阅读说明：本技术 一种偶氮分散染料化合物及其制备与应用方法 (Azo disperse dye compound and preparation and application method thereof ) 是由 冯高峰 郭小燕 钱红飞 于 2020-06-30 设计创作，主要内容包括：本申请提供一种偶氮分散染料化合物及其制备与应用方法,属于偶合方法制备的单偶氮染料技术领域。在有机溶剂中,将N-乙基-N-羟乙基苯胺、丁二酸酐、DMAP、三乙胺在室温下反应生成酸组分,减压浓缩；在有机溶剂中,将上一步合成的酸与苯甲醛、4-溴苯胺、环己基异腈进行Ugi四组分反应,反应液经过滤、有机溶剂洗涤得到偶合组分；在有机溶剂中,将所得偶合组分与4-硝基苯基重氮盐类化合物在一定温度下偶合,固体经过滤、洗涤、干燥等得到光谱性能多样的新型偶氮分散染料化合物。该制备方法方便并有效调控染料分子量和分子体积,引入酯基和酰胺基,提高染料与纤维的相互作用,在锦纶上的染色性能和色牢度得到很大的提升。(The application provides an azo disperse dye compound and preparation and application methods thereof, belonging to the technical field of monoazo dyes prepared by a coupling method. In an organic solvent, reacting N-ethyl-N-hydroxyethyl aniline, succinic anhydride, DMAP and triethylamine at room temperature to generate an acid component, and concentrating under reduced pressure; in an organic solvent, carrying out Ugi four-component reaction on the acid synthesized in the last step, benzaldehyde, 4-bromoaniline and cyclohexyl isonitrile, filtering reaction liquid, and washing with the organic solvent to obtain a coupling component; in an organic solvent, coupling the obtained coupling component with a 4-nitrophenyldiazonium compound at a certain temperature, filtering, washing, drying and the like, so as to obtain the novel azo disperse dye compound with various spectral properties. The preparation method is convenient and can effectively regulate and control the molecular weight and the molecular volume of the dye, introduce ester groups and amide groups, improve the interaction between the dye and fibers, and greatly improve the dyeing performance and the color fastness on the polyamide fiber.)

1. an azo disperse dye compound, wherein the azo disperse dye compound has the following structural formula:wherein R is₁Is H or Cl, R₂Is H or Cl.

2. The azo disperse dye compound according to claim 1, wherein the structural formula of the azo disperse dye compound is as follows:

3. the azo disperse dye compound according to claim 2, wherein the azo disperse dye compound is prepared by the following steps:

(1) acid synthesis:

adding 14.4mmol succinic anhydride, 1.2mmol DMAP and CH in turn₂Cl₂(15mL), 12.0mmol triethylamine and 12.0mmol N-ethyl-N-hydroxyethylaniline form a reaction mixed solution, the reaction mixed solution is placed at room temperature and stirred for 4 hours, and after the reaction is finished, the reaction solution is subjected to reduced pressure concentration and vacuum drying by using a rotary evaporator;

(2) ugi four-component reaction:

adding 70mL of anhydrous methanol, 14.4mmol of 4-bromoaniline and 14.4mmol of benzaldehyde in sequence, transferring the anhydrous methanol to the acid synthesized in the step (1), and finally adding 12.0mmol of cyclohexyl isonitrile; heating and stirring the reaction mixed solution in an oil bath at the temperature of 80 ℃ for 48h, cooling the reaction solution to room temperature after the reaction is finished, continuously cooling until a large amount of white solid is separated out, performing suction filtration, washing by using an ethyl ester/petroleum ether organic mixed solvent with the volume ratio of 1:5, and drying to obtain a coupling component;

