阅读说明：本技术 一种蓝色酸性染料的制备方法 (Preparation method of blue acid dye ) 是由 曹世川 于富田 赵腾飞 于 2020-11-17 设计创作，主要内容包括：本发明涉及一种蓝色酸性染料的制备方法,该方法包括如下步骤:(a).1,2-重氮氧基萘-4-磺酸溶解；(b).制备2-萘酚溶液；(c).偶合；将步骤(b)的2-萘酚溶液加入步骤(a)制备的溶液中,进行偶合反应,得偶合液。(d).制备铬化剂溶液；(e).络合：将步骤(d)制备好的铬化剂溶液放入步骤(c)偶合液中,控制pH＝4.5-5.5,升温至105-110℃,保温3小时,降温至80℃以下,取样检测,合格后,得络合液,备用；(f)过滤,干燥。本发明提供的蓝色酸性络合染料的制备方法,具有如下优点：偶合转化率高。缩短反应周期,废水产生少,节省能源。(The invention relates to a preparation method of blue acid dye, which comprises the following steps of (a), dissolving 1, 2-diazoxynaphthalene-4-sulfonic acid; (b) preparing a 2-naphthol solution; (c) coupling; and (c) adding the 2-naphthol solution obtained in the step (b) into the solution prepared in the step (a) for coupling reaction to obtain a coupling solution. (d) Preparing a chromizing agent solution; (e) complexing: putting the chromizing agent solution prepared in the step (d) into the coupling solution in the step (c), controlling the pH value to be 4.5-5.5, heating to 105-; (f) filtering and drying. The preparation method of the blue acid complex dye provided by the invention has the following advantages: the coupling conversion rate is high. The reaction period is shortened, the waste water is less, and the energy is saved.)

1. A preparation method of blue acid complex dye is characterized in that: the method comprises the following steps:

(a) dissolution of 1, 2-diazoxynaphthalene-4-sulfonic acid: adding 1, 2-diazoxynaphthalene-4-sulfonic acid into water, heating to 30-40 ℃, adding ammonium bicarbonate, adjusting pH to 2.0-2.5, and standing until the 1, 2-diazoxynaphthalene-4-sulfonic acid is completely dissolved.

(b) Preparing a 2-naphthol solution;

(c) coupling

And (c) adding the 2-naphthol solution obtained in the step (b) into the solution prepared in the step (a) for coupling reaction to obtain a coupling solution.

(d) Preparing a solution of a chromizing agent

(e) Complexing

And (c) putting the chromizing agent solution prepared in the step (d) into the coupling solution prepared in the step (c), controlling the pH value to be 4.5-5.5, heating to 105-plus 110 ℃, preserving the heat for 3 hours, cooling to below 80 ℃, sampling and detecting, and obtaining a complexing solution for later use after the complexing solution is qualified.

(f) Filtering and drying

And (e) adding diatomite into the complexing solution prepared in the step (e), stirring, clarifying and filtering, collecting filtrate, and spray-drying to obtain the blue acidic complex dye.

2. The process for preparing a blue acid complex dye according to claim 1, wherein: the step (b) is as follows: adding water into 2-naphthol, adding 30% caustic soda liquid, heating to 50-55 deg.C, stirring to dissolve to obtain 2-naphthol solution, and keeping.

3. The process for preparing a blue acid complex dye according to claim 1, wherein: the step (c) is as follows: and (b) adding the 2-naphthol solution obtained in the step (b) into the solution prepared in the step (a), controlling the temperature to be 25-35 ℃ and the pH value to be 10-10.5, maintaining the pH value by using 30% sodium hydroxide, and stirring until the diazonium salt completely disappears to obtain a coupling solution.

4. The process for preparing a blue acid complex dye according to claim 1, wherein: the step (d) is as follows: adding water into a beaker, starting stirring, adding acetic acid, adding sodium bichromate (the content is more than or equal to 98%) while stirring, stirring and dissolving, heating to 70-75 ℃, adding white granulated sugar, stirring and reacting for 2 hours, taking 1ml of sample, spotting on filter paper, observing that a seepage ring is uniform, and determining that no water ring is qualified, and the product can be used for chromizing.

5. The process for preparing a blue acid complex dye according to claim 1, wherein: the pH in step (e) is controlled by using 30% liquid alkali.

