A REACTIVE DYE COMPOUND AND PREPARATION METHOD AND APPLICATION THEREOF

Abstract

A reactive dye compound and preparation method and application thereof. The reactive dye compound is a compound of the following formula (I) or an alkali metal salt thereof, in formula (I), D.sup.1 and D.sup.2 are each independently the group of the following formula (a) or (b). The reactive dye compound is capable of applying in printing and dyeing of cellulosic fibers, polyamide fibers or their fabrics. The reactive dye compound of the present invention has a novel structure, good washing fastness and rubbing fastness, and good fiber-bonding stability, and are suitable for dyeing and printing of fibers such as cotton, rayon, silk, viscose, and wool.

##STR00001##

Claims

1. A reactive dye compound, which is a compound of the following formula (I) or an alkali metal salt thereof: ##STR00096## in formula (I): D.sup.1 and D.sup.2 are each independently the group of the following formula (a) or (b): ##STR00097## in the above formulae (I), (a) and (b): R.sup.1 and R.sup.2 are each independently hydrogen, —COR.sup.7, C.sub.1˜C.sub.4 alkyl or C.sub.1˜C.sub.4 alkyl substituted by hydroxyl, sulfo or carboxyl, in which R.sup.7 is C.sub.1˜C.sub.4 alkyl, C.sub.2˜C.sub.4 alkenyl or —NH.sub.2; R.sup.3 is hydrogen, C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkoxy, carboxyl or sulfo; R.sup.4˜R.sup.6 are each independently hydrogen, C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkoxy or sulfo; X.sup.1 and X.sup.2 are each independently —SO.sub.2Y.sup.1, —NHCO(CH.sub.2).sub.pSO.sub.2Y.sup.2 or —CONH(CH.sub.2).sub.qSO.sub.2Y.sup.3, in which Y.sup.1˜Y.sup.3 are each independently —CH═CH.sub.2, —CH.sub.2CH.sub.2OSO.sub.3H or —CH.sub.2CH.sub.2Cl, p=1-3 and q=1-3.

2. The reactive dye compound as claimed in claim 1, wherein both D.sup.1 and D.sup.2 are the group of formula (a) or (b).

3. The reactive dye compound as claimed in claim 1, wherein both D.sup.1 and D.sup.2 are the group of formula (a).

4. The reactive dye compound as claimed claim 1, wherein R.sup.1 and R.sup.2 are each independently hydrogen, —COR.sup.7, in which R.sup.7 is methyl or —NH.sub.2; and R.sup.3 is hydrogen, methyl, methoxy, carboxyl or sulfo.

5. The reactive dye compound as claimed in claim 1, wherein R.sup.4˜R.sup.6 are each independently hydrogen, methyl, methoxy or sulfo; X.sup.1 and X.sup.2 are each independently —SO.sub.2Y.sup.1, —NHCOCH.sub.2CH.sub.2SO.sub.2Y.sup.2 or —CONHCH.sub.2CH.sub.2SO.sub.2Y.sup.3, in which Y.sup.1˜Y.sup.3 are each independently —CH═CH.sub.2 or —CH.sub.2CH.sub.2OSO.sub.3H.

6. The reactive dye compound as claimed in claim 1, wherein the group of formula (a) is selected from the group consisting of the following groups: ##STR00098## ##STR00099##

7. The reactive dye compound as claimed in claim 1, wherein the group of formula (b) is selected from the group consisting of the following groups: ##STR00100##

8. The reactive dye compound as claimed in claim 1, wherein the compound of formula (I) is selected from the group consisting of the following structures: ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117##

9. The reactive dye compound as claimed in claim 1, wherein the alkali metal salt is sodium salt or potassium salt.

10. A preparation method of the reactive dye compound as claimed in claim 1, comprising: (1) diazotization reaction: according to needs, the aromatic amine compounds of formulae (IIa), (IIb) and/or (IIc) are subjected to diazotization reaction, respectively, thereby obtaining corresponding diazonium salts; (2) coupling reaction: 3,5-dihydroxybenzoic acid is added with water and beaten, and the resulting 3,5-dihydroxybenzoic acid solution is subjected to the first coupling reaction with the diazonium salt of the aromatic amine compound formula (IIa) obtained in the step (1), then the first-coupling product is subjected to the second coupling reaction with the diazonium salt of the aromatic amine compound formula (IIb) or (IIc) next, the second-coupling product is subjected to the third coupling reaction with the diazonium salt of the aromatic amine compound formula (IIb) or (IIc), thereby obtaining the reactive dye compound; ##STR00118## each substituent of formulae (IIa)˜(IIc) is the same as defined in formula (I).

