CN115521636A - Dicyan-containing sun-proof anthraquinone disperse dye and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of chemical industry, and particularly relates to a dicyan-containing sun-proof anthraquinone disperse dye and a preparation method thereof. The structural general formula of the dicyan-containing sun-proof anthraquinone-containing disperse dye is as follows:

Description

A kind of dicyano group-containing sunfast type anthraquinone disperse dye and its preparation method

technical field

The invention belongs to the field of chemical industry, and in particular relates to a dicyano group-containing light-resistant anthraquinone disperse dye and a preparation method thereof.

technical background

Disperse dyes can be divided into azo type and anthraquinone type according to their chemical structure. Anthraquinone type disperse dyes are the most used dyes except azo dyes. They have the characteristics of bright color, stability, light fastness and good fastness. However, with the increasing application of dyes in the modern printing and dyeing industry, people's requirements for light fastness of dyes continue to increase, and traditional anthraquinone-type disperse dyes have been difficult to meet the light fastness requirements of dyes in some special environments.

The photofading process of anthraquinone disperse dyes is a very complicated process, which can be divided into photooxidative fading and photoreduction fading according to the mechanism. The two fading mechanisms are closely related to the molecular structure of the dye, and the light fastness of the dye is related to the color body structure of the dye and ultraviolet radiation and other factors. It is generally believed that the higher the electron cloud density of the amino group in the anthraquinone structure, the easier it is to be oxidized to hydroxylamine, resulting in lower light fastness. Therefore, the conventional method is to introduce an electron-withdrawing group at the ortho position of the amino group of anthraquinone disperse dyes to reduce the electron cloud density of the amino group, thereby improving the light fastness of the dye.

The invention of 201610046791.0 "A Preparation Method for 1,4-Diamino-2,3-Dicyanoanthraquinone" provides a dye with a cyano group directly introduced into the ortho position of the anthraquinone amino group, but due to the strong absorption of the cyano group Electricity, the shade of the dye has shifted, it is not a pure blue dye, and the dyeing performance is poor.

The invention of 201010142513.8 "A Preparation Method of Disperse Blue 60 and Its Homologs" provides an anthraquinone type disperse dye C.I. Disperse Blue 60 with good light fastness (level 7), which can meet the requirements of most conventional textiles. Application requirements for light fastness. However, C.I. Disperse Blue 60 still cannot meet the light fastness requirements of textiles in special environments.

The invention of 202111316457X "Sun-fast Anthraquinone Disperse Dyes and Its Preparation Method" provides two light-fast anthraquinone disperse dyes, whose molecular structure contains hindered amine light-stable fragments and has excellent light fastness. However, due to its poor color fastness to washing, it still cannot meet the color fastness requirements of some textiles.

Contents of the invention

The technical problem solved by the present invention is to provide a light-fast anthraquinone disperse dye and a preparation method thereof. The disperse dye has the characteristics of higher dye uptake, color fastness to washing and light fastness.

In order to solve the above-mentioned technical problems, the present invention provides a dicyano-containing sunfast type anthraquinone disperse dye, the general formula of its molecular structure is as follows:

In the formula: R is -CH ₂ -CH ₂ - or

As a further improvement of the light-resistant anthraquinone disperse dye of the present invention, the structural formula of the disperse dye is any of the following:

The present invention also simultaneously provides a preparation method for the above-mentioned light-fast type anthraquinone disperse dye, comprising the following steps:

1) Dissolving N,N-dicyanoethyl derivatives and 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride in DMF, raising the temperature to 105-110°C and stirring for 3-5 hours to obtain Target disperse dye solution;

The molar ratio of the N,N-dicyanoethyl derivative to 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride is 3:2;

2) Post-treat the target disperse dye solution obtained in step 1) to obtain light-fast anthraquinone disperse dye.

Specifically:

Add ethanol to the target disperse dye solution obtained in step 1) for isolation, reduce the temperature to 25±5°C and filter with suction, wash the filter cake with ethanol, then wash it with hot water (about 60-70°C) and dry it (Dried to constant weight at 80°C) to obtain the finished product---sunfast anthraquinone disperse dye.