6. The process for preparing a blue acid complex dye according to claim 1, wherein: and (e) sampling and detecting in the step (e), developing by using a developing agent (methyl isobutyl ketone: triethylamine: water 5:2:2) through a thin-layer plate method, and observing that the conjugate has no residue, namely the conjugate is qualified.

7. The process for preparing a blue acid complex dye according to claim 1, wherein: the step (f) is as follows: and (d) adding diatomite into the complexing solution prepared in the step (d), stirring for 5 minutes, clarifying and filtering, collecting filtrate, and spray-drying to obtain the blue acidic complex dye.

Technical Field

The invention relates to a preparation method of an acid complex dye, in particular to a novel preparation method of a blue acid complex dye.

Background

The acid dye is a dye containing acid groups in a dye structure, and is divided into strong acid, weak acid, acid medium, acid complex dye and the like according to the difference of the chemical structure and dyeing conditions. The acid dye is combined with amino groups in protein fiber molecules through ionic bonds, and dyeing is carried out under the acidic, weak-acid or neutral conditions. Wherein the acid complex dye has the best light fastness, soaping fastness and dry-wet rubbing fastness. The acid complex dye is prepared by complexing certain acid dye with chromium, cobalt and other metals. It is soluble in water, and its dye product is light-fast and light-fast. Its dye parent body is similar to acid mordant dye, but when preparing dye, metal atom is introduced into azo dye molecule, the ratio of metal atom to dye molecule is 1:1, so that it is also called 1:1 metal complex dye. The dyeing process does not need mordant treatment. Such as acid complex yellow GR (i.e. c.i. acid yellow 99). The other kind of acid complex dye contains hydrophilic groups such as sulfonamido and no sulfonic group in the molecule, and the ratio of metal atoms in the molecule to dye molecules is 1:2, so the acid complex dye is also called as 1:2 metal complex dye. It dyes in neutral or weakly acidic media and is therefore called a neutral dye. Such as neutral gray 2BL (i.e., c.i. acid black 60).

The invention relates to a preparation method of a blue acidic complex dye. In particular, c.i. acid blue 193, and the known published product structure is as follows

The existing synthesis process comprises the following steps:

(1) dissolving 1, 2-diazoxynaphthalene-4-sulfonic acid

Adding 1, 2-diazoxynaphthalene-4-sulfonic acid into a beaker, adjusting the pH value to 2.0-2.2 by using 30% liquid alkali, controlling the temperature to 35-40 ℃, and stirring and dissolving for later use.

(2) Dissolution of 2-naphthol

Adding 2-naphthol into a beaker, adding water, adding 30% liquid caustic soda, heating to 70-80 ℃ for dissolution, and cooling to 50 ℃ after dissolution. And (5) standby.

(3) Coupling of

The dissolved 2-naphthol was added to 1, 2-diazoxynaphthalene-4-sulfonic acid, and the pH was controlled to 10-10.5. Keeping the temperature at 35-40 ℃ for 4 hours, and then heating to 65-70 ℃ for 2 hours. After the coupling is finished, sodium chloride salt is added to separate out a filter cake,

(4) preparation of chromizing agents

Adding water into a beaker, starting stirring, adding acetic acid, adding sodium bichromate (the content is more than or equal to 98 percent) while stirring, stirring and dissolving, heating to 70-75 ℃, slowly adding white granulated sugar, stirring and reacting for 2 hours, and using the mixture for chromizing after the mixture is qualified.

(5) Chromising

Adding water into the coupling compound filter cake, stirring uniformly, complexing with a chromizing agent at 100 ℃ for 10 hours, filtering by salting out after the coupling compound filter cake is qualified, pulping the filter cake, and spraying to obtain the finished dye.

The preparation process has the advantages of long reaction period, high energy consumption, viscous materials in the coupling process, low coupling conversion rate, large amount of wastewater generated by two-step filtration, and great difficulty in wastewater treatment, and is not beneficial to sustainable development of products.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method of a blue acid complex dye.

