WO2014059877A1

WO2014059877A1 - Reactive yellow dye compound

Info

Publication number: WO2014059877A1
Application number: PCT/CN2013/084579
Authority: WO
Inventors: 王晓红; 欧其; 汪仁良; 吕建君
Original assignee: 浙江科永化工有限公司
Priority date: 2012-10-18
Filing date: 2013-09-29
Publication date: 2014-04-24
Also published as: CN103773071A

Abstract

A reactive yellow dye compound as shown in formula (I), said compound being applicable during the printing and dyeing of fibrous materials such as cellulose fibers and polyamide fibers, and also having outstanding sweat resistance and light resistance, exhibiting a high rate of dye uptake and color fixation, having excellent build-up properties, promoting even dyeing and dye-color stability, and being bright and rich in color.

Description

Reactive yellow dye compound

(1) Technical field

The present invention relates to a reactive yellow dye compound, and in particular to an active yellow dye compound having a fluorene structure.

(2) Background Art In the dyeing process, a reactive dye is covalently bonded to a fiber, and a reaction with a medium, particularly an aqueous solution, is carried out to form a dye such as a hydrolyzed dye which cannot be covalently bonded, resulting in solidification. The color ratio is low, generally only 50~80%, which not only causes waste of resources, but also reduces the color fastness of textiles, especially wet processing fastness. Unfixed dyes enter the wastewater and seriously pollute the environment.

In addition, with the improvement of the eco-friendly performance requirements of textiles, higher requirements are imposed on the fastness to light of reactive dyes. When people are working outdoors or exercising outdoors, they often sweat a lot. While sweating the textile, it is also exposed to the sun, and its fading is more severe than when sweat and light act alone. Dyes that are detached from textiles and their by-products of reaction can also directly contact the skin, causing damage to the safety of the human body. The problem of sweat resistance and light fastness of reactive dyes for cotton is currently outstanding.

(III) SUMMARY OF THE INVENTION The object of the present invention is to provide an economical novel active yellow dye compound having a fluorene structure which not only has excellent sweat-light fastness but also has a high fixation rate and Good dyeing, better levelness and wet handling fastness, and non-fixed parts are easy to wash off.

The technical solution adopted by the invention is:

A reactive yellow dye compound having the structure shown in the following formula (I):

In formula ( I ):

Yi and Y ₂ are each independently -CH=CH ₂

Mi. M ₂ is H or alkali gold

-S0 ₂ Yi> -S0 ₂ Y ₂ is preferably a meta or para substitution.

The compound of the formula (I) is preferably one of the following formulas:

( 1 -2)

Among the compounds, Mi and M _{2 are} preferably H, Li, Na or K, more preferably H or Na. The invention also relates to a process for preparing the reactive yellow dye compound, the active yellow dye compound of the formula (I) according to the invention, which can be prepared as a free acid or preferably in the form of an alkali metal salt, according to the usual method, It is conveniently converted from the free acid form to the alkali metal salt form or from the alkali metal salt form to the free acid form, which may be a lithium salt, a sodium salt or a potassium salt. Specifically, the method comprises: firstly, the compounds of the formulae (a), (b) and (c) are weighted in the presence of hydrochloric acid according to a conventional method in the art, and sodium nitrite at 0 ° C to 10 ° C. After nitriding, the obtained diazotide is further reacted with the compound represented by the formula (d) at a pH of 2 to 7.

(b) ( _C )

In the formula (a) ~ (d):

Yi and Y ₂ are each independently -CH=CH ₂

Mi. M ₂ is H or an alkali metal, and the alkali metal is selected from Li, Na or K. Mi, M ₂ is preferably H or Na, and the method can be as follows:

(1) Diazotization: Add the compound of the formula (a) to water and mix well, then cool to 0-5 ° C, add hydrochloric acid, and slowly add 0.5 μC of sodium nitrite solution at 0-5 ° C. Stir at this temperature for 1-3 hours, and remove excess sodium nitrite with sulfamic acid to obtain the diazonium salt of compound (a);

(2) Diazotization: Add compound (b) or (c) to water and mix well, then cool to 0-5 ° C, maintain 0-5 ° C slowly add hydrochloric acid and sodium nitrite, here Stir at a temperature for 0.5 to 2 hours, and remove excess sodium nitrite with sulfamic acid to obtain a diazonium salt of compound (b) or (c), respectively; compounds (b) and (c) are preferably aromatic amines of the same structure. In the formula (I), -S0 ₂ Yi -SO2Y2 is preferably the same substituent and the substitution positions are the same;

(3) One coupling: Add compound (d) to water, dissolve it, add the diazonium salt of step (2) to the solution, control pH 2~3, temperature 5~10 °C, stir until clarification Adjust pH to 5.5~6.5 and control temperature 10 °C, coupling reaction for 2~5 hours to obtain a coupling solution;

(4) Secondary coupling: The diazonium salt obtained by the reaction in the step (1) is added dropwise to the primary coupling solution obtained in the step (3), and the pH is adjusted to 5.8 to 6.2 and the temperature is controlled to 0 to 5 ° C. The reaction is carried out for 2 to 8 hours to obtain a secondary coupling liquid, which is dried to obtain a hydrazine structure represented by the formula (I). Dye compound.

