阅读说明：本技术 一种紫色染料化合物及其制备方法、分散紫染料、黑色分散染料及其应用 (Purple dye compound and preparation method thereof, disperse purple dye, black disperse dye and application thereof ) 是由 王喆 王淑香 辛德吉 冯英杰 纪晓云 高登君 隋晓梅 于 2021-06-22 设计创作，主要内容包括：本发明提供了一种紫色染料化合物及其制备方法、分散紫染料、黑色分散染料及其应用,涉及染料技术领域。本发明提供的紫色染料化合物,具有式I所示的结构,所述式I中,X为卤素；R-1包括-H或-CH-3；R-2包括-C-2H-5、-CH-2CH＝CH-2、-CH-2CH-2CN或-CH-2CH-2CH-2CH-2Cl；R-3包括-CH-2CH-2CH-2CH-2Cl、-CH-2CH-2OCH-2CH-2CN、-CH-2CH(OH)CH-2Cl或-CH-2CH(OCOCH-3)CH-2Cl。本发明提供的紫色染料化合物给色深、牢度佳,移染性好；本发明提供的紫色染料化合物成本低,属于环保型染料。(The invention provides a purple dye compound and a preparation method thereof, a disperse purple dye, a black disperse dye and application thereof, and relates to the technical field of dyes. The purple dye compound provided by the invention has a structure shown in a formula I, wherein in the formula I, X is halogen; r 1 comprising-H or-CH 3 ；R 2 comprising-C 2 H 5 、‑CH 2 CH＝CH 2 、‑CH 2 CH 2 CN or-CH 2 CH 2 CH 2 CH 2 Cl；R 3 comprising-CH 2 CH 2 CH 2 CH 2 Cl、‑CH 2 CH 2 OCH 2 CH 2 CN、‑CH 2 CH(OH)CH 2 Cl or-CH 2 CH(OCOCH 3 )CH 2 And (4) Cl. The purple dye compound provided by the invention has the advantages of deep color, good fastness and good migration property; the purple dye compound provided by the invention is low in cost and belongs to an environment-friendly dye.)

1. A violet dye compound having the structure of formula I:

in the formula I, X is halogen;

R₁comprising-H or-CH₃；

R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；

R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

2. The violet dye compound according to claim 1, wherein in the formula I,

when the X is-Br, the R₁is-H, said R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl；

When the X is-Br, the R₁is-CH₃Said R is₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl；

When the X is-Cl, the R₁is-H, said R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl；

When the X is-Cl, the R₁is-CH₃Said R is₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

3. The violet dye compound of claim 1 or 2, wherein the violet dye compound has a structure represented by any one of formulas I-1 to I-6:

4. a process for preparing a violet dye compound according to any one of claims 1 to 3, which comprises the steps of:

mixing 2, 4-dinitro-6-haloaniline, nitrosyl sulfuric acid and sulfuric acid, and performing diazotization reaction to obtain a diazonium salt solution;

mixing the diazonium salt solution, substituted aniline, sulfamic acid, sulfuric acid solution and ice, and then carrying out coupling reaction to obtain a purple dye compound with a structure shown in a formula I;

the substituted aniline has a structure represented by formula II:

in the formula II, R₁including-H or-CH; r₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

5. A disperse violet dye, which is characterized by comprising a violet dye compound and a dispersing agent; the purple dye compound is the purple dye compound as set forth in any one of claims 1-3 or the purple dye compound prepared by the preparation method as set forth in claim 4.

6. The disperse violet dye according to claim 5, wherein the disperse violet dye compound is 15-70% by mass.

7. A black disperse dye composition, which is characterized by comprising a purple dye compound and/or a disperse purple dye, a disperse blue dye compound and a disperse orange dye compound;

the purple dye compound is the purple dye compound as defined in any one of claims 1-3 or the purple dye compound prepared by the preparation method as defined in claim 4;

the disperse violet dye is the disperse violet dye as set forth in any one of claims 5 to 6;

the disperse blue dye compound has a structure shown in formula III:

x in the formula III is halogen;

the disperse orange dye compound has a structure shown in formula IV:

8. the black disperse dye composition according to claim 7, wherein the black disperse dye composition comprises, in mass percent: 5-15% of a purple dye compound, 10-25% of a disperse blue dye compound, 14-20% of a disperse orange dye compound and 45-62% of a dispersing agent.