The technical scheme adopted by the invention is as follows:

a preparation method of a blue acid complex dye comprises the following steps:

(a) dissolution of 1, 2-diazoxynaphthalene-4-sulfonic acid: adding 1, 2-diazoxynaphthalene-4-sulfonic acid into water, heating to 30-40 ℃, adding ammonium bicarbonate, adjusting pH to 2.0-2.5, and standing until the 1, 2-diazoxynaphthalene-4-sulfonic acid is completely dissolved.

(b) Preparing a 2-naphthol solution;

(c) coupling

And (c) adding the 2-naphthol solution obtained in the step (b) into the solution prepared in the step (a) for coupling reaction to obtain a coupling solution.

(d) Preparing a solution of a chromizing agent

(e) Complexing

And (c) putting the chromizing agent solution prepared in the step (d) into the coupling solution prepared in the step (c), controlling the pH value to be 4.5-5.5, heating to 105-plus 110 ℃, preserving the heat for 3 hours, cooling to below 80 ℃, sampling and detecting, and obtaining a complexing solution for later use after the complexing solution is qualified.

(f) Filtering and drying

And (e) adding diatomite into the complexing solution prepared in the step (e), stirring, clarifying and filtering, collecting filtrate, and spray-drying to obtain the blue acidic complex dye.

Preferably, the step (b) is: adding water into 2-naphthol, adding 30% caustic soda liquid, heating to 50-55 deg.C, stirring to dissolve to obtain 2-naphthol solution, and keeping.

Preferably, the step (c) is: and (b) adding the 2-naphthol solution obtained in the step (b) into the solution prepared in the step (a), controlling the temperature to be 25-35 ℃ and the pH value to be 10-10.5, maintaining the pH value by using 30% sodium hydroxide, and stirring until the diazonium salt completely disappears to obtain a coupling solution.

Preferably, the step (d) is: adding water into a beaker, starting stirring, adding acetic acid, adding sodium bichromate (the content is more than or equal to 98%) while stirring, stirring and dissolving, heating to 70-75 ℃, adding white granulated sugar, stirring and reacting for 2 hours, taking 1ml of sample, spotting on filter paper, observing that a seepage ring is uniform, and determining that no water ring is qualified, and the product can be used for chromizing.

Preferably, the pH in step (e) is controlled with 30% liquid alkali.

Preferably, the sample in step (e) is detected, and the coupling compound is developed by a thin layer plate method with a developing agent (methyl isobutyl ketone: triethylamine: water 5:2:2), and the coupling compound is observed to have no residue, namely the coupling compound is qualified.

Preferably, the step (f) is: and (d) adding diatomite into the complexing solution prepared in the step (d), stirring for 5 minutes, clarifying and filtering, collecting filtrate, and spray-drying to obtain the blue acidic complex dye.

The reaction equation related to the invention is as follows:

1) dissolution

2) Coupling of

3) Preparation of chromizing agents

4) Chromising

The invention has the following beneficial effects:

the preparation method of the blue acid complex dye provided by the invention has the following advantages:

1) and the 1, 2-diazoxynaphthalene-4-sulfonic acid adopts ammonium bicarbonate when being dissolved, and the material after coupling has good fluidity and high coupling conversion rate.

2) The chromizing temperature is controlled at 105-110 ℃, and the reaction period is shortened;

3) the coupling compound is directly chromated without filtering;

4) the spraying of the finished product primary pulp does not generate waste water;

5) and the dissolving temperature of the 2-naphthol is reduced to 50-55 ℃, so that the energy is saved.

Detailed Description

In order to understand the present invention, the following examples are further illustrative, but not intended to limit the scope of the present invention.

Example 1

A preparation method of a blue acid complex dye comprises the following steps:

(a) dissolving 1, 2-diazoxynaphthalene-4-sulfonic acid (hereinafter referred to as an oxygen body): adding 100ml of water into a beaker, adding 27.2g of 1, 2-diazoxynaphthalene-4-sulfonic acid with the content of 100 percent, heating to 35-40 ℃, adjusting the pH value to 2.0-2.5 by using ammonium bicarbonate, and standing until the oxygen is completely dissolved.

(b) Dissolution of 2-naphthol

Adding 13.96g of 100 percent 2-naphthol into a beaker, adding 150ml of water and 9.2ml of 30 percent liquid caustic soda, heating to 50-55 ℃, and stirring for dissolving. For standby

(c) Coupling

Adding the material obtained in the step (b) into the material obtained in the step (a), controlling the temperature to be 25-30 ℃ and the pH to be 10-10.2, maintaining the pH by using 30% of sodium hydroxide, and stirring until the diazonium salt completely disappears.

