Active dark blue dye with high fixation rate as well as preparation method and application thereof

Abstract

The invention provides a high-fixation-rate active navy blue dye, the structure of the high-fixation-rate active navy blue dye is as shown in formula I: # imgabs0 # imgabs1 #, in the formula I, R1 is selected from C1-C6 alkylene, R2 is selected from C1-C6 alkylidene, R3 is selected from C1-C6 alkylidene, R4 is selected from C1-C6 alkylidene, and R4 is selected from C1-C6 alkylidene; r2 and R3 are independently selected from halogens respectively; r4 and R5 are respectively and independently selected from-H,-SO3M,-CH3,-COOM and-CHO; m is Na, K or Li. The high-fixation-rate active dark blue dye is good in color fastness and high in fixation rate. The invention further provides a preparation method of the high-fixation-rate active dark blue dye and application of the high-fixation-rate active dark blue dye in textile dyeing.

Description

Technical Field

[0001] The present application relates to the technical field of reactive dyes, and in particular to a reactive navy blue dye with a high fixation rate and a preparation method and application thereof. Background Art

[0002] Reactive dyes, also known as reactive dyes, contain active groups that can react with hydroxyl groups in cellulose and amino groups in protein fibers. When dyeing, they form covalent bonds with fibers to form "dye-fiber" compounds. Reactive dyes have the characteristics of bright colors, good levelness, simple dyeing methods, high color fastness, complete color spectrum and low cost. They are mainly used in the dyeing and printing of fibers such as cotton, linen, viscose, silk and wool and their blended fabrics.

[0003] However, most of the reactive dyes currently used in China are based on single or double reactive groups of cyanuric chloride and para-ester or para-ester derivatives as the active groups of the dyes, and all of them have the disadvantages of low fixation rate and insufficient dyeing performance.

[0004] Therefore, it is necessary to provide a dye with a high fixation rate. Summary of the invention

[0005] In order to solve at least one of the above technical problems, the present invention provides a high fixation rate active navy blue dye and its preparation method and application. In order to increase the fixation rate of the dye, the inventors found that using multiple active groups and modifying the molecular structure is a very effective path. The fixation rate and various color fastness indicators of the dye can be well improved.

[0006] The present application provides a high-fixation rate active navy blue dye, the structure of which is shown in Formula I:

[0007]

[0008] Wherein, R1 is selected from C1-C6 alkylene; R2 and R3 are independently selected from halogen; R4 and R5 are independently selected from -H, -SO3M, -CH3, -COOM and -CHO; M is Na, K or Li.

[0009] Preferably, R1 is -C2H4-, -C3H6- or -C4H8-; R2 and R3 are both Cl.

[0010] Preferably, R4 and R5 are both -SO3M; M is Na.

[0011] Preferably, the high fixation rate active navy blue dye is selected from the following structures:

[0012]

[0013]

[0014] In the second aspect of the present application, the present application provides a method for preparing the above-mentioned active navy blue dye with high fixation rate, wherein the active navy blue dye with high fixation rate is prepared by condensation reaction of compound a and NH2R1NH2, and the reaction formula for preparing the high fastness royal blue active dye from compound a and NH2R1NH2 is as follows:

[0015]

[0016] Preferably, when preparing the active navy blue dye with high fixation rate, the reaction temperature is controlled at 50-55° C. and the pH is controlled at 5.0-5.5.

[0017] Preferably, compound a is obtained by coupling reaction of compound b, compound c and compound d. The reaction formula for preparing compound a by reaction of compound b, compound c and compound d is as follows:

[0018]

[0019] When preparing compound a, the reaction temperature is controlled at 8-12°C.

[0020] Preferably, compound b is obtained by diazo reaction of compound e and sodium nitrite, and compound c is obtained by diazo reaction of compound f and sodium nitrite, and the reaction formula is as follows:

[0021]

[0022] Preferably, compound e is obtained by condensation reaction of compound g and compound h, and compound f is obtained by condensation reaction of compound g and compound j. The reaction formula is as follows:

[0023]

[0024] In the third aspect of the present application, the present application provides a high fixation rate active navy blue dye composition, the high fixation rate active navy blue dye composition comprises at least two of compound I-1, compound I-2, and compound I-3, and the structural formulas of compound I-1, compound I-2, and compound I-3 are as follows:

[0025]

[0026] Preferably, the active navy blue dye composition with a high fixation rate comprises the compound I-1 and the compound I-2, and the weight ratio of the compound I-1 to the compound I-2 is 0.8-1.2:1.