9. The black disperse dye composition according to claim 7 or 8, further comprising a dispersing agent; the dispersing agent comprises MF and/or lignin.

10. Use of a black disperse dye composition according to any one of claims 7 to 9 for dyeing polyester or polyester blend fabrics.

Technical Field

The invention relates to the technical field of dyes, and particularly relates to a purple dye compound and a preparation method thereof, a disperse purple dye, a black disperse dye and application thereof.

Background

The disperse dyes comprise disperse orange dyes, disperse blue dyes, disperse yellow, disperse red, disperse violet and the like, and the disperse black dyes can be obtained by matching a plurality of different disperse dyes according to a certain proportion. Common disperse violet dyes include C.I. disperse violet 26 (formula IV-1), C.I. disperse violet 77 (formula IV-2) and C.I. disperse violet 93 (formula IV-3). Among them, c.i. disperse violet 93 has low production cost and is widely used for preparing disperse black ECT 300%. However, c.i. disperse violet 93 is disclosed as a sensitizing dye that blackens with disperse blue and disperse violet to obtain a disperse black ECT of 300% that is not an environmentally friendly dye and is costly.

Disclosure of Invention

In view of the above, the present invention aims to provide a violet dye compound and a preparation method thereof, a disperse violet dye, a black disperse dye and an application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a purple dye compound, which has a structure shown in a formula I:

in the formula I, X is halogen;

R₁comprising-H or-CH₃；

R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；

R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

Preferably, when X is-Br, R is₁is-H, said R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl；

When the X is-Br, the R₁is-CH₃Said R is₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl；

When the X is-Cl, the R₁is-H, said R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl；

When the X is-Cl, the R₁is-CH₃Said R is₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

Preferably, the violet dye compound has a structure represented by any one of formulas I-1 to I-6:

the invention provides a preparation method of the purple dye compound in the technical scheme, which comprises the following steps:

mixing 2, 4-dinitro-6-haloaniline, nitrosyl sulfuric acid and sulfuric acid, and performing diazotization reaction to obtain a diazonium salt solution;

mixing the diazonium salt solution, substituted aniline, sulfamic acid, sulfuric acid solution and ice, and then carrying out coupling reaction to obtain a purple dye compound with a structure shown in a formula I;

the substituted aniline has a structure represented by formula II:

in the formula II, R₁comprising-H or-CH₃；R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

The invention provides a disperse violet dye, which comprises a violet dye compound and a diffusant; the purple dye compound is the purple dye compound in the technical scheme or the purple dye compound prepared by the preparation method in the technical scheme.

The invention provides a black disperse dye composition, which comprises a purple dye compound and/or a disperse purple dye, a disperse blue dye compound and a disperse orange dye compound;

the purple dye compound is the purple dye compound in the technical scheme or the purple dye compound prepared by the preparation method in the technical scheme;

the disperse violet dye is the disperse violet dye in the technical scheme;

the disperse blue dye compound has a structure shown in formula III:

x in the formula III is halogen;

the disperse orange dye compound has a structure shown in formula IV:

preferably, the black disperse dye composition comprises the following components in percentage by mass: 5-15% of a purple dye compound, 10-25% of a disperse blue dye compound, 14-20% of a disperse orange dye compound and 45-62% of a dispersing agent.

Preferably, the black disperse dye composition further comprises a dispersing agent; the dispersing agent comprises MF and/or lignin.

The invention provides application of the black disperse dye composition in dyeing of polyester or polyester blended fabrics.

The invention provides a purple dye compound, which has a structure shown in a formula I:

in the formula I, X is halogen; r₁comprising-H or-CH₃；R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂And (4) Cl. The purple dye compound provided by the invention has the advantages that through reasonable collocation of electron-absorbing and electron-supplying groups, the dye has deep color, good fastness and good migration property; the purple dye compound provided by the invention does not contain 24 banned azo dyes proposed by European Union in the structure, and belongs to environment-friendly dyes; moreover, the cost of the purple dye compound provided by the invention is obviously reduced compared with that of C.I. disperse violet 93.

The preparation method of the purple dye compound provided by the technical scheme is simple to operate, cheap and easily available in raw materials and low in preparation cost.

The invention provides a disperse violet dye, which comprises a violet dye compound and a diffusant. The disperse violet dye provided by the invention has the advantages of deep color, good fastness, good migration property, low cost, safety and environmental protection.