The reaction formula of invention is as follows:

R is -CH ₂ -CH ₂ - or

When the N,N-dicyanoethyl derivative is N,N-dicyanoethyl-1,2-ethylenediamine, the resulting product is

When the N,N-dicyanoethyl derivative is N,N-dicyanoethyl-1,4-phenylenediamine, the resulting product is

The preparation method of light-resistant anthraquinone disperse dyes of the present invention selects 1,4-diaminoanthraquinone-2,3-dicarboxylic acid anhydride and N,N-dicyanoethyl derivatives as raw materials. The introduction of cyano groups on the basis of the anthraquinone chromophore effectively improves the color fastness to washing and light fastness of the dye.

The light-fast anthraquinone disperse dye of the present invention is used for dyeing hydrophobic polyester (PET) fibers, and its dyeing process refers to the invention of 202111316457X "Sun-fast anthraquinone disperse dye and its preparation method".

The light-resistant anthraquinone disperse dye of the present invention is improved on the basis of the 1,4-diaminoanthraquinone color body structure, and a cyano group (ie N,N-dicyanoethyl-1,2- Ethylenediamine or N,N-dicyanoethyl-1,4-phenylenediamine group), using the function of cyano group to effectively absorb ultraviolet rays, inhibit the photofading reaction of anthraquinone dyes, thereby improving the light fastness of dyes . This type of dye has broad application prospects in the field of demanding light fastness.

It should be emphasized that the present invention is a cyano-containing disperse dye, while 201610046791.0, 201010142513.8, and 202111316457X provide conventional disperse dye structures. The present invention improves the color brightness of the dye by introducing cyano groups, and the dye has good fastness , excellent application performance.

In summary, the light-fast anthraquinone disperse dye of the present invention makes up for the deficiency that traditional commercial anthraquinone disperse dyes are not suitable for special environments requiring high light fastness. While having excellent light fastness, it enriches the varieties of high light fastness disperse dyes.

detailed description

The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:

1,4-diamino-2,3-dicarboxylic anhydride anthraquinone (CAS: 3176-87-2), N, N-dicyanoethyl-1,2-ethylenediamine (CAS: 55534-79-7 ), N,N-dicyanoethyl-1,4-phenylenediamine (CAS: 104851-97-0) are known compounds.

Embodiment 1, a kind of dicyano group-containing sunfast type anthraquinone disperse dye and its preparation method are carried out according to the following steps:

Add 0.03mol (about 5.0g) of N,N-dicyanoethyl-1,2-ethylenediamine and 0.02mol (about 7.7 g), make it completely dissolved in DMF (40mL), heat and stir the reaction at 105°C for 5 hours to the end of the reaction, then add an appropriate amount (about 30ml) of ethanol for isolation, cool to normal temperature (25±5°C), and then suction filter, After the filter cake is washed with ethanol (about 30ml), it is washed with hot water (about 100ml of hot water at 60°C), and dried in an oven at 80°C to constant weight. The dried product is 8.34g (0.0182mol), with a purity of 94.5%, the yield is 91.4%, and the target product A1 is obtained.

¹ H NMR (400MHz, DMSO-d6): δ8.29(t, 2H), 7.85(d, 2H), 4.82(s, 4H), 3.59(t, 2H), 3.01(t, 4H), 2.73( t, 4H), 2.60 (t, 2H); ESI MS (m/z, %): 457.2 ([M+H] ⁺ , 100).

