Preparation method of disperse blue 60

Abstract

The invention discloses a preparation method of disperse blue 60, which comprises the following steps: (1) adding 1, 4-diamino-2, 3-dicarboximide anthraquinone and 3-methoxypropylamine into a mixed medium, heating, and carrying out condensation reaction; the mixed medium is a mixture of 1, 4-dioxane, aniline / nitrobenzene and water; (2) after the reaction is finished, cooling, carrying out suction filtration, and washing a filter cake with hot water until filtrate is neutral, so as to obtain a filter cake, namely the disperse blue 60; and (3) recovering the filtrate generated in the suction filtration process in the step (2) for the condensation reaction in the step (1). The production process is simple, the production cost is low, the dye quality is good, the problem of residual chlorobenzene in the disperse blue 60 product is solved, and the colored light can reach the quality standard of using chlorobenzene as a solvent.

Description

Technical Field

[0001] The invention relates to the technical field of organic dyes, and in particular to a preparation method of Disperse Blue 60. Background Art

[0002] Disperse Blue 60 is a bright green blue, mainly used for dyeing emerald blue, emerald green and peacock blue. Due to its special color and excellent color fastness, it is an important dye for dyeing bright green polyester and its blended fabrics in the printing and dyeing process. In recent years, with the increasing awareness of environmental protection, environmental problems and international trade barriers have become increasingly severe, and the country's environmental protection requirements for the production and use of dyes have become increasingly higher, and the improvement of dye production technology is imminent.

[0003] At present, the production process of Disperse Blue 60 is to use 1,4-diamino-2,3-dicarboximide anthraquinone as raw material, and to react with 3-methoxypropylamine in chlorobenzene and water medium for condensation reaction. This method has bright color, but chlorobenzene is insoluble in water and it is difficult to completely remove it in the subsequent processing. The product does not meet the requirements of OEKO-TEX100 and BLUE SIGN for ecological textiles. At the same time, if chlorobenzene is not used as a solvent, the color becomes worse.

[0004] Therefore, many manufacturers have made a lot of efforts to solve the problem of chlorobenzene residue in the production of Disperse Blue 60 and the deterioration of color caused by not using chlorobenzene. For example, in patent CN101130640A, 1,4-diamino-2,3-dicarboximide is refined and then condensed. Although this method has greatly improved the color, it still cannot reach the color of using chlorobenzene as a solvent. At the same time, the refining of imine increases activated carbon solid waste and wastewater containing sodium sulfate, which is not good for environmental protection. In patent CN 115386241A, 1,4-diamino-2,3-dicarboxylic anhydride anthraquinone is used as raw material, and in a mixed medium of 3-methoxypropylamine, DMF, methanol and water, the temperature is raised to 80-90℃ and kept for 3-5h to the end of the reaction, but the color is poor. In the patent CN103497142A, water is used as solvent, 1,4-diamino-2,3-dicarboximide anthraquinone and 3-methoxypropylamine are used as raw materials, and the condensation reaction is carried out at 85-95°C for 2-5h under reduced pressure distillation to obtain Disperse Blue 60. Although this method reduces the cost, the color light is not good. In the patent CN101817989A, 1,4-diamino-2,3-dicarboximide anthraquinone and 3-methoxypropylamine are carried out in water for condensation reaction, but because 1,4-diamino-2,3-dicarboximide anthraquinone is insoluble in water, water is used as solvent, resulting in high reaction temperature and long reaction time. It is necessary to keep the temperature at 95-105°C for 4-6h to reach the end point, and because the impurities generated during the condensation process are also water-insoluble, they will precipitate with the dye, so the quality of the dye is difficult to guarantee, and the energy consumption is high. In patent CN116855099A, 1,4-diamino-2,3-dicarboximide anthraquinone and 3-methoxypropylamine are subjected to condensation reaction at 80-90°C in the presence of a small amount of n-butylamine and ethanol, and the mixture is diluted with water to obtain a mixture of disperse blue 60 and its derivatives. The yield of this method is below 82%, which is about 10% lower than that of the traditional method, and the color light is unstable. Due to the dye generated by mixing with n-butylamine, the sublimation fastness of the mixed dye deteriorates. In patent CN117024328A, 1,4-diamino-2,3-dicarboximide anthraquinone and a large proportion of 3-methoxypropylamine are subjected to condensation reaction at 80-95°C. After the reaction is completed, methanol is added to obtain disperse blue 60. This method has high 3-methoxypropylamine unit consumption, and methanol precipitation easily causes isomeric dyes to precipitate to varying degrees, resulting in unstable color light. Summary of the invention

[0005] In view of the above problems existing in the prior art, the present invention provides a method for preparing Disperse Blue 60. The present invention has a simple production process, low production cost, good dye quality, solves the problem of residual chlorobenzene in the Disperse Blue 60 product, and the color light can also reach the quality standard of using chlorobenzene as a solvent.