The invention provides a black disperse dye composition, which comprises a purple dye compound and/or a disperse purple dye, a disperse blue dye compound and a disperse orange dye compound; the purple dye compound is the purple dye compound in the technical scheme or the purple dye compound prepared by the preparation method in the technical scheme; the disperse violet dye is the disperse violet dye in the technical scheme. The purple dye compound contained in the black disperse dye provided by the invention has the advantages of deep color, good fastness and good migration property; moreover, compared with the disperse black dye containing C.I. disperse violet 93, the black disperse dye composition provided by the invention has low cost and better economic benefit.

Further, the purple dye with the structure shown in the formula I, the disperse blue dye with the structure shown in the formula III and the disperse orange dye with the structure shown in the formula IV are mixed to obtain a black disperse dye composition, the dye composition has good compatibility and high lifting force, and the pH value of a dye bath can reach 9 at most. High color fastness and good dyeing performance.

Detailed Description

The invention provides a purple dye compound, which has a structure shown in a formula I:

in the invention, in the formula I, X is halogen, preferably-Br or-Cl; r₁comprising-H or-CH₃；R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂And (4) Cl. In the present invention, when said X is-Br, said R₁is-H, said R₂Preferably comprises-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃Preferably comprises-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl; when the X is-Br, the R₁is-CH₃Said R is₂Preferably comprises-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃Preferably comprises-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂And (4) Cl. In the present invention, when said X is-Cl, said R is₁is-H, said R₂Preferably comprises-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃Preferably comprises-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl; when the X is-Cl, the R₁is-CH₃Said R is₂Preferably comprises-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl, said R₃Preferably comprises-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

In the present invention, the violet dye compound preferably has a structure represented by any one of formulas I-1 to I-6:

the invention provides a preparation method of the purple dye compound in the technical scheme, which comprises the following steps:

mixing 2, 4-dinitro-6-haloaniline, nitrosyl sulfuric acid and sulfuric acid, and performing diazotization reaction to obtain a diazonium salt solution;

mixing the diazonium salt solution, substituted aniline, sulfamic acid, sulfuric acid solution and ice, and then carrying out coupling reaction to obtain a purple dye compound with a structure shown in a formula I;

the substituted aniline has a structure represented by formula II:

in the formula II, R₁comprising-H, -CH₃or-NHCOCH₃；R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

The invention mixes 2, 4-dinitro-6-haloaniline, nitrosyl sulfuric acid and sulfuric acid to carry out diazotization reaction, thus obtaining diazonium salt liquid.

In the present invention, the 2, 4-dinitro-6-halogenoaniline preferably includes 2, 4-dinitro-6-bromoaniline or 2, 4-dinitro-6-chloroaniline. In the present invention, the molar ratio of the 2, 4-dinitro-6-haloaniline to nitrosylsulfuric acid is preferably 1: (1.01-1.10). In the invention, the sulfuric acid is preferably used in the form of an aqueous sulfuric acid solution, and the concentration of the aqueous sulfuric acid solution is preferably 90-98%. In the invention, the concentration of the nitrosyl sulfuric acid solution is preferably 17-43 wt%.

In the invention, the mixing is preferably carried out by mixing 2, 4-dinitro-6-haloaniline and sulfuric acid for 0.1-3 h, then adding nitrosyl sulfuric acid, and mixing at the temperature of preferably 25-30 ℃; the addition mode of the nitrosyl sulfuric acid is preferably dropwise. The mixing method of the invention is not particularly limited, and the raw materials can be uniformly mixed.

In the invention, the diazotization reaction temperature is preferably 25-30 ℃, and the time is preferably 2-5 h; the reaction equation of the diazotization reaction is as follows:

and mixing the diazonium salt solution, the substituted aniline, sulfamic acid, sulfuric acid solution and ice, and then carrying out coupling reaction to obtain the purple dye compound with the structure shown in the formula I.

In the present invention, the molar ratio of the diazonium salt, the substituted aniline, the sulfamic acid and the sulfuric acid in the diazonium salt solution is preferably 1:1.02:0.05: 4.2.

In the invention, the preferred coupling reaction after mixing is to mix the substituted aniline, sulfamic acid and sulfuric acid water solution, ice is added to cool to 0-5 ℃ after the substituted aniline is completely dissolved, and then diazo liquid is added to carry out the coupling reaction.

