CN104559311A - Polyazo reactive dye compound and preparation method thereof - Google Patents

Abstract

A polyazo reactive dye compound and its preparation method, the compound having a polyazo dye structure of the following formula (I), wherein:, G₁、G₂Each independently represents a structure as shown in formula (II) or formula (III), and is not simultaneously a structure as shown in formula (II) or formula (III). In formulas (I) to (III):R₁、R₂、R₅、R₆Each independently as hydrogen-SO₃M₃、C₁～C₄Alkyl orC₁～C₄Alkoxyl group;R₃For hydrogen orC₁～C₄Alkoxyl group;R₄For -NH₂Or C₁～C₄The alkyl group；Y₁、Y₂Each independently-CH＝CH₂Or-C₂H₄OSO₃M₄；M₁～M₄Each independently represents hydrogen or alkali metal. The multi azo reactive dye compound described in the present invention has good lifting power, dye depth, high fixation rate, and exhaustion rate when applied to the printing and dyeing of the above-mentioned fiber materials. It has excellent color fastness, especially outstanding resistance to washing and rubbing, good dependence on alkali during dyeing, and the alkali dosage can be reduced to one-third of the conventional dosage. It is also suitable for small bath ratio dyeing, with significant economic and social benefits.

Description

A kind of polyazo reactive dye compound and preparation method thereof

(1) Technical field

The invention relates to a polyazo reactive dye compound and a preparation method thereof.

(2) Background technology

Reactive dyes have become the most important type of dyes for textile dyeing such as cellulose fibers due to their bright color, complete chromatogram, simple application, low cost and good fastness. Soda ash is used as a color-fixing agent during dyeing, and the dosage is large (generally 15g/L). After dyeing, a large amount of water is needed to wash away the residual alkali agent, which consumes water resources and increases sewage discharge. Therefore, in recent years, the research on reducing the amount of alkali agent used in dyeing with reactive dyes has become an important topic in domestic research. Researchers and others use substitute alkali instead of soda ash to fix the color of reactive dyes, reducing the amount of alkali agent, but there is still a certain gap between substitute alkali and soda ash in terms of performance.

The direction of the development of new reactive dyes is how to make them have a high degree of dye uptake and color fixation. Because reactive dyes with high dye uptake can reduce the amount of dye contained in wastewater after dyeing, and high color fixation value can simplify the traditional dyeing process "soap elution process" related to fiber reactive dyes, making the whole printing and dyeing The time is reduced and the cost of printing and dyeing is reduced.

As we all know, the extension of the dye conjugate system is beneficial to improve the directness of the dye, thereby improving its dye uptake and color fixation rate. There are also many reports on the development of polyazo novel reactive dyes in the prior art, such as the published patents JPS60130652A, CN103342901A, CN102876077A, etc., due to the increase of the conjugated system, the dye exhaustion rate and color fixation rate have improved a lot, but its lifting power The dyeing and depth are still unsatisfactory, and the washing and rubbing fastness are not good.

(3) Contents of the invention

The object of the present invention is to provide a polyazo reactive dye compound, which not only has good lifting power and deep dyeing property, but also has high color fixation rate and exhaustion rate, and has excellent color fastness, especially water resistance and friction resistance. Excellent fastness, good dependence on alkali during dyeing, can significantly reduce the amount of alkali, and is suitable for dyeing with small liquor ratio, with remarkable economic and social benefits.

The technical scheme adopted in the present invention is:

A kind of polyazo reactive dye compound, described compound has the polyazo dye structure of following formula (I):

In the above formula, G ₁ and G ₂ are each independently a structure shown in formula (II) or formula (III), and are not at the same time the structure shown in formula (II) or formula (III):

In formula (I)～(III):

R ₁ , R ₂ , R ₅ , and R ₆ are each independently hydrogen, -SO ₃ M ₃ , C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy;

R ₃ is hydrogen or C ₁ -C ₄ alkoxy;

R ₄ is -NH ₂ or C ₁ ~ C ₄ alkyl;

Y ₁ and Y ₂ are each independently -CH=CH ₂ or -C ₂ H ₄ OSO ₃ M ₄ ;

M ₁ to M ₄ are each independently hydrogen or an alkali metal.