[0027] In the fourth aspect of the present application, the present application provides an application of the above-mentioned high fixation rate active navy blue dye and / or the high fixation rate active navy blue dye obtained by the above-mentioned preparation method and / or the above-mentioned high fixation rate active navy blue dye composition in textile dyeing.

[0028] Preferably, the high fixation rate active navy blue dye or the composition is used in an amount of 0.5-12% owf.

[0029] In summary, the present invention includes at least one of the following beneficial technical effects:

[0030] 1. The present application provides an active navy blue dye with a high fixation rate, which uses 3,5-diaminophenylethyl sulfone sulfate as an active group and can be condensed with another active group (cyanuric chloride) to form a double active group combination, and 3,5-diaminophenylethyl sulfone sulfate can be condensed and then diazotized with 1-amino 8-naphthol 3,6-disulfonic acid on both sides to form a combination of four active groups, and ethylenediamine is used to connect the second chlorine atom of cyanuric chloride on both sides to form a ring structure of the dye molecule, so that the hydrolyzed dye molecules that have not been dyed after dyeing are easier to fall off during the post-treatment process, thereby improving the washing fastness and rubbing fastness of the dye, and finally obtaining an active navy blue dye with a high fixation rate.

[0031] 2. The present application provides a method for preparing the above-mentioned active navy blue dye with high fixation rate, which has a simple preparation process and is easy to industrialize.

[0032] 3. The present application provides a high-fixation-rate active navy blue dye composition comprising the above-mentioned high-fixation-rate active navy blue dye, which has good color fastness and high fixation rate.

[0033] 4. The present application provides the use of the above-mentioned active navy blue dye with high fixation rate and / or the above-mentioned active navy blue dye composition with high fixation rate in textile dyeing. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with specific examples, but the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. In the following examples, if specific conditions are not specified, they are carried out according to normal conditions or conditions recommended by the manufacturer. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise specified, the professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the recorded content may also be applied to the present invention.

[0035] Example 1

[0036] This embodiment provides a high fixation rate active navy blue dye, the structural formula of which is as follows:

[0037]

[0038] The preparation method of the active navy blue dye with high fixation rate shown in formula I-1 comprises the following steps:

[0039] Step 1): Dissolving: Add 8 times the mass of water to 0.2 mol of 3,5-diaminophenylethyl sulfone sulfate and slurry the mixture evenly, and adjust the pH of the system to 6.5-7.0 with liquid alkali to obtain a dissolved product;

[0040] The reaction formula is as follows:

[0041]

[0042] Step 2): a shrinkage reaction: 0.2 mol of cyanuric chloride is slurried with an ice-water mixture, and the dissolved product obtained in step 1) is added dropwise to the cyanuric chloride slurry. During the process, the temperature is controlled at 10-15° C. and the pH is maintained at 3.0-3.5 with baking soda. The reaction is performed for 4 hours to obtain a shrinkage product;

[0043] The reaction formula is as follows:

[0044]

[0045] Step 3): Diazo reaction: add 0.25 mol hydrochloric acid with a concentration of 30-36% to the condensed product obtained in step 2), stir evenly, cool to 0-5°C, add 0.22 mol sodium nitrite over 1 hour, react at 5-8°C for 2 hours to obtain a diazonium salt product;

[0046] The reaction formula is as follows:

[0047]

[0048] Step 4): Dissolving: Add 6 times the mass of water to 0.1 mol of 1-amino-8-naphthol-3,6-disulfonic acid (H acid) and mix well, adjust the pH of the system to 6.8-7.0 with baking soda to obtain a dissolved product;

[0049] The reaction formula is as follows:

[0050]

[0051] Step 5): coupling reaction: add the dissolved product obtained in step 4) to the diazonium salt product obtained in step 3), maintain the temperature at 8-12° C., adjust the pH to 2.5-3.0 with baking soda, react for 3 hours, then adjust the pH to 5.5-6.0, react for 4 hours, and obtain a disazo coupling product;

[0052] The reaction formula is as follows:

[0053]

[0054] Step 6): Dicondensation reaction: Add an ethylenediamine solution containing 0.1 mol of ethylenediamine to the bisazo coupling product obtained in step 5). Adjust the pH to 5.0-5.5 with baking soda, then raise the temperature to 50-55°C, maintain the temperature and pH for 6 hours, and purify to obtain the final product;

