阅读说明：本技术 一种用于碱性染色的双偶氮杂环类分散染料及其制备方法 (Bisazo heterocyclic disperse dye for alkaline dyeing and preparation method thereof ) 是由 李敏 付少海 苏婧 王刘阳 于 2021-01-06 设计创作，主要内容包括：本发明公开了一种用于碱性染色的双偶氮杂环类分散染料及其制备方法,属于精细化工技术领域。本发明提供了一种用于碱性染色的双偶氮杂环分散染料的制备方法,第一步以杂环衍生物为重氮组分制备杂环重氮盐,并与二萘酚在酸性条件发生偶合反应制备单偶氮杂环分散染料滤饼；第二步以制备的单偶氮杂环分散染料为偶合组分与另一份重氮盐在碱性条件下发生偶合反应制备双偶氮杂环分散染料。用于解决现有的耐碱型分散染料可以在7≤pH≤14条件下应用,但碱剂只能为碳酸钠、碳酸氢钠、磷酸三钠、磷酸二氢钠或磷酸氢二钠等而不能为强碱NaOH的问题,这限制了该类染料在涤纶织物前处理和染色一浴染色法中的应用。(The invention discloses a bisazo heterocyclic disperse dye for alkaline dyeing and a preparation method thereof, belonging to the technical field of fine chemical engineering. The invention provides a preparation method of a bisazo heterocyclic disperse dye for alkaline dyeing, which comprises the following steps of preparing heterocyclic diazonium salt by taking a heterocyclic derivative as a diazo component, and performing coupling reaction with dinaphthol under an acidic condition to prepare a filter cake of the monoazo heterocyclic disperse dye; and the second step takes the prepared monoazo heterocyclic disperse dye as a coupling component to carry out coupling reaction with another part of diazonium salt under the alkaline condition to prepare the disazo heterocyclic disperse dye. The method is used for solving the problem that the existing alkali-resistant disperse dye can be applied under the condition that the pH value is more than or equal to 7 and less than or equal to 14, but the alkali agent can only be sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium dihydrogen phosphate or disodium hydrogen phosphate and the like, but can not be strong-base NaOH, thereby limiting the application of the dye in the pretreatment and dyeing one-bath dyeing methods of polyester fabrics.)

1. The disazo heterocyclic disperse dye is characterized by having a structural general formula as follows:

wherein R is₁、R₂＝-H、NO₂；

Wherein R is₁、R₂、R₃＝-H、-OCH₃Halogen, NO₂；

Wherein R is₁、R₂＝-H、NO₂；

Wherein R is₁、R₂、R₃＝-H、-OCH₃Halogen, NO₂；

Wherein R is₁、R₂、R₃-H, -CN, halogen, NO₂。

2. A process for preparing a disazo heterocyclic disperse dye according to claim 1, comprising the steps of: firstly, preparing heterocyclic diazonium salt by taking heterocyclic derivative as a diazo component, and performing coupling reaction with dinaphthol under an acidic condition to prepare a monoazo heterocyclic disperse dye filter cake; and the second step takes the prepared monoazo heterocyclic disperse dye as a coupling component to carry out coupling reaction with another part of diazonium salt under the alkaline condition to prepare the disazo heterocyclic disperse dye.

3. Method according to claim 2, characterized in that it comprises the following steps:

(1) preparation of a filter cake of the monoazo heterocyclic disperse dye: dissolving heterocyclic diazo component in acid, adding diazo reagent at 0-5 deg.C, and reacting for 0.5-2h at the temperature to obtain arylamine diazonium salt; dissolving dinaphthol in alkali, cooling to 10-15 ℃, adding the dinaphthol into the prepared arylamine diazonium salt, reacting for 30-90min, and then carrying out suction filtration, water washing and drying;

(2) preparing a filter cake of the bisazo heterocyclic disperse dye: dissolving the prepared monoazo disperse dye in a mixed solution of sodium hydroxide and a surfactant at 50-60 ℃, cooling for later use, slowly dripping the other part of diazonium salt, reacting at 10-15 ℃ for 1-5h after dripping is finished, and performing suction filtration, washing and drying;

(3) preparation of disazo heterocyclic disperse dye: uniformly mixing a certain amount of the bisazo heterocyclic disperse dye filter cake and a high-temperature dispersing agent, and uniformly grinding in a sand mill to obtain the bisazo heterocyclic disperse dye.