Embodiment 2,

Add 0.03mol (about 6.5g) of N,N-dicyanoethyl-1,4-phenylenediamine and 0.02mol (about 7.7 g), make it completely dissolved in DMF (40mL), heat the reaction at 105°C for 5 hours to the end of the reaction, add an appropriate amount of ethanol (about 30mL) for isolation, cool to normal temperature and then suction filter, wash the filter cake with ethanol, and then Wash in hot water, dry in an oven at 80°C to constant weight, and the dried product is 8.94g (0.0177mol), with a purity of 96.4%, and a yield of 92.3%, to obtain light-fast anthraquinone disperse dye A2, the structure of which is as follows:

¹ H NMR (400MHz, DMSO-d6): δ8.31(t,2H),7.83(d,2H),7.09(d,2H),6.90(d,2H),4.80(s,4H),3.72( t,4H), 3.14(t,4H); ESI MS (m/z,%): 505.2 ([M+H] ⁺ , 100).

Experiment 1,

Get dyestuff (A1/A2) 0.25g of the present invention, dispersant NNO 0.5g, zirconium bead (1mm) 12g, water 20mL in sand mill sand mill 8 hours, after treating that sand mill finishes, filter with fine nylon cloth , dilute the collected dispersion to 500mL (in a 500mL volumetric flask) with deionized water, and make a dye paste; pipette the disperse dye paste according to the chromaticity requirement of 2% owf, and add it at a liquor ratio of 1:50 Transfer deionized water to the dyeing cup, add the PET fabric to be dyed, place the dyeing cup in a high-temperature and high-pressure dyeing machine, set the dyeing program as follows: heat up to 90°C at 2°C/min, Raise the temperature to 130°C for 1 hour, cool down to room temperature at 2°C/min after keeping it warm for 1 hour, take out the dyed cloth sample, absorb 1mL each of the pre-dyeing and post-dyeing solutions into a 10mL volumetric flask, dilute to the mark with acetone, and use UV- Visible spectrophotometer measures the absorbance at the maximum absorption wavelength of the dye (λ _max ), and calculates the dye uptake rate by using the Lambert-Beer law.

The dye uptake rate of A1 was 98.6%, and the dye uptake rate of A2 was 97.9%.

The above-mentioned dyed cloth samples were tested according to the national standards "Test of Textile Fastness to Sublimation" (GB/T 5718-1997), "Textile Color Fastness Test to Washing Color Fastness" (GB/T 3921-2008), "Textile Color Fastness Color fastness to artificial light in degree test: xenon arc" (GB/T 8427-2008) requires reduction cleaning (reduction cleaning process: 2g/L hydrosulfite, 1g/L NaOH, bath ratio 1:50, 70°C, 15min), the cloth sample after reduction cleaning was tested for sublimation fastness, color fastness to washing and light fastness. The test results showed:

The color fastness to sublimation and the color fastness to washing of dyes A1 and A2 are both grade 5 and the light fastness is grade 8.

Comparative experiment 1,

C.I. Disperse Blue 60 dye is substituted for the dyestuff of the present invention, and is detected according to the method described in the above-mentioned experiment 1: its dye uptake rate is 92.5%, the sublimation fastness is 4-5 grades, and the light fastness is 8 grades.

The specific performance comparison is shown in Table 1 below.

Table 1

dye Dyeing rate/% Sublimation fastness Light fastness C.I. Disperse Blue 60 92.5 4-5 7 A1 98.6 5 8 A2 97.9 5 8

According to the results in Table 1, it can be seen that the light fastness of A1 and A2 is better than that of C.I. The introduction of cyano groups can further improve the sublimation fastness and light fastness, and the dye uptake rates of A1 and A2 are higher than C.I. Disperse Blue 60, which has good dye uptake performance.

Comparative Example 1. Change N,N-dicyanoethyl-1,2-ethylenediamine in Example 1 to N,N-diethyl-1,2-ethylenediamine, and the rest are the same as in Example 1 . The resulting product is:

Detected according to the method described in Experiment 1 above, the dye uptake rate was 89.7%; the sublimation fastness was grade 4, and the light fastness was grade 6-7. The performance comparison with A1 is shown in Table 2 below.

Comparative example 2, changing product A1 into 1,4-diamino-2,3-dicyanoanthraquinone,

Detected according to the method described in the above-mentioned experiment 1, the dye uptake rate was 78.5%; the sublimation fastness was grade 4, and the light fastness was grade 6-7. The performance comparison with A1 is shown in Table 2 below.

