability and color fastness, high stability after dyeing and bright color and light, and can be widely applied to the dip dyeing, pad dyeing and ink-jet printing of the cotton, hemp, cellulosic fiber, protein fiber or artificial cotton fiber fabrics; the production cost is low, and large-scale popularization and application can be realized.

Description

Technical Field

[0001] The invention belongs to the field of fine chemicals, and specifically relates to a multi-purpose high-performance functional environmentally friendly reactive brilliant blue dye and a preparation method thereof, and their application in fiber fabric printing and dyeing; in particular, in dip dyeing, pad dyeing or inkjet printing of cotton, linen, cellulose fiber, protein fiber or artificial cotton fiber. Background Art

[0002] Reactive brilliant blue is one of the important chromatographic dyes of reactive dyes. It can be used for single color and color matching. It has bright colors, excellent fastness, simple dyeing process and wide application. It is an important chromatographic dye for cellulose fiber dyeing and printing.

[0003] The mainstream reactive brilliant blue variety on the current market is CI Reactive Blue 19, which is mainly used for dyeing cotton and viscose fibers. It has high affinity and excellent levelness, and its fixation rate is generally around 70%. Dyeing is sensitive to electrolytes, has poor salt-alkali resistance, and is prone to color fringing. It is difficult to apply to low-salt, small bath ratio dyeing, and low-urea printing. It is especially suitable for cold pad-batch dyeing and preparation of digital inkjet printing.

[0004] In view of the excellent properties and defects of reactive brilliant blue, it is necessary to develop more varieties of reactive brilliant blue, and to fundamentally solve the problems of color spots, difficulty in applying to low salt, small bath ratio dyeing, low urea printing, and multi-purpose high-performance functional types by improving or finding new structures, so that it can be applied to more types of materials and provide a wider range of applications. Summary of the invention

[0005] The purpose of the present invention is to provide a multi-purpose high-performance functional environmentally friendly reactive brilliant blue dye on the basis of the prior art. The dye has high solubility, good color fixation rate, salt and alkali stability, color fastness, high stability after dyeing, bright color, can be widely used in dip dyeing, pad dyeing and inkjet printing of cotton, linen, cellulose fiber, protein fiber or artificial cotton fiber fabrics, and has low production cost and can be widely promoted and applied on a large scale.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned reactive brilliant blue dye.

[0007] A third object of the present invention is to provide the application of the above-mentioned reactive brilliant blue dye in fiber fabric printing and dyeing, particularly in the application of cotton, linen, cellulose fiber, protein fiber or artificial cotton fiber in dyeing, pad dyeing or ink-jet printing.

[0008] The technical solution of the present invention is as follows:

[0009] The reactive brilliant blue dye shown in formula I,

[0010]

[0011] in,

[0012] Ring A represents phenyl or naphthyl;

[0013] R1 represents SO2CH2CH2OSO3M or SO2CH2CH2;

[0014] R2 represents H, SO3M, C1-C4 alkyl or C1-C4 alkoxy;

[0015] M represents H, Na or K.

[0016] For the present invention, in a preferred embodiment, R2 represents H, SO3Na, methyl, ethylmethoxy or ethoxy.

[0017] In a more preferred embodiment, R2 represents H, SO3Na or methoxy.

[0018] In a more preferred embodiment, M represents Na or K; in a more preferred embodiment, M represents Na.

[0019] For the present invention, the reactive brilliant blue dye shown in Formula I can be selected from the following compounds, but is not limited to one of the following compounds:

[0020]

[0021]

[0022] The present invention also provides a method for preparing the reactive brilliant blue dye shown in formula I, and the synthesis route is as follows: 1) When R1 represents SO2CH2CH2OSO3M, the synthesis route is as follows:

[0023]

[0024] 2) When R1 represents SO2CH2CH2, its synthesis route is as follows:

[0025]

[0026] Here, M represents Na or K.

[0027] In a preferred embodiment, the method for preparing the reactive brilliant blue dye shown in the above formula I comprises the following steps:

[0028] 1) When R1 represents SO2CH2CH2OSO3M, it comprises the following steps: dissolving bromoamic acid in water, adding compound a, copper powder and cuprous chloride in an alkaline solution and mixing them evenly, adjusting the pH value to 8.0-8.5, carrying out condensation reaction at a temperature of 65-75°C to obtain a dye product solution, and drying to obtain a reactive brilliant blue dye shown in formula I;

[0029] 2) When R1 represents SO2CH2CH2, it comprises the following steps: adding an alkaline solution to the finished dye solution obtained in step 1) to adjust its pH value to 8.5-9.5, carrying out a hydrolysis reaction at a temperature of 20-30°C, and drying the obtained reaction solution to obtain a reactive brilliant blue dye shown in formula I.