4. A colorant comprising the disazo heterocyclic disperse dye according to claim 1.

5. Use of a disazo heterocyclic disperse dye according to claim 1 or a colorant according to claim 4 for dyeing textiles.

6. The use of claim 5, wherein the textile comprises any one of a fiber, yarn, carpet-like fabric, woven fabric, knitted fabric, thermal wadding, nonwoven fabric, apparel, home textiles, upholstery, medical hygiene products, or special work wear.

7. A method for dyeing textile materials, characterized in that the method is to dye textile materials with the disazo heterocyclic disperse dye according to claim 1.

8. Dyeing process according to claim 7, characterized in that the dyeing system has a pH of between 3 and 14.

9. The dyeing method according to claim 8, characterized in that when the dyeing system pH is an alkaline environment, the alkaline agent is a strong base or a weak base.

Technical Field

The invention relates to a bisazo heterocyclic disperse dye for alkaline dyeing and a preparation method thereof, belonging to the technical field of fine chemical engineering.

Background

The current situations of energy conservation and emission reduction, clean production technology, high water consumption, high energy consumption and high pollution discharge of textile printing and dyeing are important problems to be solved urgently at present in the textile printing and dyeing industry. Because of its excellent physical and chemical properties, polyester fiber is widely used in clothing, home textile, military special fabric and industrial textile, and is the most widely used synthetic fiber variety with the largest output in the world. However, in the dyeing and finishing process of the terylene and the blended fabrics thereof, the fabric pretreatment (including desizing, scouring, alkali decrement and other steps) and the reduction cleaning after dyeing are carried out under alkaline conditions, particularly the scouring and the alkali decrement are carried out under the condition of strong alkalinity (NaOH), and the disperse dye dyeing in the intermediate link is an acid bath (pH 4-4.5). The whole dyeing process has the advantages of repeated neutralization and water washing, long process flow and high energy and water consumption. The development of the disperse dye for dyeing under the strong alkaline condition can realize the one-bath pretreatment and dyeing of the polyester fabric, and has the advantages of obvious energy conservation and emission reduction.

Disclosure of Invention

[ problem ] to provide a method for producing a semiconductor device

The technical problems to be solved in practice by the invention are as follows: provides a bisazo heterocyclic disperse dye which has better alkali-resistant stability under strong alkali condition and is suitable for alkali dyeing.

[ technical solution ] A

In order to solve the problems, the invention provides a preparation method of a bisazo heterocyclic disperse dye for alkaline dyeing, which is used for solving the problem that the existing alkali-resistant disperse dye can be applied under the condition that the pH value is more than or equal to 7 and less than or equal to 14, but the alkali agent can only be sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium dihydrogen phosphate or disodium hydrogen phosphate and the like but not be strong alkali NaOH, so that the application of the dye in the pretreatment and dyeing one-bath dyeing methods of polyester fabrics is limited.

The first purpose of the invention is to provide a bisazo heterocyclic disperse dye, the structural general formula of which is shown as follows:

wherein R is₁、R₂＝-H、NO₂；

Wherein R is₁、R₂、R₃＝-H、-OCH₃Halogen, NO₂；

Wherein R is₁、R₂＝-H、NO₂；

Wherein R is₁、R₂、R₃＝-H、-OCH₃Halogen, NO₂；

Wherein R is₁、R₂、R₃-H, -CN, halogen, NO₂。

The second object of the present invention is to provide a method for preparing the above-mentioned disazo heterocyclic disperse dye, which comprises the steps of: firstly, preparing heterocyclic diazonium salt by taking heterocyclic derivative as a diazo component, and performing coupling reaction with dinaphthol under an acidic condition to prepare a monoazo heterocyclic disperse dye filter cake; and the second step takes the prepared monoazo heterocyclic disperse dye as a coupling component to carry out coupling reaction with another part of diazonium salt under the alkaline condition to prepare the disazo heterocyclic disperse dye.