For the above-mentioned polyazo reactive dyes, the hydrogen atom on the hydroxyl group of the compound of formula (I) can undergo conjugation migration to form the isomer of formula (IV):

Wherein G ₁ , G ₂ , R ₁ to R ₆ , Y ₁ , Y ₂ , M ₁ and M ₂ are the same as defined in the compound of formula (I).

The compounds of formula (I) and formula (IV) described in the present invention can exist in the form of free acid (M ₁ ~ M ₄ is hydrogen) or salt (M ₁ ~ M ₄ is alkali metal), preferably in the form of salt Exist, described salt can be alkali metal salt (M ₁ ～M ₄ is alkali metal), particularly preferably sodium salt (M ₁ M ₄ is sodium), reactive dye composition of the present invention, free acid form ( M ₁ ~ M ₄ is hydrogen) and salt form (M ₁ ~ M ₄ is alkali metal) can be transformed into each other without affecting the dyeing effect. Usually, the dye exists in the form of salt during the preparation process, and it can also be acidified Obtain the free acid form.

The compound of formula (I) described in the present invention is preferably the following structure:

The polyazo reactive dye compound of the present invention can be easily synthesized in a manner well known to those skilled in the art, such as prepared according to conventional diazotization and coupling methods, or prepared as follows:

In the above formula, R ₁ to R ₆ , Y ₁ and Y ₂ have the same definitions as in the compound of formula (I) above;

(1) After stirring the compound of formula (II-1) with water evenly, add sodium nitrite solution at 10-15°C for diazotization reaction, remove unreacted nitrous acid with sulfamic acid after the reaction is completed, and then add For the compound of formula (II-2), control the pH to 3-5, carry out the coupling reaction at 10-15°C, and detect the disappearance of the diazonium salt as the end point;

Adjust the pH of the above reaction solution to 6.0-7 to make it completely dissolved, add sodium nitrite solution, stir evenly, add the mixed solution to hydrochloric acid and carry out diazotization reaction at 10-15°C, use Sulfamic acid removes unreacted nitrous acid to obtain the first diazonium liquid for subsequent use;

(2) After stirring the compound of formula (III-1) with ice water evenly, add hydrochloric acid, and then add sodium nitrite solution at 0-5°C to carry out diazotization reaction. After the reaction is completed, use sulfamic acid to remove unreacted The nitrous acid, obtains the second diazo liquid, for subsequent use;

(3) Add H acid to the second diazonium solution obtained in step (2), control pH 1-2 and heat up to 10-15°C for acidic coupling reaction, and then add the second diazo solution obtained in step (1) after the reaction is completed. A diazonium solution, the pH of which is controlled at 5-6 and the basic coupling reaction is carried out at 10-15°C, and the compound of formula (I) is obtained by drying after the reaction;

Or add H acid to the first diazonium solution obtained in step (1), control the pH to 1-2 and heat up to 10-15°C for acidic coupling reaction, and then add the first diazo solution obtained in step (2) after the reaction is over. The diazotine solution is controlled to have a pH of 5-6, and an alkaline coupling reaction is carried out at 10-15°C. After the reaction is completed, the polyazo reactive dye compound of formula (I) is obtained by drying.

In step (3), those skilled in the art can choose different synthesis methods according to the specific compound of formula (I).