11. The preparation method as claimed in claim 10, wherein the preparation method of the reactive dye compound are specifically as follows: (1) diazotization reaction: according to needs, the aromatic amine compounds of formulae (IIa), (IIb) and/or (IIc) are each beaten with ice water for 1 to 2 hours; after the beating, a certain amount of hydrochloric acid is added, and then a sodium nitrite solution is added within 20-30 min, the diazotization reaction is carried out by controlling pH at between 0.5 and 3.0 and temperature T at between 0° C. and 30° C., the end point of the reaction is detected with an ethanol solution of 4-dimethylaminobenzaldehyde; after the end point is reached, excess sodium nitrite is eliminated with sulfamic acid, and the diazonium salt solution of aromatic amine compound of the formula (IIa), (IIb) or (IIc) is obtained and stored for use; wherein the molar ratio of the aromatic amine compound of formula (IIa), (IIb) or (IIc) to hydrochloric acid and sodium nitrite is 1:(1-3):(1-1.1), preferably is 1:(1-1.8):(1-1.05); (2) coupling reaction: first, 3,5-diaminobenzoic acid is dissolved with water, the pH of the solution is controlled to be between 8.0 and 12.0, and the temperature of the solution is controlled to be between 15° C. and 25° C.; the dissolved 3,5-diaminobenzoic acid solution is added to the diazonium salt solution of the aromatic amine compound of formula (IIa) prepared in the above step (1), the pH is controlled to be between 2.0 and 6.0 with liquid alkali or baking soda, the temperature is controlled to be between 0° C. and 20° C., and the first coupling reaction is carried out, the first reaction solution is tested with H acid test solution, if the bleed circle is colorless, it means that the diazonium has been reacted completely to the end point, thereby obtaining coupling product 1; second, the diazonium salt solution of formula (IIb) or (IIc) prepared in step (1) is added to coupling product 1, the pH is controlled to be between 5.0 and 8.0 with liquid alkali or baking soda, the temperature is controlled to be between 0° C. and 20° C., and the second coupling reaction is carried out, the second reaction solution is tested with H acid test solution, if the bleed circle is colorless, it means that the diazonium has been reacted completely to the end point, thereby obtaining coupling product 2; third, the diazonium salt solution of formula (IIb) or (IIc) prepared in step (1) is added to coupling product 2, the pH is controlled to be between 5.0 and 8.0 with liquid alkali or baking soda, the temperature is controlled to be between 0° C. and 20° C., and the third coupling reaction is carried out, the third reaction solution is tested with H acid test solution, if the bleed circle is colorless, it means that the diazonium has been reacted completely to the end point, thereby obtaining the reactive dye compound; wherein the molar ratio of the aromatic amine compounds of formula (IIa), (IIb) or (IIc) in every coupling to 3,5-diaminobenzoic acid is controlled to be (0.95-1.2):1.

12. A method for applying of the reactive dye compound as claimed in claim 1 in printing and dyeing of cellulosic fibers, polyamide fibers and fabrics thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0050] FIG. 1 is the mass spectrum of the compound (I-1) obtained in example 1.

[0051] FIG. 2 is the mass spectrum of the chromophore (A) obtained in example 1.

SPECIFIC EMBODIMENTS

[0052] The present invention will be further described in conjunction with the specific examples, but the scope of protection of the present invention is not limited thereto:

[0053] The dye compounds used in the examples of the present invention were prepared and separated in the form of their sodium salt in the actual synthesis process, and are also used for dyeing in the form of their sodium salt, but for the convenience of writing, all the chemical formulae of the dye compounds in the examples are expressed in the form of their free acid, and their substantial dyeing properties are equivalent to the form of sodium salt.

EXAMPLE 1

(1) Diazotization

[0054] 23.0 g (0.1 mol) of 4-(acetylamino)-2-amino-benzenesulfonic acid were added into 100 g of water and 100 g of ice, beaten for about 1 h, added with 20 g of 31% hydrochloric acid (containing 0 17 mol of HCl), and added with 24g of a 30% sodium nitrite solution (containing 0.104 mol of sodium nitrite) within 20 min to 30 min. The diazotization reaction was carried out for 1˜2 hours by controlling pH at between 0.5 and 2.0 and temperature T at between 0° C. and 20° C., and the end point of the reaction was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (ie, if no color change within 5 s, the end point was reached). After the diazotization, excess sodium nitrite was eliminated with sulfamic acid, and the diazonium solution of 4-(acetylamino)-2-amino-benzenesulfonic acid was obtained and stored for use.