[0006] The technical solution of the present invention is as follows:

[0007] The first object of the present invention is to provide a method for preparing Disperse Blue 60, comprising the following steps:

[0008] (1) adding 1,4-diamino-2,3-dicarboximide anthraquinone and 3-methoxypropylamine to a mixed medium, heating, and causing a condensation reaction; the mixed medium is a mixture of 1,4-dioxane, aniline / nitrobenzene, and water;

[0009] (2) After the reaction is completed, the temperature is lowered, the filter is filtered, and the filter cake is washed with hot water until the filtrate is neutral. The filter cake is the Disperse Blue 60;

[0010] (3) The filtrate produced during the filtration process of step (2) is recovered and used for the condensation reaction of step (1).

[0011] In one embodiment of the present invention, in step (1), the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to 3-methoxypropylamine is 1:0.3-0.7.

[0012] Preferably, the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to 3-methoxypropylamine is 1:0.35-0.5.

[0013] In one embodiment of the present invention, in step (1), the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to 1,4-dioxane is 1:0.8-2.5.

[0014] Preferably, the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to 1,4-dioxane is 1:1.2-2.0.

[0015] In one embodiment of the present invention, in step (1), the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to aniline / nitrobenzene is 1:0.05-0.3.

[0016] Preferably, the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to aniline / nitrobenzene is 1:0.08-0.2.

[0017] In one embodiment of the present invention, aniline / nitrobenzene means selecting one of aniline and nitrobenzene or a mixture of the two.

[0018] In one embodiment of the present invention, in step (1), the heating is to raise the temperature to 85-100° C. within 1-1.5 hours, and then keep the temperature for 3-5 hours.

[0019] Preferably, the condensation reaction temperature is 88-92°C.

[0020] In one embodiment of the present invention, in step (2), the condensation reaction is terminated when the raw material content is detected by liquid chromatography to be below 1.5%.

[0021] In one embodiment of the present invention, in step (2), the temperature is lowered to below 40°C.

[0022] In one embodiment of the present invention, in step (2), the hot water washing uses hot water at a temperature of 85-90°C.

[0023] In one embodiment of the present invention, in step (3), the concentrations of 3-methoxypropylamine and 1,4-dioxane are adjusted during the recovery of the filtrate.

[0024] The beneficial technical effects of the present invention are:

[0025] The invention has simple production process, low production cost and good dye quality, solves the problem of residual chlorobenzene in disperse blue 60 products, and the color light can also reach the quality standard of using chlorobenzene as solvent. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Schematic diagram of the synthetic route of the present invention. DETAILED DESCRIPTION

[0027] The present invention is described in detail below with reference to the accompanying drawings and examples. Unless otherwise specified, the raw materials in the examples are all commercially available industrial products suitable for use as dyes and intermediates.

[0028] Example 1

[0029] In a 500mL three-necked flask equipped with a reflux condenser, add 21.5g of 3-methoxypropylamine, 78.8g of 1,4-dioxane, 4g of aniline, 10.71g of water, and 50g of 1,4-diamino-2,3-dicarboximide anthraquinone. Heat to 90°C for 1h and keep warm for 4.15h. HPLC detection reaches the reaction endpoint, cool to 40°C, filter the material, wash with 90°C hot water, and dry to obtain 57.05g of Disperse Blue 60 filter cake.

[0030] The chromatographic purity was 98.02%, and the yield was 92.42%. The mother liquor was collected and recovered to obtain 90.2 g, which contained 6.5 g of 3-methoxypropylamine, 9.2 g of water, and 74.5 g of 1,4-dioxane.

[0031] Example 2

[0032] In a 500mL three-necked flask equipped with a reflux condenser, add 90.2g of the recovered liquid of Example 1, add 3-methoxypropylamine, 1,4-dioxane, water according to the formula of Example 1, and add 7.0g of aniline and 50g of 1,4-diamino-2,3-dicarboximide anthraquinone at the same time, heat to 90℃ for 1h and keep warm for 4.15h, detect to the end point of the reaction by HPLC, cool to 40℃, filter the material, wash with 90℃ hot water, and dry to obtain 57.8g of Disperse Blue 60 filter cake. The chromatographic purity is 97.95%, and the yield is 93.64%.