The dyestuff compound of the present invention can exist as solid particle, powdery or liquid form, can be directly used for dyeing, usually in order to stabilize performance, can add auxiliary agent, usually contain the electrolyte salt in common active dyestuff synthesis (as sodium chloride , Potassium Chloride and Sodium Sulfate), the dyes in solid form also contain auxiliary agents commonly used in commercial dyes, such as buffer substances (such as sodium borate, sodium bicarbonate, citric acid) that can stabilize the pH of the aqueous solution at 3 to 7 Sodium, sodium dihydrogen phosphate and disodium hydrogen phosphate), and a small amount of desiccant; when the dye exists as a liquid or aqueous solution, it usually contains common thickeners and stabilizers used in printing and dyeing pastes.

The polyazo reactive dyes of the present invention are applicable to the printing and dyeing of fiber materials such as cellulose fibers, polyamide fibers and fabrics thereof, wherein the cellulose fibers are preferably cotton fibers and regenerated fibers, and can certainly be other vegetable fibers Materials, such as hemp fibers or fabrics; polyamide fibers are preferably animal fiber materials such as leather, wool or silk, and synthetic fiber materials such as nylon 6 and nylon 66.

The beneficial effects of the present invention are: when the polyazo reactive dye compound is applied to the printing and dyeing of the above-mentioned fiber materials, it has good lifting power, good dyeing depth, high color fixing rate and exhaustion rate, and excellent color fastness. , especially for washing and rubbing fastness, good dependence on alkali during dyeing, the amount of alkali can be reduced to 1/3 of the conventional amount, and it is suitable for small liquor ratio dyeing, with remarkable economic and social benefits.

(4) Description of drawings

Figure 1 is a comparison of the lifting power of dyes obtained in Example 1, Example 2 and Comparative Examples 1-3 of the present invention.

(5) Specific implementation methods

The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto (the compound described as formula in the embodiment is expressed in the form of its sodium salt, because it is preferred sodium salt or potassium salt with salt usually Form preparation and separation, those skilled in the art can easily acidify it into an acid form, and will not affect its dyeing performance):

Example 1:

In a 1000ml beaker, add 150g of water and 36.1g of sulfonated para-ester (II-1), stir and beat for 1h, add 23g of 30% sodium nitrite solution at 10-15°C to carry out diazotization reaction for 2h, until the end point Finally, add sulfamic acid to destroy excess nitrous acid, then add 15.1g m-ureidoaniline (II-2), control pH3~5 with baking soda, react at 10~15°C for 4~6h, and detect the disappearance of diazonium salt. end. Adjust the pH of the reaction solution to 6.5-7 to make it completely dissolved, add 23g of 30% sodium nitrite solution, mix well, add the mixed solution to 30g of 30% hydrochloric acid and carry out diazotization reaction at 10-15°C 2 hour, add sulfamic acid to destroy excess nitrous acid after reaching the end point, obtain the first diazonium liquid, and set aside.

In a 1000ml beaker, add 150g of ice water and 28.1g of para-ester (III-1), stir and beat for 1 hour, add 30g of 30% hydrochloric acid, and add 23g of 30% sodium nitrite solution at 0-5°C to carry out diazotization reaction After 2 hours, add sulfamic acid to destroy excess nitrous acid after reaching the end point to obtain the second diazonium solution.

Add 34.1g of H acid to the second diazonium solution, adjust the pH to 1-2, raise the temperature to 10-15°C, perform acidic coupling for 4-6 hours, and detect the disappearance of the diazonium salt as the end point. After the reaction finishes, add the first diazonium liquid again, adjust pH5.5～6 with sodium bicarbonate and carry out alkaline coupling 2～3h, until the disappearance of the diazonium salt is the end point, the gained reaction solution is directly dried to obtain the formula (I- 1) The compound, λmax=635nm in the aqueous solution, can dye the fabric green when applied to dyeing.

Example 2:

According to the preparation method described in Example 1, change 15.1g m-ureidoaniline into 15.0g m-acetamidoaniline to obtain the compound of formula (I-2), λmax=640nm in the aqueous solution, when applied to dyeing, the The fabric is dyed green.