The compounds of the formulae (a) to (d) are known dye intermediates and are conveniently prepared or commercially available. The obtained dye compound of the formula (I) can be isolated according to a known method, for example, salting out with an alkali metal salt (preferably a sodium salt or a potassium salt), filtering and drying.

It should be noted that during the preparation of the compound of the formula (I) of the present invention, one or more by-products of the formula (II) to (VI) are allowed to exist, and the by-products are not particularly separated and may be present in The dyes of formula (I) are commonly used for the coloration of fibrous materials:

(IV) (V)

(VI)

In the above formula (II) to formula (VI), Yi and Y ₂ are each independently -CH=CH ₂ or -Csi^OSC Mi, Mi, M ₂ is H or an alkali metal, and the alkali metal is selected from Li, Na or K. SC Y SO2Y2 is preferably a meta or para substitution, and Mi, M ₂ is preferably H or Na.

The finished dye product prepared by using the compound of the present invention may be present in the form of solid particles, powder or liquid, and usually contains electrolyte salts in the synthesis of common reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, in solid form. Dyes also contain auxiliaries commonly found in commercial dyes, such as buffers that stabilize the pH of aqueous solutions at 3 to 7, such as sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, and disodium hydrogen phosphate. And a small amount of desiccant, or if they are present as a liquid or aqueous solution (including the usual thickeners used in printing pastes).

The reactive dye compound of the invention is suitable for printing and dyeing cellulose fibers, polyamide fibers and fabrics thereof, wherein the cellulose fibers are preferably cotton fibers and recycled fibers, and of course other vegetable fibers such as hemp fibers or fabrics. The polyamide fiber is preferably an animal fiber material including leather, wool or silk, and a synthetic fiber material such as nylon 6, nylon 66 or the like. When the above-mentioned fiber material is printed by using the reactive dye of the present invention, it can be carried out according to a known reactive dye dyeing method, such as a commonly used reactive dye dip dyeing method and pad dyeing method, and the dip dyeing method is to impregnate the fabric with dyeing. In the liquid, the method of gradually dyeing the dye to the fabric is usually carried out by dyeing, fixing, washing, soaping, washing, dehydrating, drying, and the like. The padding is done by first immersing the fabric in dyeing. In the liquid, the fabric is then passed through a roll, the dyeing solution is evenly rolled into the interior of the fabric, and then subjected to steaming or hot-melting treatment, usually by dipping the dyeing solution, drying one (dip-fixing liquid) FAW Steaming or baking, washing with water, soaping, washing, drying, etc.

Generally, the amount of dye used will vary depending on the dyeing requirements on the fabric. When dyeing by dip dyeing, the dyeing depth is generally 0.1 to 10% (dye to fabric weight), bath ratio 1: 2 to 60, preferably. 1 : 10~30, initial dyeing temperature control 30~60°C, dyeing time 10~30 minutes, soaping temperature 85~95 °C, soaping time 10~15 minutes, fixing temperature 60~100°C, solid The color time is 10~50 minutes, and the fixing pH is 9~11. When dyeing by padding method, the rolling rate of cellulose fibers is generally 60-80%, the steaming temperature is 100-103 °C, and the steaming time is 1-3 minutes. In the padding method, the cold-rolled pile dyeing method is used more frequently, and the dye and the alkaline substance are introduced into the pad dyeing machine, and are piled up for 2 to 30 hours at room temperature for fixing, and then thoroughly rinsed. .

When the reactive dye compound of the present invention is applied to the printing and dyeing of fibrous materials such as cellulose fibers and polyamide fibers, it has excellent sweat-resistant performance, high dye uptake rate and high fixing rate, and is improved in liftability, leveling, and dyeing. Good stability, bright and full color.

(4) Description of the drawings

Figure 1 is an iH NMR spectrum of the compound of Example 1.

(5) Specific implementation methods

The present invention is further described below in conjunction with specific embodiments, but the scope of protection of the present invention is not limited thereto:

The dyes characterized by the chemical formula in the examples are the free acid forms of the compounds. It should be noted, however, that they are usually prepared and isolated in the form of an alkali metal salt, preferably a lithium salt, a sodium salt or a potassium salt, and used in the form of a salt thereof for dyeing. Similarly, in the following examples, the starting compound can be used in the synthesis as a free acid or as an alkali metal salt. Example 1:

(1) Diazotization: 20.2 g of o-aminobenzenesulfonic acid was added to 85 mL of water and stirred well, then cooled to 0-5 ° C with ice, and 13.6 g of 31% (w/w) hydrochloric acid was added to maintain 0-5. 27.5g of 30% (w/w) sodium nitrite aqueous solution was slowly added dropwise at °C, and the pH was maintained at 1.0-1.2 for 1.5 hours at this temperature. The excess sodium nitrite was eliminated with sulfamic acid to obtain o-aminobenzene. A diazo solution of sulfonic acid.