[0030] The present invention can use appropriate acid, alkali or salt (such as hydrochloric acid, soda ash) to adjust the pH value of the solution as needed. In a preferred embodiment, in step 1), the alkaline solution is sodium hydroxide solution, sodium bicarbonate solution, potassium hydroxide solution or potassium bicarbonate solution.

[0031] In a preferred embodiment, in step 1), the reaction temperature is 70-72°C.

[0032] In a preferred embodiment, in step 1), the molar ratio of bromoamic acid to compound a is 1:1.1-1.5, more preferably 1:1.2.

[0033] For the present invention, in step 2), the reaction temperature is 25°C.

[0034] In step 2), the pH value is adjusted to 8.8-9.2, preferably 9.0.

[0035] A dye composition, which uses the above-mentioned active red brilliant blue as an active component and is supplemented with auxiliary agents in the field of dyes. The finished dye product made of the active brilliant blue dye of the present invention can exist in the form of solid particles, powder or solution. The active component can include only one of the above-mentioned active brilliant blue dyes, or can include two or more active brilliant blue dyes. The auxiliary agents in the field of dyes include but are not limited to common cosolvents in commercial dyes, alkali-resistant agent FSN, dust-proof agents (such as polyoxyethylene ether oleate mixtures), fillers, sodium sulfate, stabilizers or electrolyte salts, etc., wherein the electrolyte salts are such as sodium chloride, potassium chloride, sodium sulfate or potassium sulfate.

[0036] The reactive brilliant blue dye disclosed by the invention can be applied to the printing and dyeing of fiber fabrics, especially to the dip dyeing, pad dyeing or inkjet printing of cotton, linen, cellulose fiber, protein fiber or artificial cotton fiber.

[0037] Adopt the technical scheme of the present invention, the advantages are as follows:

[0038] The invention provides a multi-purpose high-performance functional environmentally friendly reactive brilliant blue dye, which solves the common use defects of the existing reactive brilliant blue dye, namely, low solubility, poor salt and alkali resistance, poor level dyeing and reproducibility, low fixation rate improvement, difficulty in being applicable to low-salt, small bath ratio dyeing and low urea printing, easy occurrence of color flakes, staining, poor washing fastness and wet treatment fastness after dyeing, etc. The multi-purpose high-performance functional environmentally friendly reactive brilliant blue dye has high solubility, good fixation rate, salt and alkali resistance stability, color fastness, high stability after dyeing, bright color, can be widely used in dip dyeing, pad dyeing and inkjet printing of cotton, linen, cellulose fiber, protein fiber or artificial cotton fiber fabrics, has low production cost, and can be widely promoted and applied on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is the liquid chromatogram of the alkali-resistant agent FSN. DETAILED DESCRIPTION

[0040] The reactive brilliant blue dye of the present invention is further described by the following examples, but these examples do not constitute any limitation to the present invention.

[0041] Example 1

[0042] 0.1 mol of bromoamic acid and water were added to a reaction flask, heated to 80-90°C, stirred until fully dissolved, and then 0.12 mol of compound a1, copper powder and sodium bicarbonate solution were added. After stirring evenly, the pH value was adjusted to 8.0-8.5, and a cuprous chloride aqueous solution was added dropwise. A condensation reaction was carried out at a temperature of 70-72°C to obtain a dye product solution, which was dried to obtain a reactive brilliant blue dye shown in Formula 1. The synthetic route is as follows:

[0043]

[0044] Among them, the mass spectrum data of compound 1 is as follows: MS (EI, m / z): 652.98 [MH] - .

[0045] Example 2

[0046] Referring to the preparation method in Example 1, sodium hydroxide solution was added to the obtained dye product solution to adjust its pH value to 9.0, and a hydrolysis reaction was carried out at a temperature of 25° C. The obtained reaction solution was dried to obtain a reactive brilliant blue dye shown in Formula 6. The synthesis route thereof is as follows:

[0047]

[0048] Among them, the mass spectrum data of compound 6 is as follows: MS (EI, m / z): 534.03 [MH] - .

[0049] Example 3

[0050] Referring to the preparation method in Example 1, compound a1 is replaced by compound a2 to obtain a reactive brilliant blue dye shown in formula 2. The synthetic route is as follows:

[0051]

[0052] Among them, the mass spectrum data of compound 2 is as follows: MS (EI, m / z): 652.97 [MH] - .