In the present invention, the substituted aniline has the structure shown in formula II:

in the formula II, R₁comprising-H or-CH₃；R₂comprising-C₂H₅、-CH₂CH＝CH₂、-CH₂CH₂CN or-CH₂CH₂CH₂CH₂Cl；R₃comprising-CH₂CH₂CH₂CH₂Cl、-CH₂CH₂OCH₂CH₂CN、-CH₂CH(OH)CH₂Cl or-CH₂CH(OCOCH₃)CH₂Cl。

In the present invention, the substituted aniline preferably includes N-cyanoethyl-N-2-hydroxy-3-chloropropyl m-toluidine, N-ethyl-N-cyanoethoxyethyl m-toluidine, N-ethyl-N- (2-acetoxyethyl-3-chloro) propanetoluidine, N-N-dichlorobutyl m-toluidine or N-cyanoethyl-N-chlorobutylaniline.

After the coupling reaction, the method preferably further comprises the steps of heating the coupling reaction system to 40-60 ℃, preserving heat for 2-4 hours, filtering, washing the obtained solid product to be neutral, and obtaining the purple dye compound with the structure shown in the formula I.

The invention provides a disperse violet dye, which comprises a violet dye compound and a diffusant; the purple dye compound is the purple dye compound in the technical scheme or the purple dye compound prepared by the preparation method in the technical scheme.

In the invention, the mass percentage of the purple dye compound in the disperse purple dye is preferably 30-50%. In the present invention, the diffusing agent preferably includes lignin and/or sodium methylenebismethylnaphthalene sulfonate (diffusing agent MF).

In the present invention, the preparation method of the disperse violet dye preferably comprises the following steps: and grinding and mixing the purple dye compound, the dispersing agent and water, and drying to obtain the disperse purple dye.

The invention also provides a black disperse dye composition, which comprises a purple dye compound and/or a disperse purple dye, a disperse blue dye and a disperse orange dye; the purple dye compound is the purple dye compound in the technical scheme or the purple dye compound prepared by the preparation method in the technical scheme; the disperse violet dye is the disperse violet dye in the technical scheme.

In the present invention, the disperse blue dye compound has a structure represented by formula III:

in the present invention, X in the formula III is a halogen, and preferably includes chlorine (abbreviated III-Cl, i.e., C.I. disperse blue 291:2) or bromine (abbreviated III-Br, i.e., C.I. disperse blue 291: 1).

In the present invention, the disperse orange dye compound is preferably c.i. disperse orange 288, which has the structure shown in formula IV:

in the present invention, the black disperse dye composition preferably includes the following components in mass percentage: 5-15% of a purple dye compound, 10-25% of a disperse blue dye compound, 14-20% of a disperse orange dye compound and 45-62% of a dispersing agent.

In the present invention, the method for preparing the black disperse dye composition preferably comprises the steps of: mixing a purple dye compound and/or a disperse purple dye, a disperse blue dye compound, a disperse orange dye compound, a dispersing agent and water to obtain slurry; and drying the slurry to obtain the black disperse dye composition.

The invention also provides application of the black disperse dye composition in dyeing of polyester or polyester blended fabrics.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Adding 24mL of 93% sulfuric acid solution into a 250mL three-necked bottle, controlling the temperature at 20-30 ℃, adding 26.8g of 98% 2, 4-dinitro-6-bromoaniline under stirring, stirring for 0.5h until the 2, 4-dinitro-6-bromoaniline is dissolved, then dropwise adding 32.3g of 39% nitrosyl sulfuric acid solution at 25-30 ℃ and reacting for 3h to obtain a diazonium salt solution;

adding 350mL of water and 10mL of sulfuric acid with the concentration of 93% into a 1000mL beaker, adding 27g of N-cyanoethyl-N-2-hydroxy-3-chloropropyl m-toluidine with the purity of 97% and 1g of sulfamic acid under stirring, stirring for 1h, then adding 150g of ice, dropwise adding the diazo liquid under the condition of controlling the temperature to be 0-2 ℃, reacting at the temperature of 0-5 ℃ until diazonium salt disappears, heating to 40-60 ℃, keeping the temperature for 2h, filtering, washing with water to be neutral, draining to obtain 210g of filter cake, and drying to obtain a purple dye compound (51.4g, with the maximum absorption wavelength lambda) with the structure shown in the formula I-1 (51.4g, the maximum absorption wavelength lambda)_max＝545nm)。