(2) Diazotization: Add 65.9g of para-ester (ie (β-hydroxyethyl sulfone sulfate) aniline) to 100mL of water and mix well, then add ice to cool to 0-5 ° C, maintain 0- 24.1 g of 31% hydrochloric acid and 54.6 g of 30% sodium nitrite were slowly added dropwise at 5 ° C, and the mixture was stirred at 0-5 ° C and pH 1.2 for 1 hour. The excess sodium nitrite was removed with sulfamic acid to obtain the weight of the para-ester. Nitrogen solution.

(3) First coupling: 17.8 g of 3,5-diaminobenzoic acid is added to 55 mL of water, and the pH is adjusted to 8.0-8.5 with baking soda. After stirring to dissolve, the para-ester of step (2) is weighed. Nitrogen solution was added to the solution to control pH 2.5-2.8, temperature 5-8 ° C, and stirred until clear. Then, the baking soda was adjusted to pH 5.5-6.5 and the temperature was controlled at 5-10 ° C, and the coupling reaction was carried out for 3 hours to obtain a coupling solution.

(4) Second coupling: The diazonium sulfonate obtained by the reaction of the step (1) is added to the primary coupling solution obtained in the step (3), and the pH is adjusted to 5.8-6.2 and the temperature is controlled to 3. -5 ° C, coupling reaction for 5 hours, drying, mainly to obtain a dye compound of the formula ( 1-1) free acid form of the oxime structure (nuclear magnetic resonance spectrum shown in Figure 1), the dye dyed fabric is yellow

Spectral analysis: S3.71ppm 4.03ppm is equivalent to 8 protons,

Alkane hydrogen; wherein S3.71ppm is a triplet (CH ₂ -S0 ₂ ), S4.03ppm is a triplet (CH2-OSO3H aromatic hydrogen is δ7·43-7·54ρρηι; S9.90ppm, δ10·21, δ10 • 60, S11.30 ppm is a single peak, indicating the presence of four independent hydrogens of different chemical environments, consistent with nitrogen hydrogen at four different positions in the structure. Examples 2 to 4:

According to the preparation method described in Example 1, or a similar method, the difference is that the arylamine in the step (1) and the step (2) is replaced by the intermediate molar amount of the aromatic amine 1 and the aromatic amine 2 in Table 1. The dye of the enamel dye shown in Table 1 can be obtained, and the dyed fabric exhibits a bright yellow color.

Table 1

100 g of cotton fabric was separately added to a dye bath of 1500 g of 45 g/L of sodium chloride and 2 g of the reactive dyes obtained according to Examples 1 to 8 at 60 °C. After dyeing at this temperature for 45 minutes, 20 g/L of sodium carbonate solution was added, and the temperature was maintained for another 45 minutes. Then, the dyeing was rinsed, soaped with a non-ionic detergent for 15 minutes, rinsed and dried, and the basic dyeing performance characteristics were measured as shown in Table 2:

Table 2: Basic staining characteristic values S.E.R.F

In the above table:

The S value represents the amount of dye affinity for the fiber. The large S value indicates that the affinity of the dye to the fiber is large, the color absorption is fast, but the transferability is deteriorated, and the unbonded dye after dyeing is poor in washability.

The E value represents the exhaustion rate of the dye. The value of E is large, indicating that the dye has a high absorption rate. The utilization rate of the material is high, the dyeing depth is good, and the pollution degree of the dyeing sewage is small.

The F value represents the fixing rate of the dye. The large F value indicates that there are many dyes fixed by the covalent bond reaction, and there are few dyes and unreacted dyes which are hydrolyzed, and the dye utilization rate is high.

The R value indicates the level of dye reactivity. The large R value indicates that the dye has a strong covalent bond reaction with the fiber under alkaline conditions, and the reaction rate is fast, but it is too high to cause head-to-tail color difference. It can be seen from the above Table 1 that the S and R values of the reactive dyes of the present invention are moderate, indicating that the affinity and levelness are good; the E value and the F value are large, indicating that the dye has good dyeing depth, high fixing rate, and dye utilization rate! 3⁄4 °

In addition, the color fastness to washing, rubbing and sweat-resistant composites were tested according to the methods specified in GB/T392 GB/T3920 and GB/T14576. The results are shown in Table 3:

Table 3: Color fastness

In summary, the 腙-type structurally active dye of the present invention has good comprehensive dyeing performance when applied to dyeing, has good dyeing depth, high fixing rate, good leveling property, and excellent wet processing fastness.

Claims

A reactive yellow dye compound with the following structure (I)

(J) Formula (I):

Yi and Y2 are each independently -CH=CH ₂

Mb M ₂ is H or an alkali metal. One of the formulas:

(I-2)

Mi, M ₂ is H or alkali metal.

3. The reactive yellow dye compound according to claim 1 or 2, characterized in that in the compound, Mi, M ₂ H, Li, or M

4. The reactive yellow dye compound according to claim 1 or 2, characterized in that in the compound, M _and M are H or Na.