(d) Preparation of chromizing agent

Adding 100ml of water into a beaker, starting stirring, adding 30g of acetic acid, adding 6.75g (the content is more than or equal to 98%) of sodium bichromate while stirring, stirring and dissolving, heating to 70-75 ℃, slowly adding 1.5g of white granulated sugar, stirring and reacting for 2 hours, and obtaining the chromium compound after the product is qualified.

(e) Complexing

And (c) putting the prepared chromium solution into the step (c), adjusting the pH value to 4.5-5.0 by using 30% liquid alkali, slowly heating to 105-110 ℃, preserving the temperature for 3 hours, cooling to below 80 ℃, sampling, detecting by TLC, taking the disappearance of the coupling compound as an end point, and reserving after the coupling compound is qualified.

(f) Filtering and drying

Adding diatomite into the step (e), stirring for 5 minutes, clarifying and filtering, collecting filtrate, and spray drying. 112g of 100% dry dye was obtained.

Example 2

A preparation method of a blue acid complex dye comprises the following steps:

(a) dissolving 1, 2-diazoxynaphthalene-4-sulfonic acid (hereinafter referred to as an oxygen body): adding 100ml of water into a beaker, adding 27.2g of 1, 2-diazoxynaphthalene-4-sulfonic acid with the content of 100 percent, heating to 30-35 ℃, adjusting the pH value to 2.0-2.5 by using ammonium bicarbonate, and standing until the oxygen is completely dissolved.

(b) Dissolution of 2-naphthol

Adding 13.96g of 100 percent 2-naphthol into a beaker, adding 150ml of water and 9.2ml of 30 percent liquid caustic soda, heating to 50-55 ℃, and stirring for dissolving. For standby

(c) Coupling

Adding the material obtained in the step (b) into the material obtained in the step (a), controlling the temperature at 30-35 ℃ and the pH value at 10-10.2, maintaining the pH value by using 30% sodium hydroxide, and stirring until the diazonium salt completely disappears.

(d) Preparation of chromizing agent

Adding 100ml of water into a beaker, starting stirring, adding 30g of acetic acid, adding 6.75g (the content is more than or equal to 98%) of sodium bichromate while stirring, stirring and dissolving, heating to 70-75 ℃, slowly adding 1.5g of white granulated sugar, stirring and reacting for 2 hours, and obtaining the chromium compound after the product is qualified.

(e) Complexing

And (c) putting the prepared chromium solution into the step (c), adjusting the pH value to 4.5-5.0 by using 30% liquid alkali, slowly heating to 105-110 ℃, preserving the temperature for 3 hours, cooling to below 80 ℃, sampling, detecting by TLC, taking the disappearance of the coupling compound as an end point, and reserving after the coupling compound is qualified.

(f) Filtering and drying

Adding diatomite into the step (e), stirring for 5 minutes, clarifying and filtering, collecting filtrate, and spray drying. 110g of 100% dry dye is obtained.

Example 3

A preparation method of a blue acid complex dye comprises the following steps:

(a) dissolving 1, 2-diazoxynaphthalene-4-sulfonic acid (hereinafter referred to as an oxygen body): adding 100ml of water into a beaker, adding 27.2g of 1, 2-diazoxynaphthalene-4-sulfonic acid with the content of 100 percent, heating to 30-35 ℃, adjusting the pH value to 2.0-2.5 by using ammonium bicarbonate, and standing until the oxygen is completely dissolved.

(b) Dissolution of 2-naphthol

Adding 13.96g of 100 percent 2-naphthol into a beaker, adding 150ml of water and 9.2ml of 30 percent liquid caustic soda, heating to 50-55 ℃, and stirring for dissolving. For standby

(c) Coupling

Adding the material obtained in the step (b) into the material obtained in the step (a), controlling the temperature to be 30-35 ℃, maintaining the pH value to be 10.2-10.5, and stirring until the diazonium salt is completely disappeared.