Example 2

Adding 28mL of 93% sulfuric acid solution into a 250mL three-necked bottle, controlling the temperature at 20-30 ℃, adding 26.8g of 98% pure 2, 4-dinitro-6-bromoaniline under stirring, stirring for 0.5h until the 2, 4-dinitro-6-bromoaniline is dissolved, dropwise adding 32.3g of 39% nitrosyl sulfuric acid at 25-30 ℃, and reacting for 3h to obtain a diazonium salt solution;

adding 350mL of water and 5mL of sulfuric acid with the concentration of 93 wt% into a 1000mL beaker, adding 22.9g of N-ethyl-N-cyanoethoxyethylaniline with the purity of 97% and 1g of sulfamic acid under stirring, stirring for 1h, then adding 150g of ice, dropwise adding the diazonium solution under the condition of controlling the temperature to be 0-2 ℃, carrying out heat preservation reaction at the temperature of 0-5 ℃ until diazonium salts disappear, heating to 40-60 ℃, carrying out heat preservation stirring for 2h, filtering, washing with water to be neutral, draining to obtain 180g of filter cake, and then drying to obtain a purple dye compound (48.1g, lambda) with the structure shown in formula I-2 (48.1g, lambda)_max＝543nm)。

Example 3

Adding 28mL of 93% sulfuric acid solution into a 250mL three-necked bottle, controlling the temperature at 20-30 ℃, adding 26.8g of 98% pure 2, 4-dinitro-6-bromoaniline under stirring, stirring for 0.5h until the 2, 4-dinitro-6-bromoaniline is dissolved, dropwise adding 32.3g of 39% nitrosyl sulfuric acid at 25-30 ℃, and reacting for 3h to obtain a diazonium salt solution;

adding 400mL of water and 5mL of sulfuric acid with the concentration of 93% into a 1000mL beaker, adding 24.4g of N-ethyl-N-cyanoethoxyethyl m-toluidine solution with the concentration of 97% and 1g of sulfamic acid under stirring, stirring for 1h, then adding 150g of ice, dropwise adding the heavy nitrogen solution under the condition that the temperature is controlled to be 0-2 ℃, carrying out first coupling reaction for 2h under the condition of 0-5 ℃, heating to 40-60 ℃, keeping the temperature and stirring for 2h, filtering, washing with water to be neutral, draining to obtain 118.8g of filter cake, and then drying to obtain the purple dye compound (49.9g, lambda) with the structure shown in formula I-3 (49.9g, lambda)_max＝560nm)。

Example 4

Adding 28mL of 93% sulfuric acid solution into a 250mL three-necked bottle, controlling the temperature at 20-30 ℃, adding 26.8g of 98% pure 2, 4-dinitro-6-bromoaniline under stirring, stirring for 0.5h until the 2, 4-dinitro-6-bromoaniline is dissolved, dropwise adding 32.3g of 39% nitrosyl sulfuric acid solution at 25-30 ℃, and reacting for 3h to obtain a diazonium salt solution;

adding 400mL of water and 5mL of sulfuric acid with the concentration of 93% into a 1000mL beaker, adding 27.6g of N-ethyl-N- (2-acetoxyethyl-3-chloro) propyl m-toluidine solution with the purity of 97% and 1g of sulfamic acid under stirring, stirring for 1h, adding 150g of ice, dropwise adding the diazo solution under the condition of controlling the temperature to be 0-2 ℃, coupling/reacting for 2h under the condition of 0-5 ℃, heating to 40-60 ℃ after the diazo salt disappears, keeping the temperature and stirring for 2h, washing to be neutral by filtering water, pumping to obtain 156.8g of filter cake, and then drying to obtain the purple dye compound (52.7g, lambda) with the structure shown in formula I-4 (the formula I-4 is obtained by adding 52.7g of lambda-ethyl-3-chloro) and stirring for 1h_max＝558nm)。

Example 5

Adding 24mL of 93% sulfuric acid solution into a 250mL three-necked bottle, controlling the temperature at 20-30 ℃, adding 22.2g of 98% 2, 4-dinitro-6-bromoaniline under stirring, stirring for 0.5h until the 2, 4-dinitro-6-bromoaniline is dissolved, dropwise adding 32.3g of 39% nitrosyl sulfuric acid solution at 25-30 ℃, and reacting for 3h to obtain a diazonium salt solution;