(3) and (3) diazonium salt synthesis:

dissolving 2.37mmol of sodium nitrite with 5mL of water, placing the mixture in an ice water bath for 2min to form a sodium nitrite aqueous solution, mixing the 5mL of water with 5mL of 36.5% hydrochloric acid, dropwise adding the mixture into 2.37mmol of 2-chloro-4-nitroaniline, dissolving the mixture at 40-60 ℃, cooling the solution to room temperature, placing the cooled solution in the ice water bath, dropwise and slowly adding the sodium nitrite aqueous solution, and reacting the solution in the ice water bath for 1h to obtain 2-chloro-4-nitrophenyldiazonium salt after dropwise adding;

(4) coupling reaction:

adding 30mL of methanol into 1.58mmol of coupling component, heating and stirring in an oil bath at 80 ℃ until the coupling component is completely dissolved, cooling to room temperature, slowly dropwise adding 2-chloro-4-nitrophenyldiazonium salt under the condition of ice-water bath, stirring for 24 hours at 0-5 ℃, carrying out suction filtration after the reaction is finished, and washing and drying by using an ethyl acetate/petroleum ether organic mixed solvent with the volume ratio of 1: 5.

4. A preparation method of an azo disperse dye compound is characterized by comprising the following steps:

(1) acid synthesis: adding N-ethyl-N-hydroxyethyl aniline, succinic anhydride, DMAP and triethylamine into an organic solvent at room temperature, reacting to generate corresponding acid, and concentrating a reaction solution under a reduced pressure condition;

(2) ugi four-component reaction: in an organic solvent, benzaldehyde, 4-bromoaniline, cyclohexyl isonitrile and the synthetic acid concentrated in the step (1) are subjected to an Ugi four-component reaction, and then filtering and washing with the organic solvent are carried out to obtain a coupling component;

(3) coupling reaction: coupling the coupling component with a 4-nitrophenyldiazonium compound in an organic solvent, filtering, washing and drying the solid obtained by coupling to obtain the azo disperse dye compound of claim 1.

5. The process for producing an azo disperse dye compound according to claim 4, wherein: in the step (1), the organic solvent is any one of dichloromethane, dichloroethane and acetonitrile; in the step (2), the organic solvent is any one of toluene, methanol, ethanol and acetonitrile.

6. The process for producing an azo disperse dye compound according to claim 4, wherein: in the step (1), the molar ratio of N-ethyl-N-hydroxyethylaniline to succinic anhydride to DMAP to triethylamine is 1: 1.2-1.5: 0.1-0.2: 1-1.5, the reaction temperature is from room temperature to 50 ℃, and the reaction time is 1-5 h.

7. The process for producing an azo disperse dye compound according to claim 4, wherein: in the step (2), the molar ratio of the synthetic acid to the benzaldehyde to the cyclohexyl isonitrile to the 4-bromoaniline is 1:1.2:1:1.2, the reaction temperature is 40-100 ℃, and the reaction time is 36-48 h.

8. The process for producing an azo disperse dye compound according to claim 4, wherein: in the step (3), the molar ratio of the coupling component to the 4-nitrophenyldiazonium salt is 1: 1.5-1.2, the reaction temperature is 0-5 ℃, and the reaction time is 12-36 hours.

9. An application method of an azo disperse dye compound is characterized in that: the azo disperse dye compound according to claim 1, which is used as a dye or as one of the components of a disperse dye in nylon dyeing.

10. The method for using an azo disperse dye compound according to claim 9, wherein the dyeing process comprises: weighing an azo disperse dye compound, fully mixing the azo disperse dye compound with a dispersant NNO according to the mass ratio of 1:1, and adding water to prepare 1g/L dye mother liquor; 1g/L of dye mother liquor, 5g/L of ammonium sulfate mother liquor and 5g/L of dispersant NNO solution are taken, water is added to prepare dye liquor, the dye concentration is 0.5 percent (o.w.f), the ammonium sulfate concentration is 1g/L, the NNO concentration is 1g/L, and the bath ratio is 50: 1; putting chinlon into a dye solution at room temperature, starting dyeing at 40 ℃, increasing the temperature to 120 ℃ at a heating rate of 1 ℃/min, then keeping the temperature for 70min, and then cooling to 90 ℃ at full speed; after dyeing is finished, soaping the dyed sample by using a 2g/L standard soap powder aqueous solution, washing for 15min at 95 ℃ in a bath ratio of 50:1, taking out, washing by using tap water, and airing in a natural state.