In one embodiment of the invention, the method comprises the steps of:

(1) preparation of a filter cake of the monoazo heterocyclic disperse dye: dissolving heterocyclic diazo component in acid, adding diazo reagent at 0-5 deg.C, and reacting for 0.5-2h at the temperature to obtain arylamine diazonium salt; dissolving dinaphthol in alkali, cooling to 10-15 ℃, adding the dinaphthol into the prepared arylamine diazonium salt, reacting for 30-90min, and then carrying out suction filtration, water washing and drying;

(2) preparing a filter cake of the bisazo heterocyclic disperse dye: dissolving the prepared monoazo disperse dye in a mixed solution of sodium hydroxide and a surfactant at 50-60 ℃, cooling for later use, slowly dripping the other part of diazonium salt, reacting at 10-15 ℃ for 1-5h after dripping is finished, and performing suction filtration, washing and drying;

(3) preparation of disazo heterocyclic disperse dye: uniformly mixing a certain amount of the bisazo heterocyclic disperse dye filter cake and a high-temperature dispersing agent, and uniformly grinding in a sand mill to obtain the bisazo heterocyclic disperse dye.

In one embodiment of the present invention, preferably, in step (1), the acid may be any one or more of hydrochloric acid, propionic acid, concentrated sulfuric acid (98%), diluted sulfuric acid (40 to 70%), phosphoric acid, and the like, and the mass ratio of the intermediate of the diazo component to the acid is 1: (2.5-3.5) to ensure the complete dissolution of the raw materials.

In one embodiment of the present invention, in step (1), the diazotizing agent is sodium nitrite or nitrosylsulfuric acid, and the molar ratio of the intermediate diazo component to the diazotizing agent is 1: (1.1-1.2) to ensure the diazotization component to be completely diazotized.

In one embodiment of the present invention, in step (1), the coupling component is 1, 4-dinaphthol or 1, 3-dinaphthol.

In one embodiment of the present invention, the diazo component in step (1) may be aminobenzothiazole, aminobenzoisothiazole, aminothiazole, aminoisothiazole or aminothiophene.

In one embodiment of the present invention, in the step (1), the base is any one or more of sodium hydroxide, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, etc., and has a concentration of 2 to 8g/L, so as to sufficiently dissolve the coupling component.

In one embodiment of the present invention, in the step (2), the concentration of sodium hydroxide is 100 to 250g/L to sufficiently dissolve the naphthol type monoazo disperse dye.

In one embodiment of the present invention, in step (2), the diazonium salt may be the same as or different from the diazonium salt in step (1).

In one embodiment of the present invention, in step (2), the surfactant is one or more of nekal BX, Tween-80, JFC, SDS, NNO, MF, etc., and is used in an amount of 0.05-1.0% by weight.

In one embodiment of the present invention, in step (3), the high temperature type dispersant is one or more of MF, NNO, 85A and AD-4600, and the amount of the high temperature type dispersant is: the dosage of the disperse dye is (0.45-0.85): 1.0, w/w.

It is a third object of the present invention to provide a colorant comprising the above-mentioned disazo heterocyclic disperse dye.

The fourth purpose of the invention is to provide an application of the double-azo heterocyclic disperse dye or the colorant in textile dyeing.

In one embodiment of the present invention, the textile includes any one of a fiber, a yarn, a carpet-like fabric, a woven fabric, a knitted fabric, a thermal wadding, a filling, a nonwoven fabric, a garment, a clothing accessory, a home textile, a decorative accessory, a medical hygienic article, or a special work garment.

A fifth object of the present invention is to provide a method for dyeing textile materials with the above-mentioned disazo disperse dyes.

In one embodiment of the invention, the dyeing system has a pH of from 3 to 14.

In one embodiment of the present invention, when the dyeing system pH is an alkaline environment, the alkaline agent is a strong base or a weak base.