400mL of water and 5mL of 93% sulfuric acid were added to a 1000mL beaker, and 29.2g of 97% strength N-N-bis (methylene chloride) was added under stirringStirring the chlorobutyl-m-toluidine solution and 1g of sulfamic acid for 1 hour, adding 150g of ice, dropwise adding the diazo liquid at the controlled temperature of 0-2 ℃, carrying out heat preservation coupling reaction for 2 hours at the temperature of 0-5 ℃, then heating to 40-60 ℃, carrying out heat preservation stirring for 2 hours, filtering, washing with water to be neutral, pumping to dry to obtain 180g of filter cake, and drying to obtain the purple dye compound (50.1g, lambda) with the structure shown in formula I-5_max＝567.5nm)。

Example 6

Adding 24mL of 93% sulfuric acid solution into a 250mL three-necked bottle, controlling the temperature at 20-30 ℃, adding 22.2g of 98% pure 2, 4-dinitro-6-bromoaniline under stirring, stirring for 0.5h until the 2, 4-dinitro-6-bromoaniline is dissolved, dropwise adding 32.3g of 39% nitrosyl sulfuric acid solution at 25-30 ℃, and reacting for 3h to obtain a diazonium salt solution;

adding 350mL of water and 10mL of sulfuric acid with the concentration of 93% into a 1000mL beaker, adding 24.1g of N-cyanoethyl-N-chlorobutylaniline solution with the purity of 97% and 1g of sulfamic acid under stirring, stirring for 1h, then adding 150g of ice, dropwise adding the diazo liquid under the condition of controlling the temperature to be 0-2 ℃, performing coupling reaction for 2h under the condition of 0-5 ℃, heating to 40-60 ℃, then preserving heat, stirring for 2h, filtering, washing with water to be neutral, draining to obtain 170g of filter cake, and then drying to obtain a purple dye compound (48.4g, lambda, of which the structure is shown as a formula I-6) (48.4g, lambda, of the purple dye compound_max＝544nm)。

Comparative example 1

Disperse violet 93 at c.i. having the formula:

the purple dye compound provided by the invention is the same as the diazo component of the C.I. disperse violet 93, the parent bodies of the coupling components are different, the coupling component (namely aniline raw material) of the C.I. disperse violet 93 is synthesized by taking m-phenylenediamine as an initial raw material, and the synthetic route is as follows:

the coupling component (i.e. the substituted aniline raw material) is synthesized by taking m-toluidine or aniline as an initial raw material, and the synthetic route is as follows:

R₁h or-CH₃。

The cost of m-phenylenediamine is 6.8 ten thousand yuan/ton, and the cost of m-toluidine is 1.9 ten thousand yuan/ton, so that the production cost of the purple dye compound provided by the invention is obviously lower than that of C.I. disperse violet 93. From the reaction process and the analysis of the introduced group, when R is₂＝R₃Only one step is needed in the reaction process, so that the production cost is lower than two steps; when R is₂≠R₃When the reaction requires two steps, R₂、R₃All are aliphatic compound groups, the cost of raw materials has difference, the difference is not large, the molecular weight is more than or equal to the molecular weight of ethyl, the obtained intermediate has large molecular weight, more dyes are obtained, the cost difference generated in the process can be offset, and the cost of the second step alkylation reaction of the invention is basically the same as the alkylation cost of the disperse violet 93 C.I.

The purple dye compounds prepared in the embodiments 1-6 of the invention and the C.I. disperse violet 93 in the comparative example 1 are tested according to GB/T30398-2013, and the test shows that the purple dye compounds prepared in the embodiments 1-6 of the invention are not sensitizing dyes, and the C.I. disperse violet 93 is sensitizing dye.

Example 7

10g of the purple dye compound prepared in example 1, 6g of lignin, 14g of a dispersing agent MF and 70g of water are placed in a sand mill, sand-milled until the diffusivity is 4-5 levels, and then dried to constant weight at 80 ℃ to obtain the purple disperse dye.

Examples 8 to 12

A violet disperse dye was prepared according to the method of example 7, which is different from example 7 in that the violet dye compounds used in examples 8 to 12 were prepared in the order of example 2, example 3, example 4, example 5 and example 6. Experimental operations are carried out according to the test of the color light and the intensity of the disperse dye by a high-temperature high-pressure dyeing method GB/T2394-2006 and the standard conditions of soaping color fastness test are implemented by standards such as AATCC 61:2007, GB/T8431-1998 test and evaluation of textile color fastness test and photochromic change, GB/T6152-1997 hot-pressing color fastness test of textile color fastness and the like, wherein the dyeing depth, the sublimation fastness and the light fastness are the test results of the polyester fiber.