[0033] Example 3

[0034] In a 500mL three-necked flask equipped with a reflux condenser, add 18g of 3-methoxypropylamine, 50g of 1,4-dioxane, 4g of aniline, 13g of water, and 50g of 1,4-diamino-2,3-dicarboximide anthraquinone, heat to 90°C for 1h and keep warm for 3.5h, detect the end point of the reaction by HPLC, cool to 40°C, filter the material, wash with 90°C hot water, and dry to obtain 56.9g of Disperse Blue 60 filter cake. The chromatographic purity is 98.03% and the yield is 92.18%.

[0035] Example 4

[0036] In a 500mL three-necked flask equipped with a reflux condenser, add 15.5g of 3-methoxypropylamine, 65g of 1,4-dioxane, 5g of nitrobenzene, 12g of water, and 50g of 1,4-diamino-2,3-dicarboximide anthraquinone, heat to 90℃ for 1h and keep warm for 4.2h, detect by HPLC until the end of the reaction, cool to 40℃, filter the material, wash with 90℃ hot water, and dry to obtain 57.65g of Disperse Blue 60 filter cake. The chromatographic purity is 97.49%, the yield is 93.4%, and the mother liquor is collected to recover 71.5g. After analysis, it contains 0.5g of 3-methoxypropylamine, 10.2g of water, and 60.8g of dioxane.

[0037] Example 5

[0038] In a 500mL three-necked flask equipped with a reflux condenser, add 71.5g of the recovered liquid of Example 4, add 3-methoxypropylamine, 1,4-dioxane, and water according to the formula of Example 4, and add 3.5g of nitrobenzene and 50g of 1,4-diamino-2,3-dicarboximide anthraquinone at the same time, heat to 90°C for 1h and keep warm for 4.25h, detect the reaction end point by HPLC, cool to 40°C, filter the material, wash with 90°C hot water, and dry to obtain 57.19g of Disperse Blue 60 filter cake. The chromatographic purity is 97.63%, and the yield is 92.65%.

[0039] Example 6

[0040] In a 500mL three-necked flask equipped with a reflux condenser, add 20g of 3-methoxypropylamine, 78.8g of 1,4-dioxane, 2.5g of nitrobenzene, 1.5g of aniline, 10.71g of water, and 50g of 1,4-diamino-2,3-dicarboximide anthraquinone, heat to 90°C for 1h and keep warm for 4.15h, detect the reaction end point by HPLC, cool to 40°C, filter the material, wash with 90°C hot water, and dry to obtain 58.05g of Disperse Blue 60 filter cake. The chromatographic purity is 97.36%, and the yield is 94.04%.

[0041] 21.5 g of the filter cake prepared in Example 1-6, 10.5 g of sodium lignin sulfonate, and 15.3 g of dispersant MF were added with 65 g of water and stirred well, ground, dispersed, and dried to obtain disperse blue 60 commercial dye.

[0042] The same batch of 1,4-diamino-2,3-dicarboximide anthraquinone as in Examples 1-6 was used to prepare Disperse Blue 60 filter cake using the methods of patents CN115386241A (Comparative Example 1), patent CN103497142A (Comparative Example 2), patent CN101817989A (Comparative Example 3), patent CN116855099A (Comparative Example 4), and patent CN 117024328A (Comparative Example 5). 21.5 g of the filter cake, 10.5 g of sodium lignin sulfonate, 15.3 g of dispersant MF, 65 g of water were added and stirred thoroughly, ground, dispersed and dried to obtain Disperse Blue 60 commercial dye.

[0043] Test example:

[0044] Color light detection: The detection method is GB / T 2394-2013.

[0045] Sublimation fastness test: The test method adopts the test standard "ISO 105-P01: 1993 Color fastness to dry heat (excluding hot pressing)" (test conditions: temperature 180℃±2℃30s; pressure: 4kPa±1kPa; rating: gray card rating) to test sublimation fastness.

[0046] Organic chlorine carrier detection method: The organic chlorine carrier content is tested using "DIN 54232: 2010-08 Textiles. Determination of adhesive content based on chlorobenzene and chlorotoluene".

[0047] The dyes prepared in Examples 1-6 and Comparative Examples 1-5 were dyed according to the GB / T 2394-2013 method, and the obtained polyester fiber fabrics were tested for sublimation fastness and organic chlorine carrier content according to the methods of "ISO 105-P01: 1993 Color fastness to dry heat (excluding hot pressing)" and "DIN 54232: 2010-08 Textiles. Determination of adhesive content based on chlorobenzene and chlorotoluene". The test results are shown in Table 1.