Embodiment 3～19:

According to the preparation method described in Example 1, the difference is that (II-1), (II-2) and (III-1) are replaced with the raw materials in the following Table 1 to obtain the dye compounds shown in the table, Can be used to dye fabrics green when applied to dyeing:

Embodiment 20～21:

According to the preparation method described in Example 1, the difference is that (II-1), (II-2) and (III-1) are replaced with the raw materials in the following Table 2, and the first diazo solution and the second The order of the coupling of diazotine solution and H acid is changed, that is, the first diazo solution is first acidicly coupled with H acid, and then alkaline coupled with the second diazo solution to obtain the dye compounds shown in the table, which are used in Fabric can be dyed green when dyed:

Table 2 Raw materials and dye compounds

Comparative Example 1:

Prepare the dye compound of structure shown in formula (1) by the method described in the embodiment 1 of published patent JPS60130652A:

Comparative example 2:

Prepare the dye compound of structure shown in formula (2) by the method described in the embodiment 1 of published patent CN103342901A:

Comparative example 3:

The dye compound of the structure shown in formula (3) is obtained by the method described in the published patent CN102876077A embodiment 2:

Examples of lifting force:

Weigh the dye compounds obtained in Example 1, Example 2 and Comparative Examples 1 to 3 respectively, and measure the lifting force according to the determination method in GB/T21875-2008. The results are shown in Figure 1. As can be seen from Figure 1, Example 1 and The lifting power of the dye compound obtained in 2 is better than that of the dye compound obtained in Comparative Examples 1-3.

Dyeing example:

At 30°C, the dye compounds obtained in Examples 1 to 21 and the dye compounds obtained in Comparative Examples 1 to 3 were added to the dye bath containing 60g/L sodium sulfate (dye concentration 2.0%, bath ratio 1: 25 ), raise the temperature to 60°C at 2°C/min, dye the fabric for 30 minutes according to this method, add 15g/L soda ash, and dye at this temperature for 60 minutes, then rinse the dyed matter, and use Detergent soap for 15 minutes, rinse and dry. Test its color fastness to washing and rubbing according to the methods determined in ISO105-CO3 and ISO105×12 respectively, and the results are shown in Table 3 below:

Table 3 Color Fastness

As can be seen from Table 3, the washing resistance and the color fastness to rubbing of the reactive dyes obtained by the method for the present invention 1 to 21 are compared with the washing resistance and the color fastness to rubbing of the reactive dyes obtained in comparative examples 1 to 3 0.5 to 1 level higher.

Example of dependence on base:

With the dye compound that embodiment 1 obtains, according to the dyeing method in the above-mentioned dyeing embodiment respectively, just change soda ash concentration, do reference sample with 15g/L soda ash, change soda ash concentration into 5g/L, 10g/L, 20g/L L, 25g/L, measure the intensity under different dyeing conditions according to the method determined in GB/T 2387-2013, the results are shown in Table 4:

Table 4 The influence of the amount of dyeing alkali

Dyeing Process/Soda Ash strength 5g/L 101.73%

10g/L 98.29% 15g/L 100.00% 20g/L 95.26% 25g/L 98.02%

As can be seen from Table 4, the amount of soda ash can be reduced to 5g/L when the dyeing of the embodiment 1 reactive dyes prepared by the method of the present invention is only 1/3 of the conventional amount.

Dependence example on bath ratio:

With the dye compound that embodiment 1 obtains, according to the dyeing method in the above-mentioned dyeing embodiment respectively, just change bath ratio, do reference sample with bath ratio 1: 25, and bath ratio is changed into 1: 10, 1: 20, 1:30, 1:40, according to the method determined in GB/T 2387-2013 to measure the intensity under different dyeing conditions, the results are shown in Table 5:

Table 5 Effect of dyeing bath ratio

Dyeing Process/Liquor Ratio strength 1:10 105.56% 1:20 103.77% 1:25 100.00% 1:30 97.13% 1:40 95.84%

As can be seen from Table 5, the reactive dyes of Example 1 prepared by the method of the present invention are suitable for dyeing with a small liquor ratio of 1:10.