Technical Field

The application relates to an azo disperse dye compound and preparation and application methods thereof, belonging to the technical field of monoazo dyes prepared by a coupling method.

Background

Disperse dyes are the most widespread dye class of the current hydrophobic fiber dyeing dyes. The disperse dyes may be azo type, anthraquinone type, heterocyclic type depending on the type of color body. The azo disperse dye compound is the most important type of disperse dye, accounts for about 60 percent, has complete chromatogram, and can obtain different spectral properties and dyeing properties by changing the electronic effect of substituent groups on the diazo component and the coupling component.

Disperse dyes have been developed with the development of synthetic fibers. At present, with the appearance of superfine polyester fibers, environment-friendly polylactic acid fibers, differential terylene easy-to-dye fibers and novel fibers, most of the existing disperse dyes have poor affinity with the fibers, and are easy to generate heat migration after being heated, so that the fibers have poor washing fastness and poor application performance. Therefore, new synthetic methods and strategies are needed to be developed to rapidly obtain novel high-performance disperse dyes with various structures so as to meet the dyeing requirements of the dyes on various fibers.

The magnitude of the acting force between the disperse dye and the fiber fundamentally determines the dyeing performance and the color fastness of the disperse dye. From the analysis of the disperse dye coloring mechanism, the fiber structure and the like, the following methods can be adopted to improve the disperse dye dyeing performance and the color fastness:

1. according to the principle of 'similar compatibility', special functional groups such as ester groups, amide groups and the like are introduced into the disperse dye, and the functional groups such as the ester groups, the amide groups and the like can form hydrogen bonds with fibers, so that stronger interaction is obtained to improve the dyeing performance of the disperse dye;

2. effectively increase the molecular weight of the dye. Along with the increase of molecular weight, the acting force between dye molecules and fibers is increased, and the dyeing properties such as heat migration resistance fastness, sublimation resistance fastness and the like are improved.

The development of a proper synthetic method and a proper synthetic strategy, the effective regulation and control of the molecular weight of the disperse dye and the introduction of a special functional group capable of interacting with fibers are the key points of the development of the high-performance disperse dye. The method has the advantages of simple and easily obtained multi-component reaction raw materials, rapid and efficient reaction, various product skeleton structures and substituent groups, easy regulation and control of molecular weight, and introduction of special groups capable of interacting with fibers, and is an ideal method and strategy for obtaining high-performance disperse dyes.

Disclosure of Invention

The first aspect of the invention aims to provide a novel high-performance azo disperse dye compound which has a remarkable effect on the dyeing performance and color fastness of chinlon as a disperse dye or a disperse dye component.

Specifically, the technical scheme adopted by the scheme is as follows:

an azo disperse dye compound, which has a structural formula as follows:

wherein: r¹Is H or Cl, R²Is H or Cl.

The structural characteristics of the azo disperse dye compound are as follows: has moderate molecular weight and volume, and contains one ester group and two amide groups (RCOO-, -CONR)₂-CONHR), which structural features have a significant influence on the improvement of the dyeing properties and of the colorfastness of the novel dyes, as summarized in detail below:

(1) the effective increase of the molecular volume and the molecular weight of the dye improves the contact surface between the dye and the fiber, and enhances the Van der Waals force between the dye and the fiber, thereby improving the affinity between the dye and the fiber, and improving the dyeing performance and the color fastness of the dye.

(2) By introducing characteristic groups such as ester group and amide group, hydrogen bonds can be formed with hydrogen receiving groups and hydrogen supplying groups in the fibers, and the characteristic groups are suitable for the structure of the polyester fibers, so that the acting force between the characteristic groups and the polyester fibers is enhanced, and the dyeing performance can be improved.