The invention has the beneficial effects that:

the invention provides a disazo heterocyclic disperse dye for alkaline dyeing, which is used for solving the problem that the existing alkali-resistant disperse dye can be applied under the condition that the pH value is more than or equal to 7 and less than or equal to 14, but the alkali agent can only be sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium dihydrogen phosphate or disodium hydrogen phosphate and the like but not be strong-base NaOH, and the application of the dye in the pretreatment and dyeing one-bath dyeing methods of polyester fabrics is limited.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

Example 1: bisazo heterocyclic disperse dye

A disazo heterocyclic disperse dye has a structural formula as follows:

the preparation method of the disazo heterocyclic disperse dye comprises the following steps: in a 500mL three-necked flask, 19.50g (0.10mol) of 3-amino-5-nitrobenzoisothiazole and 78.00g of 98% concentrated sulfuric acid were added and stirred to be completely dissolved. At-5-0 deg.c, 31.75g (M127, 40%) nitrosyl sulfuric acid is slowly added, and then a certain amount of propionic acid is slowly added, and the starch potassium iodide paper shows slight blue color. The reaction was maintained at 0-5 ℃ for 4h and excess nitrous acid was eliminated with sulfamic acid. 5.50g (0.05mol) of 1, 3-dinaphthol were weighed out in 10g of 10% sodium hydroxide and 0.11g of JFC, and the diazo salt was added dropwise to the coupling component while maintaining the reaction temperature at 10-15 ℃. The end of the reaction was detected with H acid. After the reaction is finished, carrying out suction filtration, washing with water and drying. The obtained dye is recrystallized in absolute ethyl alcohol, filtered and dried. Weighing 10g of prepared bisazo heterocyclic disperse dye and 6g of 85A, adding water, pulping, mixing uniformly, grinding and dispersing by using a grinder, and spray drying to obtain a finished product.

Example 2: bisazo heterocyclic disperse dye

A disazo heterocyclic disperse dye has a structural formula as follows:

the preparation method of the disazo heterocyclic disperse dye comprises the following steps: a150 mL beaker was charged with 6.24g of ice and 37.38g of 98% concentrated sulfuric acid by mass, and 8.76g of 5, 6-dichlorobenzothiazole (0.04mol) was slowly added and stirred until completely dissolved. The beaker is placed in an ice bath environment, 13.97g of nitrosyl sulfuric acid (0.044mol) with the mass fraction of 40 percent is slowly added after the temperature is reduced to 0-5 ℃. 44.38g of ice and 44.38g of concentrated sulfuric acid with the mass fraction of 98 percent are weighed and cooled to 0-5 ℃ in an ice bath. The 5, 6-dichlorobenzothiazole solution was slowly added to the diluted sulfuric acid solution and reacted at 0-5 ℃ for 3 hours. The end of the reaction was judged by adding a drop of diazo liquid to an ice water solution and observing the presence of solid particles. After the diazotization reaction reaches the end point, urea is added to eliminate the excess nitrous acid. 2.20g (0.02mol) of 1, 3-dinaphthol were weighed out in 5g of 10% sodium hydroxide and 0.55g of JFC, and the diazo salt was added dropwise to the coupling component while maintaining the reaction temperature at 10-15 ℃. The end of the reaction was detected with H acid. After the reaction is finished, carrying out suction filtration, washing with water and drying. The obtained dye is recrystallized in absolute ethyl alcohol, filtered and dried. Weighing 10g of prepared bisazo heterocyclic disperse dye and 6g of 85A, adding water, pulping, mixing uniformly, grinding and dispersing by using a grinder, and spray drying to obtain a finished product.

Example 3: application of disazo heterocyclic disperse dye in dyeing aspect

The disazo heterocyclic disperse dyes prepared in the examples 1 and 2 are used for dyeing terylene under the following dyeing conditions: at the temperature of 130 ℃, the time is 30min, the addition amount of dye in the dye liquor is 20% owf, and the dye liquor also comprises 2g/L NaOH.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.