In summary, the polyazo reactive dyes of the present invention have good lifting power and deep dyeing, outstanding washing and rubbing fastness, good dependence on alkali during dyeing, and the amount of alkali can be reduced to the conventional amount. 1/3 of that, and it is suitable for dyeing with small liquor ratio, with remarkable economic and social benefits.

Claims (4)

1. a polyazo reactive dye compound, described compound has the polyazo dye structure of following formula I:

Wherein G ₁, G ₂respective is independently the structure shown in formula II or formula III, and is asynchronously the structure shown in formula II or formula III:

In formula I ~ (III):

R ₁, R ₂, R ₅, R ₆respective is independently hydrogen ,-SO ₃m ₃, C ₁~ C ₄alkyl or C ₁~ C ₄alkoxyl group;

R ₃for hydrogen or C ₁~ C ₄alkoxyl group;

R ₄for-NH ₂or C ₁~ C ₄alkyl;

Y ₁, Y ₂respective independence is-CH=CH ₂or-C ₂h ₄oSO ₃m ₄;

M ₁~ M ₄respective is independently hydrogen or basic metal.

2. polyazo reactive dye compound as claimed in claim 1, is characterized in that: conjugation migration can occur the hydrogen atom on described formula I compound hydroxyl, forms the isomer shown in formula IV:

Wherein G ₁, G ₂, R ₁~ R ₆, Y ₁, Y ₂, M ₁and M ₂identical with the definition in formula I compound.

3. polyazo reactive dye compound as claimed in claim 1 or 2, is characterized in that the polyazo dye structure of formula I is selected from one of following:

2 -->

3 -->

4. a preparation method for polyazo reactive dye compound as claimed in claim 1, comprises the steps:

(1) after the compound of formula (II-1) and water being stirred, add sodium nitrite solution at 10 ~ 15 DEG C and carry out diazotization reaction, react complete thionamic acid and remove unreacted nitrous acid, and then add the compound of formula (II-2), control pH to 3 ~ 5, at 10 ~ 15 DEG C, carry out coupled reaction, detect diazonium salt disappearance and be terminal;

Above-mentioned reaction solution is adjusted pH to 6 ~ 7, makes it complete clearly molten, add sodium nitrite solution, after stirring, mixed solution to be joined in hydrochloric acid and carry out diazotization reaction at 10 ~ 15 DEG C, reacting complete thionamic acid and remove unreacted nitrous acid, obtain the first diazo liquid, for subsequent use;

(2) after the compound of formula (III-1) and frozen water being stirred, add hydrochloric acid, at 0 ~ 5 DEG C, then add sodium nitrite solution again carry out diazotization reaction, react complete thionamic acid and remove unreacted nitrous acid, obtain the second diazo liquid, for subsequent use;

(3) H acid is added in the second diazo liquid obtained toward step (2), control pH 1 ~ 2 is also warming up to 10 ~ 15 DEG C and carries out acid coupling reaction, the first diazo liquid obtained in step (1) is added again after reaction terminates, control pH 5 ~ 6 also carries out alkaline coupling reaction under 10 ~ 15 DEG C of conditions, and reaction terminates rear drying and obtains the polyazo reactive dye compound shown in formula I;

Or add in H acid in the first diazo liquid that step (1) obtains, control pH to 1 ~ 2 are also warming up to 10 ~ 15 DEG C and carry out acid coupling reaction, the second diazo liquid obtained in step (2) is added again after reaction terminates, alkaline coupling reaction is also carried out in control pH to 5 ~ 6 under 10 ~ 15 DEG C of conditions, and reaction terminates rear drying and obtains the polyazo reactive dye compound shown in formula I;

R in above formula ₁~ R ₆, Y ₁and Y ₂identical with the definition in above-mentioned formula I compound.5 -->