[0053] Example 4

[0054] Referring to the preparation method in Example 3, sodium hydroxide solution was added to the obtained dye product solution to adjust its pH value to 9.0, and a hydrolysis reaction was carried out at a temperature of 25° C. The obtained reaction solution was dried to obtain a reactive brilliant blue dye shown in Formula 7. The synthetic route thereof is as follows:

[0055]

[0056] Among them, the mass spectrum data of compound 7 is as follows: MS (EI, m / z): 534.01 [MH] - .

[0057] Example 5

[0058] Referring to the preparation method in Example 1, compound a1 is replaced by compound a3 to obtain a reactive brilliant blue dye shown in formula 3. The synthetic route is as follows:

[0059]

[0060] Among them, the mass spectrum data of compound 3 is as follows: MS (EI, m / z): 754.90 [MH] - .

[0061] Example 6

[0062] Referring to the preparation method in Example 5, sodium hydroxide solution was added to the obtained dye product solution to adjust its pH value to 9.0, and a hydrolysis reaction was carried out at a temperature of 25° C. The obtained reaction solution was dried to obtain a reactive brilliant blue dye shown in Formula 8. The synthesis route thereof is as follows:

[0063]

[0064] Among them, the mass spectrum data of compound 8 is as follows: MS (EI, m / z): 635.96 [MH] - .

[0065] Example 7

[0066] Referring to the preparation method in Example 1, compound a1 is replaced by compound a4 to obtain a reactive brilliant blue dye shown in formula 4. The synthetic route is as follows:

[0067]

[0068] Among them, the mass spectrum data of compound 4 is as follows: MS (EI, m / z): 682.97 [MH] - .

[0069] Example 8

[0070] Referring to the preparation method in Example 7, sodium hydroxide solution was added to the obtained dye product solution to adjust its pH value to 9.0, and a hydrolysis reaction was carried out at a temperature of 25° C. The obtained reaction solution was dried to obtain a reactive brilliant blue dye shown in Formula 9. The synthetic route thereof is as follows:

[0071]

[0072] Among them, the mass spectrum data of compound 9 is as follows: MS (EI, m / z): 564.05 [MH] - .

[0073] Example 9

[0074] Referring to the preparation method in Example 1, compound a1 is replaced by compound a5 to obtain a reactive brilliant blue dye shown in formula 5. The synthetic route is as follows:

[0075]

[0076] Among them, the mass spectrum data of compound 5 are as follows: MS (EI, m / z): 820.97 [MH] - .

[0077] Example 10

[0078] Referring to the preparation method in Example 9, sodium hydroxide solution was added to the obtained dye product solution to adjust its pH value to 9.0, and a hydrolysis reaction was carried out at a temperature of 25° C. The obtained reaction solution was dried to obtain a reactive brilliant blue dye shown in Formula 9. The synthetic route thereof is as follows:

[0079]

[0080] Among them, the mass spectrum data of compound 10 is as follows: MS (EI, m / z): 685.99 [MH] - .

[0081] Printing and dyeing experiment description

[0082] According to the solubility of water-soluble dyes in GB / T 3671.1-1996, the salt and alkali stability in GB / T 29597-2013, the color fixation rate in GB / T 2391, the washing fastness in GB / T3921-2008, and the light fastness in GB / T8427-2008, the reactive brilliant blue dyes 1-10 prepared in Examples 1-10, and the dyes 1-10 respectively added with 10% of the alkali resistance agent FSN and the commercially available dye CI reactive blue 19 were tested for dyeing performance, and the results are shown in Table 1.

[0083] Table 1 Printing and dyeing test results

[0084]

[0085]

[0086] It can be seen from the printing and dyeing test results in Table 1 that the inkjet printing reactive brilliant blue dyes 1-10 disclosed in Examples 1 to 10 of the present invention have good performance in terms of light fastness, washing fastness, solubility, salt-alkali stability, and color fixation rate, especially in terms of solubility and color fixation rate, which are significantly better than the commercially available dye CI reactive blue 19, and can be used in fiber fabric printing and dyeing, especially in cotton, linen, cellulose fiber, protein fiber or artificial cotton fiber dip dyeing, pad dyeing or inkjet printing. The inkjet printing reactive brilliant blue dyes 1-10 disclosed in the present invention can significantly improve solubility, salt-alkali stability and color fixation rate when 10% of the alkali resistance agent FSN is added.