Table 2

dye Dyeing rate/% Sublimation fastness Light fastness A1 98.6 5 8 Comparative example 1 89.7 4 6-7 Comparative example 2 78.5 4 6-7

According to the results in Table 2, it can be seen that the light fastness of A1 is better than that of Comparative Example 1 with the same structure of the color matrix and the light fastness of Comparative Example 2 that directly introduces a cyano group at the ortho-position of the anthraquinone amino group. The introduction of cyano groups into the 4-diaminoanthraquinone color body structure can further improve the sublimation fastness and light fastness, and the dye uptake rate of A1 is higher than that of Comparative Examples 1 and 2, which has good dye uptake performance.

Comparative Example 3. The N,N-dicyanoethyl-1,2-ethylenediamine in Example 1 was changed to tetramethylpiperidinamine, and the rest was the same as Example 1. The resulting product is:

Detected according to the method described in the above experiment 1, the dye uptake rate was 95.8%; the sublimation fastness was grade 4, the color fastness to washing was grade 3, and the light fastness was grade 8. The performance comparison with A1 is shown in Table 3 below.

Comparative Example 4. The N,N-dicyanoethyl-1,2-ethylenediamine in Example 1 was changed to Pentamethylpiperidinamine, and the rest was the same as Example 1. The resulting product is:

Detected according to the method described in the above experiment 1, the dye uptake rate was 97.4%; the sublimation fastness was grade 4, the color fastness to washing was grade 3, and the light fastness was grade 8. The performance comparison with A1 is shown in Table 3 below.

table 3

dye Dyeing rate/% Sublimation fastness Color fastness to washing Light fastness A1 98.6 5 5 8 Comparative example 3 95.8 4 3 8 Comparative example 4 97.4 4 3 8

According to the results in Table 3, it can be seen that the sublimation fastness and color fastness to washing of A1 are better than those of Comparative Example 3 and Comparative Example 4 with the same structure of the color matrix, indicating that the 1,4-diaminoanthraquinone color body The introduction of cyano groups on the basis of the structure can further improve the fastness to sublimation and color fastness to washing. At the same time, the dye uptake rate of A1 is higher than that of Comparative Examples 3 and 4, which has good dye uptake performance.

Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many variations are possible. All deformations that can be directly derived or associated by those skilled in the art from the content disclosed in the present invention should be considered as the protection scope of the present invention.

Claims (5)

1. Anthraquinone disperse dyes containing dicyano group light fastness, characterized in that the general structural formula is:

In the formula: R is -CH ₂ -CH ₂ - or

2. the dicyano-containing sunfast type anthraquinone disperse dye according to claim 1, characterized in that the structural formula is any of the following:

3. as claimed in claim 1 or 2, the preparation method containing dicyano light fast type anthraquinone disperse dye is characterized in that comprising the steps: 1) Dissolving N,N-dicyanoethyl derivatives and 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride in DMF, raising the temperature to 105-110°C and stirring for 3-5 hours to obtain Target disperse dye solution; The molar ratio of the N,N-dicyanoethyl derivative to 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride is 3:2; 2) Post-treat the target disperse dye solution obtained in step 1) to obtain light-fast anthraquinone disperse dye. 4. the preparation method of the dicyano light-fast type anthraquinone disperse dye containing dicyano according to claim 3, is characterized in that: The N,N-dicyanoethyl derivatives are N,N-dicyanoethyl-1,2-ethylenediamine and N,N-dicyanoethyl-1,4-phenylenediamine. 5. according to the preparation method of claim 3 or 4 described containing dicyano sunfast type anthraquinone disperse dyes, it is characterized in that the aftertreatment of described step 2) is: Add ethanol to the target disperse dye solution obtained in step 1) for isolation, reduce the temperature to 25±5°C and filter with suction, wash the filter cake with ethanol, wash it with hot water, and dry it to obtain a light-fast anthraquinone dispersion dye.