[0055] The reaction formula is as follows:

[0056]

[0057] Example 2

[0058] This embodiment provides a high fixation rate active navy blue dye, the structural formula of which is as follows:

[0059]

[0060] The preparation method of the active navy blue dye with high fixation rate shown in formula I-2 comprises the following steps:

[0061] Step 1): Dissolving: Add 8 times the mass of water to 0.2 mol of 3,5-diaminophenylethyl sulfone sulfate and slurry the mixture evenly, and adjust the pH of the system to 6.5-7.0 with liquid alkali to obtain a dissolved product;

[0062] The reaction formula is as follows:

[0063]

[0064] Step 2): a shrinkage reaction: 0.2 mol of cyanuric chloride is slurried with an ice-water mixture, and the dissolved product obtained in step 1) is added dropwise to the cyanuric chloride slurry. During the process, the temperature is controlled at 10-15° C. and the pH is maintained at 3.0-3.5 with baking soda. The reaction is performed for 4 hours to obtain a shrinkage product;

[0065] The reaction formula is as follows:

[0066]

[0067] Step 3): Diazo reaction: add 0.25 mol hydrochloric acid with a concentration of 30-36% to the condensed product obtained in step 2), stir evenly, cool to 0-5°C, add 0.22 mol sodium nitrite over 1 hour, react at 5-8°C for 2 hours to obtain a diazonium salt product;

[0068] The reaction formula is as follows:

[0069]

[0070] Step 4): Dissolving: add 6 times the mass of water to 0.1 mol of 1-amino-8-naphthol-4,6-disulfonic acid (European K acid) and mix well, adjust the pH of the system to 6.8-7.0 with baking soda to obtain a dissolved product;

[0071] The reaction formula is as follows:

[0072]

[0073] Step 5): coupling reaction: add the dissolved product obtained in step 4) to the diazonium salt product obtained in step 3), maintain the temperature at 8-12°C, adjust the pH to 2.5-3.0 with baking soda, react for 3 hours, then adjust the pH to 5.5-6.0, react for 4 hours, and obtain a disazo coupling product;

[0074] The reaction formula is as follows:

[0075]

[0076] Step 6): Dicondensation reaction: Add an ethylenediamine solution containing 0.1 mol of ethylenediamine to the bisazo coupling product obtained in step 5). Adjust the pH to 5.0-5.5 with baking soda, then raise the temperature to 50-55°C, maintain the temperature and pH for 6 hours, and purify to obtain the final product;

[0077] The reaction formula is as follows:

[0078]

[0079] Example 3

[0080] This embodiment provides a high fixation rate active navy blue dye, the structural formula of which is as follows:

[0081]

[0082] The preparation method of the active navy dye with high fixation rate shown in formula I-3 is similar to that in Example 1, except that in step 6), the equimolar amount of ethylenediamine is replaced by 1,4-butanediamine.

[0083] Example 4

[0084] The active navy blue dye with high fixation rate represented by formula I-1 obtained in Example 1 and the active navy blue dye with high fixation rate represented by formula I-2 obtained in Example 2 were mixed in a weight ratio of 1:1 to obtain a dye composition.

[0085] Dyeing performance test

[0086] Experiment 1: Reactive dye fastness test

[0087] 1. The active navy blue dye with high fixation rate obtained in the above Examples 1-3, the dye composition obtained in Example 4, and the sample of active blue 194, one of the three primary colors widely used in the market, were selected as comparative example 1.

[0088] 2. The reactive dyes of Examples 1-4 and Comparative Example 1 were respectively prepared according to the following conditions: cotton fabric: 5 g, sodium sulfate concentration: 20 g / L, bath ratio: 1:20, soda ash to adjust pH = 8.0, dye concentration: 4% (owf); dyeing and fixing were carried out by 60°C heating dyeing method, and cloth samples were obtained after post-treatment.

[0089] According to the national standards, rubbing color fastness GB / T 3920 2008, washing color fastness GB / T 39212008, the color fastness of the cotton fabric samples after dyeing was measured. The results are shown in Table 1. The results show that a high fixation rate active navy dye of the present application has excellent washing and rubbing fastness on cotton fabric.

