WO2014059878A1

WO2014059878A1 - Yellow reactive dye compound

Info

Publication number: WO2014059878A1
Application number: PCT/CN2013/084656
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: 2013-09-30
Publication date: 2014-04-24
Also published as: CN103773075A

Abstract

Provided in the present invention is a yellow reactive dye compound having a hydrazone structure, the structure of said compound being shown in formula (I). The reactive dye compound of the present invention can be applied during printing and dyeing to fibrous materials such as cellulose fibers and polyamide fibers, has outstanding sweat resistance and light resistance, exhibits a high rate of dye uptake and color fixation, has excellent build-up properties, promotes even dyeing and dye-color stability, and is bright and rich in color.

Description

Yellow reactive dye compound

(1) Technical field

The present invention relates to a yellow reactive dye compound, and in particular to a yellow reactive 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 An object of the present invention is to provide an economical novel yellow reactive dye compound having a fluorene structure which has excellent sweat fastness to light fastness and an extremely high fixing ratio. 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:

In formula ( I ):

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

M!, M ₂ is H or alkali gold (I), and -SO-Yb -S0 ₂ Y ₂ is preferably a meta or para substitution.

ί one of the preferred compounds:

( 1-1)

(1-2)

Mi, M ₂ is H or an alkali metal.

Preferably, in the compound, Mi and M _{2 are} preferably Mi, 1^ ₂ is 11, Li, Na or K, and more preferably ruthenium or Na.

The invention further relates to a process for the preparation of the yellow reactive dye compound, the yellow reactive dye compound of the formula (I) according to the invention, which may be a free acid (M is H) or preferably an alkali metal salt (M is an alkali metal) Formed in the form of a free, acid form which is conveniently converted to the form of an alkali metal salt or converted from a metal salt form to a 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. Nitriding, the obtained diazotide is coupled with the compound of the formula (d) at a pH of 2 to 8, to obtain the yellow reactive dye compound;

(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 °C to slowly add sodium nitrite solution. 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 and slowly add hydrochloric acid and sodium nitrite. Stir at a temperature for 0.5 to 3 hours, and remove excess sodium nitrite with sulfamic acid to obtain a diazonium salt of compound (b) or (c), respectively; and compounds (b) and (c) are preferably aromatic amines having 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 (1) to the solution, adjust pH to 5.0~5.5 and control temperature 8 °C, coupling reaction 2~ 5 hours, get a coupling solution;

(4) Secondary coupling: The diazonium salt obtained by the reaction in the step (2) is added dropwise to the primary coupling solution obtained in the step (3), stirred to clarify, adjusted to a pH of 5.5 to 7.0, and the temperature is controlled to be 0 to 10. °C, coupling reaction for 3~10 hours, to obtain the second coupling solution, adding hydrochloric acid to adjust the pH value of 1.5-1.8, adding sodium chloride or potassium chloride salting out, filtering and drying to obtain the 腙 structure shown by 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 need not be particularly separated and can be stored ( The dyes of I) are commonly used for the coloration of fibrous materials:

(II) (III)

(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%~10% (dye is percentage of fabric weight), bath ratio is 1:2~60. , preferably 1: 10~30, initial dyeing temperature control 30~60°C, dyeing time 10~30 minutes, soap boiling temperature 85~95°C, soaping time 10~15 minutes, fixing temperature 60~100°C , fixing time is 10~50 minutes, fixing color value is 9~11. When dyeing by padding, the cellulosic fiber has a rolling rate of 60-80%, a steaming temperature of 100-103 °C, and a steaming time of 1-3 minutes. In the padding method, the cold-rolling 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. .

The reactive dye compound according to the present invention is excellent in perspiration-light resistance, high in dyeing rate and fixing rate, good in lifting property, leveling property, dyeing stability, and bright and full color when applied to the printing and dyeing of the above fiber material. .

(4) Description of the drawings

Figure 1 is a 3⁄4 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: 21.6 g of 2-aminobenzenesulfonic acid was added to 190 mL of water and stirred well. After cooling to 0-5 ° C, 15.6 g of 31% (w/w) hydrochloric acid was added to maintain 0-5 °. C slowly adding 30.6 g of a 30% (w/w) aqueous solution of sodium nitrite, stirring at this temperature for 1 hour, and removing excess sodium nitrite with sulfamic acid to obtain diazo of 2-amino-benzenesulfonic acid. liquid.

(2) Diazotization: 70.3g of para-ester (ie (β-hydroxyethylsulfone sulfate) aniline) is added to 190mL of water and stirred uniformly, then cooled to 0-5 ° C, maintaining 0-5 ° C was slowly added dropwise with 26 g of 31% hydrochloric acid and 60 g of 30% sodium nitrite, and the mixture was stirred at this temperature for 1 hour, and excess sodium nitrite was removed with sulfamic acid to obtain a diazo liquid of the para-ester.

(3) Coupling: Add 19g of 3,5-diaminobenzoic acid to 128mL of water. After dissolving, add the diazonium salt of step (1) to the solution, adjust the pH to 5.3-5.5 and control the temperature 5- The coupling reaction was carried out for 3 hours at 8 ° C to obtain a coupling solution.

(4) Coupling: the para-ester diazo solution obtained by the reaction of the step (2) is rapidly added dropwise to the monoazo dye solution obtained in the step (3), and the pH is adjusted to 6.0-7.0 and the temperature is controlled to be 5-10. °C, coupling reaction for 5 hours, to obtain a second coupling solution, adding hydrochloric acid to adjust the pH value of 1.5-1.8, salting out with 375 g of potassium chloride, filtering and drying, mainly obtaining a dye compound of the formula (1 -1) (See Figure 1 for nuclear magnetic resonance spectroscopy), the dye-dyed fabric has a yellow hue.

Spectral analysis: S3.71ppm, S4.03ppm is equivalent to 8 protons,

The alkane hydrogen; wherein S3.71ppm is an obvious quartet (the superposition of two triplets), indicating that the chemical environment of H ¹ , H ^{3 is} slightly different, one with the distal end and the other with the azo type. The structure of the substituents is consistent. For aromatic hydrogen, the oxime type is less absorptive, so the ortho-position hydrogen shift value is smaller, it should be S7.43-7.54ppm hydrogen, because it is 3 hydrogen, indicating the benzene ring of the sulfonic acid group. The 腙-type nitrogen is connected to it and conforms to the structural formula. 59.90 ppm, 510.2 δ 10.60, 511.30 ppm are single peaks, 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

At 60 ° C, 100 g of cotton fabric was separately added to 1500 g of 45 g/L of sodium chloride and gram of the reactive dye obtained in accordance with Examples 1 to 8. 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 large E value indicates that the dye has a high absorption rate. Generally, the dye utilization rate is high, the dyeing depth is good, and the staining 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, according to the methods specified in GB/T392 GB/T3920 and GB/T14576, the water fastness, rubbing resistance and sweat-resistant composite fastness are tested. 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

WO 2014/059878 The Ten Commandments 氺 PCT/CN2013/084656

1. A yellow activity:

In formula ( I ):

Υι, Υ ₂ are each independently -CH=CH ₂

Mb M ₂ is H or an alkali metal.

The yellow reactive dye compound according to claim 1, wherein the compound is one of the following formulas

3)

Mi, M2 is H or an alkali metal.

The yellow reactive dye compound according to claim 1 or 2, wherein in the compound, 1^2 is 11, Li, Na or K.

The yellow reactive dye compound according to claim 1 or 2, wherein, in the compound, Μι, M ₂ is H or Na.