[0087] The synthetic route of the alkali-resistant agent FSN mentioned in the present invention is as follows:

[0088]

[0089] The preparation method of alkali-resistant agent FSN comprises the following steps:

[0090] (1) Sulfonation reaction: Add 0.1 mol of methylnaphthalene and 0.1 mol of naphthalene to a reaction flask, mix well, heat to 110°C, dissolve the mixture completely, then heat to 130°C, dropwise add a sulfuric acid solution containing 0.28 mol of sulfuric acid, and after the addition is complete, heat to 160°C and keep warm for 3 hours. Sample the sulfonated product to measure the acidity of the end point to be 29-32%, then cool to 110°C.

[0091] (2) Hydrolysis reaction: After the sulfonation end point, water was added dropwise, and the temperature was raised to 120°C for reaction for 30 minutes. The acid value of the sample was 25-28%, and the temperature was lowered by 100°C.

[0092] (3) Condensation reaction: 0.12 mol of 37% formaldehyde solution was added dropwise to the reaction solution obtained in step (2), and the condensation reaction was carried out at a temperature of 105-110°C for 6 hours. After the reaction was completed, water was added and the temperature was lowered by 60°C.

[0093] (4) Neutralization reaction: add 0.18 mol of 30% sodium hydroxide solution to the reaction solution obtained in step (3), adjust the pH to 6.0-6.5 with calcium hydroxide solution, filter to remove impurities, and dry to obtain the alkali-resistant agent FSN. Its liquid chromatogram is as follows: Figure 1 As shown, the main peaks are located at 4.755 min and 6.023 min.

[0094] The above embodiments 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 aforementioned embodiments, a person skilled in the art should understand that it is still possible to modify the technical solutions described in the aforementioned embodiments, or to perform equivalent replacements on some of the technical features therein. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A reactive brilliant blue dye having formula I, in, Ring A represents phenyl or naphthyl; R 1 On behalf of SO 2 CH 2 CH 2 OSO 3 M or SO 2 CH 2 CH 2 ; R 2 Represents H, SO 3 M.C 1 -C 4 Alkyl or C 1 -C 4 Alkoxy; M represents H, Na or K.

2. The reactive brilliant blue dye according to claim 1, It is characterized in that R 2 Represents H, SO 3 Na, methyl, ethylmethoxy or ethoxy.

3. Reactive brilliant blue dye according to claim 2, It is characterized in that R 2 Represents H, SO 3 Na or methoxy.

4. Reactive brilliant blue dye according to claim 1, It is characterized in that M stands for Na.

5. The reactive brilliant blue dye according to claim 1, It is characterized in that The dye is selected from the following compounds:

6. A method for preparing the reactive brilliant blue dye according to claim 1, It is characterized in that The synthetic route is as follows: 1) When R 1 On behalf of SO 2 CH 2 CH 2 OSO 3 When M, its synthetic route is as follows: 2) When R 1 On behalf of SO 2 CH 2 CH 2 When, its synthetic route is as follows: Here, M represents Na or K.

7. The method for preparing the reactive brilliant blue dye according to claim 6, It is characterized in that It includes the following steps: 1) When R 1 On behalf of SO 2 CH 2 CH 2 OSO 3 M, it comprises the following steps: dissolving bromoamic acid in water, adding compound a, copper powder and cuprous chloride in an alkaline solution and mixing them evenly, adjusting the pH value to 8.0-8.5, carrying out a condensation reaction at a temperature of 65-75° C. to obtain a dye product solution, and drying to obtain a reactive brilliant blue dye shown in formula I; 2) When R 1 On behalf of SO 2 CH 2 CH 2 It comprises the following steps: adding an alkaline solution to the finished dye solution obtained in step 1) to adjust its pH value to 8.5-9.5, carrying out a hydrolysis reaction at a temperature of 20-30° C., and drying the obtained reaction solution to obtain a reactive brilliant blue dye as shown in formula I.

8. The method for preparing a reactive brilliant blue dye according to claim 7, It is characterized in that In step 1), the reaction temperature is 70-72°C, the alkaline solution is sodium hydroxide solution, sodium bicarbonate solution, potassium hydroxide solution or potassium bicarbonate solution; the molar ratio of bromoamic acid to compound a is 1:1.1-1.5, preferably 1:1.2; in step 2), the reaction temperature is 25°C; and the pH value is adjusted to 8.8-9.2, preferably 9.

0.

9. A dye composition, which uses the active brilliant blue dye described in any one of claims 1 to 5 as an active component and is supplemented with auxiliary agents in the field of dyes, wherein the auxiliary agents are one or more of alkali-resistant agent FSN, dust-proof agent, filler, and sodium sulfate.

10. Use of the reactive brilliant blue dye according to any one of claims 1 to 5 in dyeing and printing of fiber fabrics, in particular in exhaust dyeing, pad dyeing or inkjet printing of cotton, linen, cellulose fiber, protein fiber or rayon fiber.

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