[0048] Table 1

[0049]

[0050] Note: ND = Not Detected, Detection Limit = 0.1 mg / kg

[0051] DE is the total color difference (color difference formula CMC (2:1); color measurement light source is D65 light source, 10° viewing angle)

[0052] DC is the color saturation difference (color difference formula CMC (2:1); color measurement light source is D65 light source, 10° viewing angle)

[0053] DH is the hue and color difference (color difference formula CMC (2:1); color measurement light source is D65 light source, 10° viewing angle)

[0054] Da is the red-green color difference (color difference formula CIE LAB; color measurement light source is D65 light source, 10° viewing angle)

[0055] Db is the yellow-blue color difference (color difference formula CIE LAB; color measurement light source is D65 light source, 10° viewing angle)

[0056] It can be seen from the data in Table 1 that the finished dye products of Examples 1-6 provided by the present invention have brighter color than the finished dye products of Comparative Examples 1-5. At the same time, after the dyes of the embodiments and comparative examples are dyed on polyester fiber fabrics, it is tested that they do not contain organic chlorine carriers, and can meet the environmental protection requirements of the Oeko-Tex100 standard.

[0057] Using 50 g of the same batch of 1,4-amino-2,3-dicarboximide anthraquinone as raw material, refer to the method of Example 1, the only difference is that the ratio of the mixed medium is changed, and a comparative experiment is carried out on the ratio of the mixed medium. The experimental conditions and results are shown in Table 2-4 below.

[0058] Table 2

[0059]

[0060]

[0061] According to the results in Table 2, it can be seen that when one or two of the solvents are missing in the mixed medium of 1,4-dioxane, aniline / nitrobenzene and water, the color of the filter cake is greatly affected and the color of the obtained filter cake is poor. However, when 1,4-dioxane, aniline / nitrobenzene and water are mixed in a certain proportion, the color of the filter cake is greatly improved.

[0062] Table 3

[0063]

[0064] According to the results in Table 3, it can be found that the amount of 1,4-dioxane has a slight effect on the color of the finished product, and considering the viscosity of the system during the reaction, the color is best when the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to 1,4-dioxane is 1:1.2-2.0.

[0065] Table 4

[0066]

[0067] According to the results in Table 4, it can be found that the amount of aniline / nitrobenzene has a certain influence on the color of the finished product. The color is optimal when the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to aniline / nitrobenzene is 1:0.08-0.2.

[0068] The embodiments provided above are not intended to limit the scope of the present invention, and the steps described are not intended to limit the execution order thereof. Those skilled in the art may make obvious improvements to the present invention in combination with existing common knowledge, which also fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for preparing Disperse Blue 60, characterized in that: The following steps are involved: (1) adding 1,4-diamino-2,3-dicarboximide anthraquinone and 3-methoxypropylamine to a mixed medium, heating, and causing a condensation reaction; the mixed medium is a mixture of 1,4-dioxane, aniline / nitrobenzene, and water; (2) After the reaction is completed, the temperature is lowered, the filter is filtered, and the filter cake is washed with hot water until the filtrate is neutral. The filter cake is the Disperse Blue 60; (3) The filtrate produced during the filtration process of step (2) is recovered and used for the condensation reaction of step (1).

2. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to 3-methoxypropylamine is 1:0.3-0.

7.

3. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to 1,4-dioxane is 1:0.8-2.

5.

4. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone to aniline / nitrobenzene is 1:0.05-0.

3.

5. The preparation method according to claim 1, characterized in that: Aniline / nitrobenzene means selecting one of aniline and nitrobenzene or a mixture of the two.

6. The preparation method according to claim 1, characterized in that: In step (1), the temperature is raised to 85-100° C. within 1-1.5 h, and then kept warm for 3-5 h.

7. The preparation method according to claim 1, characterized in that: In step (2), the condensation reaction is terminated when the raw material content is detected by liquid chromatography to be below 1.5%.

8. The preparation method according to claim 1, characterized in that: In step (2), the temperature is lowered to below 40°C.

9. The preparation method according to claim 1, characterized in that: In step (2), the hot water temperature used for hot water washing is 85-90°C.

10. The preparation method according to claim 1, characterized in that: In step (3), the concentrations of 3-methoxypropylamine and 1,4-dioxane are adjusted during the recovery of the filtrate.

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