Table 1 comparison of dyeing performance test results of the violet disperse dyes of examples 7 to 12 and comparative example 1:

as can be seen from table 1, the performance comparison of the purple disperse dye provided by the present invention and the cloth dyed with c.i. disperse violet 93 at the same concentration shows that the sublimation fastness, light fastness, washing fastness and dye transfer rate are all higher than or equal to that of c.i. disperse violet 93.

Example 13

By mass percentage, 9.5% of the purple dye compound prepared in example 1, 20.9% of a disperse blue dye compound having a structure shown in formula III-Br, 15.5% of a disperse orange dye compound having a structure shown in formula IV, 54.1% of a dispersing agent MF and water are mixed to obtain slurry; and sanding the slurry by a sand mill until the diffusivity is 4-5 grades, and drying at 100 ℃ to obtain the black disperse dye composition.

Example 14

10.3% of the violet dye compound prepared in example 2, 12.3% of a disperse blue dye compound having a structure represented by formula III-Cl, 16.2% of a disperse orange dye having a structure represented by formula IV, 61.2% of a dispersing agent MF, 21.2% of sodium lignosulfonate and water are mixed in percentage by mass to obtain a slurry; and sanding the slurry by a sand mill until the diffusivity is 4-5 grades, and drying at 95 ℃ to obtain the black disperse dye composition.

Example 15

8.7 percent of the purple dye compound prepared in the example 3, 18.9 percent of the disperse blue dye compound with the structure shown in the formula III-Br, 16.8 percent of the disperse orange dye compound with the structure shown in the formula IV, 55.6 percent of the dispersing agent MF and water are mixed by mass percentage to obtain slurry; and sanding the slurry by a sand mill until the diffusivity is 4-5 grades, and drying at 95 ℃ to obtain the black disperse dye composition.

Example 16

By mass percentage, 9.2% of the violet dye compound prepared in example 4, 19.3% of the disperse blue dye compound having a structure shown in formula III-Cl, 16.5% of the disperse orange dye compound having a structure shown in formula IV, 55% of a dispersing agent MF, and water were mixed to obtain a slurry; and sanding the slurry by a sand mill until the diffusivity is 4-5 grades, and drying at 95 ℃ to obtain the black disperse dye composition.

Example 17

10.8% of the violet dye compound prepared in example 5, 18.3% of the disperse blue dye compound having a structure represented by formula III-Br, 16.6% of the disperse orange dye compound having a structure represented by formula IV, 54.3% of a dispersing agent MF and water are mixed by mass percentage to obtain a slurry; and sanding the slurry by a sand mill until the diffusivity is 4-5 grades, and drying at 95 ℃ to obtain the black disperse dye composition.

Example 16

By mass percentage, 11.2% of the violet dye compound prepared in example 6, 19.3% of the disperse blue dye compound having a structure represented by formula III-Cl, 16.5% of the disperse orange dye compound having a structure represented by formula IV, 53.0% of a dispersing agent MF, and water were mixed to obtain a slurry; and sanding the slurry by a sand mill until the diffusivity is 4-5 grades, and drying at 95 ℃ to obtain the black disperse dye composition.

Comparative example 2

300 percent of commercially available disperse black ECT, and the dye composition comprises the following components in percentage by mass: c.i. disperse violet 9330.46%, c.i. disperse blue 291:1 (i.e. III-Br) 32.62% and c.i. disperse orange 28836.92%.

The dyes of examples 13-18 and the dye of comparative example 2 were used to dye polyester fabric simultaneously, and the dyeing depth, sublimation fastness, pH value and six-fiber staining fastness properties were measured, with the test results shown in Table 2:

table 2 dyeing performance of polyester fabric dyed with the dyes of examples 13 to 18 and the dye of comparative example 2 simultaneously

As can be seen from Table 2, the black disperse dye composition prepared by the invention has similar color light to 300% of disperse black ECT, similar or improved sublimation strength, light fastness, washing fastness and dye transfer rate to 300% of disperse black ECT, good environmental protection property, lower production cost than 300% of disperse black ECT, and good economic benefit.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.