[0090] Table 1 List of color fastness of cotton fabric dyeing when the dye concentration is 4% (owf)

[0091]

[0092] The data in Table 1 show that the dyes of Examples 1-4 have excellent fastness to washing and rubbing on cotton fabrics. In particular, compared with the conventional reactive dye blue 194, the fastness of Example 4 has been greatly improved. In addition, the light fastness of the dye composition obtained by mixing the high-fixation active navy dye of formula I-1 obtained in Example 1 and the high-fixation active navy dye of formula I-2 obtained in Example 2 in a weight ratio of 1:1 is significantly better than that of using them alone.

[0093] Experiment 2: Fixation rate test of reactive dyes

[0094] The active navy blue dye with high fixation rate obtained in the above Examples 1-3, the dye composition obtained in Example 4, and the sample of active blue 194, one of the three primary colors widely used in the market, were selected as Comparative Example 1.

[0095] The reactive dye liquors in Examples 1-4 and Comparative Example 1 were prepared according to the following conditions: cotton fabric: 5 g, sodium sulfate concentration: 20 g / L, bath ratio 1:20, pH adjusted to 8.0 with soda ash, dye concentration: 0.5-12% (owf); dyeing was performed by 60° C. heating dyeing method, and then the color fixation rate was determined. The color fixation rate test results are shown in Table 2.

[0096] Table 2 Fixation rate table

[0097]

[0098] The results in Table 2 show that a high fixation rate active navy dye of the present application has a very excellent fixation rate on cotton fabrics, especially the fixation rate of the active dye prepared in Example 1 is increased by more than 9% over the basic fixation rate of traditional active dyes, and the high fixation rate active navy dye shown in formula I-1 obtained in Example 1 and the high fixation rate active navy dye shown in formula I-2 obtained in Example 2 are mixed in a weight ratio of 1:1 to obtain a dye composition. When the dye concentration is greater than 6% (owf), the fixation rate is significantly higher than that of the dye composition used alone.

[0099] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. A high fixation rate active navy blue dye, characterized in that: The structure of the active navy blue dye with high fixation rate is shown in Formula I: Wherein, R1 is selected from C1-C6 alkylene; R2 and R3 are independently selected from halogen; R4 and R5 are independently selected from -H, -SO3M, -CH3, -COOM and -CHO; M is Na, K or Li.

2. The active navy blue dye with high fixation rate according to claim 1, characterized in that: R1 is -C2H4-, -C3H6- or -C4H8-; R2 and R3 are both Cl.

3. The active navy blue dye with high fixation rate according to claim 1, characterized in that: R4 and R5 are both -SO3M; M is Na.

4. The active navy blue dye with high fixation rate according to claim 1, characterized in that: The active navy blue dye with high fixation rate is selected from the following structures:

5. A method for preparing a high fixation rate active navy blue dye according to any one of claims 1 to 4, characterized in that: The high-fixation-rate active navy blue dye is prepared by condensing compound a and NH2R1NH2. The reaction formula for preparing the high-fastness navy blue active dye from compound a and NH2R1NH2 is as follows: When preparing the active navy blue dye with high fixation rate, the reaction temperature is controlled to be 50-55° C. and the pH is controlled to be 5.0-5.

5.

6. The method for preparing a high fixation rate active navy blue dye according to claim 5, characterized in that: Compound a is obtained by coupling reaction of compound b, compound c and compound d. The reaction formula for preparing compound a by reaction of compound b, compound c and compound d is as follows: When preparing compound a, the reaction temperature is controlled at 8-12°C.

7. The method for preparing a high fixation rate active navy blue dye according to claim 6, characterized in that: Compound b is obtained by diazo reaction of compound e and sodium nitrite, and compound c is obtained by diazo reaction of compound f and sodium nitrite. The reaction formula is as follows:

8. A high fixation rate active navy blue dye composition, characterized in that: The high fixation rate active navy blue dye composition comprises at least two of compound I-1, compound I-2 and compound I-3, and the structural formulas of compound I-1, compound I-2 and compound I-3 are as follows:

9. Use of the high fixation rate active navy dye according to claims 1-4 and / or the high fixation rate active navy dye obtained by the preparation method according to claims 5-7 and / or the high fixation rate active navy dye composition according to claim 8 in textile dyeing.

10. The use according to claim 9, characterized in that: The dosage of the high fixation rate active navy blue dye or the composition is 0.5-12% owf.

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