(3) In the synthesis of azo disperse dyes, the number of groups on the diazo component and the electronic effect have an important influence on the maximum absorption wavelength and color of the dye. Under the condition that the coupling components are the same, the azo disperse dyes with different colors can be obtained by selecting different substituted diazo components, thereby providing great convenience for the diversity synthesis of the azo disperse dyes.

Specifically, the structural formula of the azo disperse dye compound is as follows:

the preparation process can be described as follows:

(1) acid synthesis:

succinic anhydride (1.45g, 14.4mmol, 1.2eq), DMAP (146.7mg, 1.2mmol, 0.1eq), CH were added successively₂Cl₂(15mL), triethylamine (1.52mL, 12.0mmol, 1.0eq) and N-ethyl-N-hydroxyethylaniline (1.99mL, 12.0mmol, 1.0 eq). And stirring the reaction mixed solution at room temperature for 4 hours, concentrating the reaction solution under reduced pressure by using a rotary evaporator after the reaction is finished, drying in vacuum, and directly using the residue in the bottle for the Ugi four-component reaction.

(2) Ugi four-component reaction:

anhydrous methanol (70mL), 4-bromoaniline (2.48g, 14.4mmol, 1.2eq) and benzaldehyde (1.53mL, 14.4mmol, 1.2eq) were added sequentially, the acid synthesized in step (1) was switched over with anhydrous methanol, and finally cyclohexyl isonitrile (1.50mL, 12.0mmol, 1.0eq) was added. And heating and stirring the reaction mixed solution in an oil bath at the temperature of 80 ℃ for 48 hours, cooling the reaction solution to room temperature after the reaction is finished, and cooling the reaction solution in a refrigerator until a large amount of white solid is separated out. And (3) carrying out suction filtration, washing the mixture for multiple times by using an organic mixed solvent (the volume ratio of ethyl acetate to petroleum ether is 1:5), and drying the mixture to obtain 6.31g of white solid. The reaction process of the step (1) and the step (2) can be represented by the following reaction formula:

(3) and (3) diazonium salt synthesis:

5mL of water and 5mL of concentrated hydrochloric acid (36.5%) were mixed and added dropwise to 2-chloro-4-nitroaniline (0.41g, 2.37mmol, 1.5eq) to dissolve it at 40 to 60 ℃. After cooling the solution to room temperature, it was placed in an ice-water bath. Sodium nitrite (0.17g, 2.37mmol, 1.5eq) was dissolved in 5mL of water and placed in an ice-water bath for about 2 min. And (3) slowly adding the sodium nitrite aqueous solution dropwise, and reacting in an ice water bath for 1h after the dropwise addition is finished.

(4) Coupling reaction:

30mL of methanol and coupling component 3f (1.00g,1.58mmol,1.0eq) were added, heated and stirred in an oil bath at 80 ℃ until the coupling component was completely dissolved, and then the mixture was cooled to room temperature. Under the condition of ice-water bath, slowly and dropwise adding the 2-chloro-4-nitrophenyldiazonium salt, stirring at 0-5 ℃ for 24 hours, after the reaction is finished, carrying out suction filtration, washing with an organic mixed solvent (the volume ratio of ethyl acetate to petroleum ether is 1:5), drying to obtain a dark red solid, and drying and weighing to obtain 1.06 g.

A second object of the present invention is to provide a method for producing the above azo disperse dye compound, comprising the steps of:

(1) acid synthesis: in an organic solvent, adding a certain amount of N-ethyl-N-hydroxyethylaniline, succinic anhydride, DMAP and triethylamine into a reaction flask for reaction at room temperature. After the reaction is finished, directly carrying out reduced pressure concentration on the reaction liquid to obtain corresponding carboxylic acid for the next step of Ugi reaction;

(2) ugi four-component reaction: in an organic solvent, the acid synthesized in the last step, benzaldehyde, 4-bromaniline and cyclohexyl isonitrile are subjected to an Ugi four-component reaction at a certain temperature. After the reaction is finished, filtering the reaction liquid, and washing the reaction liquid by an organic solvent to obtain a white Ugi product, namely the coupling component of the azo disperse dye.