(d) Preparation of chromizing agent

Adding 100ml of water into a beaker, starting stirring, adding 30g of acetic acid, adding 6.75g (the content is more than or equal to 98%) of sodium bichromate while stirring, stirring and dissolving, heating to 70-75 ℃, slowly adding 1.5g of white granulated sugar, stirring and reacting for 2 hours, and obtaining the chromium compound after the product is qualified.

(e) Complexing

And (c) putting the prepared chromium solution into the step (c), adjusting the pH value to 5.0-5.5 by using 30% liquid alkali, slowly heating to 105-110 ℃, preserving the temperature for 3 hours, cooling to below 80 ℃, sampling, detecting by TLC, taking the disappearance of the coupling compound as an end point, and reserving after the coupling compound is qualified.

(f) Filtering and drying

Adding diatomite into the step (e), stirring for 5 minutes, clarifying and filtering, collecting filtrate, and spray drying. 111.6g of 100% dry dye is obtained.

Comparative example 1

A preparation method of a blue acid complex dye comprises the following steps:

(1) dissolving 1, 2-diazoxynaphthalene-4-sulfonic acid

27.2g of 1, 2-diazoxynaphthalene-4-sulfonic acid with the amount of 100 percent is added into a beaker, 100ml of water is added, the pH value is adjusted to 2.0-2.2 by 30 percent liquid alkali, the temperature is controlled to be 35-40 ℃, and the mixture is stirred and dissolved for standby.

(2) Dissolution of 2-naphthol

Adding 13.96g of 100 percent 2-naphthol into a beaker, adding 150ml of water and 9.2ml of 30 percent liquid caustic soda, heating to 70-80 ℃ for dissolution, and cooling to 50 ℃ after dissolution. And (5) standby.

(6) Coupling of

The dissolved 2-naphthol was added to 1, 2-diazoxynaphthalene-4-sulfonic acid, and the pH was controlled to 10-10.5. Keeping the temperature at 35-40 ℃ for 4 hours, and then heating to 65-70 ℃ for 2 hours. After the coupling is finished, sodium chloride salt is added to separate out a filter cake,

(7) preparation of chromizing agents

Preparation of chromizing agents

Adding 100ml of water into a beaker, starting stirring, adding 30g of acetic acid, adding 6.75g (the content is more than or equal to 98%) of sodium bichromate while stirring, stirring and dissolving, heating to 70-75 ℃, slowly adding 1.5g of white granulated sugar, stirring and reacting for 2 hours, and obtaining the chromium compound after the product is qualified.

(8) Chromising

Adding water into the coupling compound filter cake, uniformly stirring, adding a chromizing agent, heating to 100 ℃, performing complex reaction for 10 hours, sampling a TLC plate, taking the coupling compound as an end point, performing salting-out filtration after the coupling compound disappears, pulping the filter cake, and performing spray drying. The 100 percent amount of the finished dye is 104 g.

Examples 1-3 are compared to the comparative example method

The present invention is compared with the comparative example as follows

(1) The temperature of the 2-naphthol is not increased to 70-80 ℃ any more when the 2-naphthol is dissolved, and is changed to 50-55 ℃, so that the steam energy is saved.

(2)1, 2-diazoxynaphthalene-4-sulfonic acid is used for adjusting the pH value, and ammonium bicarbonate is used for increasing the fluidity of the coupling compound and improving the conversion rate of the coupling reaction.

(3) The chromizing time of the invention is reduced from 10 hours to 3 hours, the heat preservation time is shortened, and the cost of electric energy, labor and the like is saved.

(4) The coupling compound of the invention is not salted out and filtered any more, and the primary pulp is chromized, thereby reducing the generation of waste water.

(5) The chromized finished dye raw pulp is sprayed without salting out and filtering, so that the waste water amount is reduced. Meanwhile, the dye loss caused by filtration is reduced, and the finished dye yield is improved by about 5 percent.

Fastness testing of the dyes prepared according to the invention

Dye batches	Soaping	Dry massage	Wet rubbing device	Crabbing	Sun drying	Alkali-resistant sweat	Resistance to chlorination
								Example 1	4	4-5	3	2-3	7	4-5	3-4
Example 2	4	4	3-4	2-3	6-7	4	3-4
								Example 3	4	4-5	3-4	2-3	6-7	4-5	3-4
Comparative example 1	4	4-5	3	2-3	6-7	4	3-4