(3) Coupling reaction: in an organic solvent, the obtained coupling component and a 4-nitrophenyldiazonium compound are coupled at a certain temperature. After the reaction is finished, filtering, washing, drying and the like are carried out on the solid to obtain the novel azo disperse dye compound.

The above preparation process can be represented by the following reaction equation:

preferably, the further settings are as follows:

in the step (1):

the organic solvent is any one of dichloromethane, dichloroethane and acetonitrile.

The molar ratio of the N-ethyl-N-hydroxyethyl aniline to the succinic anhydride to the DMAP to the triethylamine is 1: 1.2-1.5: 0.1-0.2: 1-1.5.

The reaction temperature is between room temperature and 50 ℃, and the reaction time is 1-5 h.

In the step (2):

the organic solvent is any one of toluene, methanol, ethanol or acetonitrile.

The molar ratio of the synthetic acid to the benzaldehyde to the cyclohexyl isonitrile to the 4-bromoaniline is 1:1.2:1: 1.2.

The reaction temperature is 40-100 ℃, the reaction condition is mild, and the reaction time is 36-48 h.

In the step (3):

the molar ratio of the coupling component to the 4-nitrophenyldiazonium salt is: 1: 1.5-1.2.

The reaction temperature is 0-5 ℃, and the reaction time is 12-36 h.

The third aspect of the invention aims to provide an application of the azo disperse dye compound in dyeing of nylon fabrics, and in the application process, the azo disperse dye compound can be directly used as disperse red for addition, and can also be used as one component of disperse dye to be mixed with other components for addition. The dyeing process comprises the following steps: weighing an azo disperse dye compound, fully mixing the azo disperse dye compound with a dispersant NNO according to the mass ratio of 1:1, and adding water to prepare 1g/L dye mother liquor; 1g/L of dye mother liquor, 5g/L of ammonium sulfate mother liquor and 5g/L of dispersant NNO solution are taken, water is added to prepare dye liquor, the dye concentration is 0.5 percent (o.w.f), the ammonium sulfate concentration is 1g/L, the NNO concentration is 1g/L, and the bath ratio is 50: 1; putting chinlon into a dye solution at room temperature, starting dyeing at 40 ℃, increasing the temperature to 120 ℃ at a heating rate of 1 ℃/min, then keeping the temperature for 70min, and then cooling to 90 ℃ at full speed; after dyeing is finished, soaping the dyed sample by using a 2g/L standard soap powder aqueous solution, washing for 15min at 95 ℃ in a bath ratio of 50:1, taking out, washing by using tap water, and airing in a natural state.

The preparation process has the following remarkable technical effects:

firstly, coupling components with different molecular weights and different molecular volumes can be obtained by changing any component (substituent or structure) of initial Ugi four-component reaction, and the molecular volume and molecular weight of the novel disperse dye can be effectively controlled, so that the dyeing property and color fastness of the disperse dye can be regulated and controlled.

Secondly, by the preparation method of the invention, an ester group and two amide groups are introduced into the novel disperse dye, and the ester group and the amide groups can form interaction with fibers to improve the dyeing performance.

Thirdly, the invention can obtain series of novel disperse dyes with different spectral properties by adopting different diazonium salts, provides a novel strategy and method for the diversity synthesis of novel high-performance azo disperse dyes and further embodies the application.

The invention is further described in detail below with reference to the following figures and detailed description.

Drawings

FIG. 1 is a NMR chart of a coupling component 3f prepared in example 1;

FIG. 2 is a nuclear magnetic resonance hydrogen diagram of an azo disperse dye compound 1fb prepared in example 2.

Detailed Description