[0055] 56.2 g (0.2 mol of para-ester (p-β-hydroxyethylsulfone sulfate aniline) were added into 200 g of water and 200 g of ice, beaten for about 1 h, added with 35 g of 31% hydrochloric acid (containing 0.3 mol of HCl), and added with 48 g of a 30% sodium nitrite solution (containing 0.208 mol of sodium nitrite) within 20 min to 30 min. The diazotization reaction was carried out for 1˜2 hours by controlling pH at between 0.5 and 2.0 and temperature T at between 0° C. and 20° C., and the end point of the reaction was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (ie, if no color change within 5 s, the end point was reached). After the diazotization, excess sodium nitrite was eliminated with sulfamic acid, and the diazonium solution of the para-ester was obtained and stored for use.

(2) Coupling Reaction

[0056] 15.2 g (0.1 mol) of 3,5-dihydroxybenzoic acid were added to 200 g of water for beating, the pH of the solution was controlled to be between 8.0 and 9.0 with soda ash, and the temperature of the solution was controlled to be between 20° C. and 25° C. After the beating, the diazonium solution of 0.1 mol 4-(acetylamino)-2-amino-benzenesulfonic acid obtained in step (1) was added to the 3,5-dihydroxybenzoic acid solution. The pH was controlled to be between 5 and 5.5 with 30% liquid alkali, the temperature was controlled to be between 5° C. and 10° C., the reaction was carried out for 0.5˜2 h, and when the content of the free 3,5-dihydroxybenzoic acid was detected to be below 3% by HPLC, the reaction reached the end point, thereby obtaining chromophore of the following formula (A) whose mass spectrum is shown in FIG. 2.

##STR00026##

[0057] The diazonium solution of the para-ester obtained in step (1) was added to the chromophore of formula (A), the pH was controlled to be between 5 and 5.5 with 30% liquid alkali, and the temperature T was controlled to be between 5° C. and 10° C., the coupling reaction was further carried out for 0.5 h to 10 h. The reaction solution was tested with H acid test solution, if the bleed circle was colorless, it meant that the diazonium had been reacted completely to the end point, thereby obtaining an orange reactive dye compound (I-1) whose λmax is 420 nm in water. And the mass spectrum of the compound (I-1) is shown in FIG. 1.

##STR00027##

EXAMPLE 2˜66

[0058] Referring to the preparation method of the azo dye described in example 1, the dye compounds of the structures shown in the following table 1 were respectively obtained by stepwise diazotization and coupling reactions using raw materials of intermediates well known in the art.

TABLE-US-00001 TABLE 1 λmax Examples Reactive dye compounds (nm)  2 [00028] 420  3 [00029] 420  4 [00030] 412  5 [00031] 412  6 [00032] 420  7 [00033] 420  8 [00034] 425  9 [00035] 425 10 [00036] 425 11 [00037] 425 12 [00038] 415 13 [00039] 415 14 [00040] 415 15 [00041] 420 16 [00042] 415 17 [00043] 415 18 [00044] 410 19 [00045] 410 20 [00046] 415 21 [00047] 415 22 [00048] 415 23 [00049] 410 24 [00050] 410 25 [00051] 415 26 [00052] 415 27 [00053] 425 28 [00054] 425 29 [00055] 420 30 [00056] 415 31 [00057] 410 32 [00058] 410 33 [00059] 410 34 [00060] 415 35 [00061] 410 36 [00062] 418 37 [00063] 418 38 [00064] 418 39 [00065] 435 40 [00066] 435 41 [00067] 430 42 [00068] 435 43 [00069] 435 44 [00070] 440 45 [00071] 440 46 [00072] 435 47 [00073] 435 48 [00074] 415 49 [00075] 425 50 [00076] 418 51 [00077] 418 52 [00078] 415 53 [00079] 425 54 [00080] 422 55 [00081] 422 56 [00082] 428 57 [00083] 425 58 [00084] 430 59 [00085] 420 60 [00086] 430 61 [00087] 425 62 [00088] 415 63 [00089] 420 64 [00090] 430 65 [00091] 430 66 [00092] 420

Comparative Example 1

[0059] According to example 38 in patent CN1266869A, the reactive dye compound of the formula (1) was prepared:

##STR00093##

Comparative Example 2

[0060] According to example 1 in patent CN105694530A, the reactive dye compound of the formula (2) was prepared:

##STR00094##

Comparative Example 3

[0061] According to example 1 in patent CN101319096A, the reactive dye compound of the formula (3) was prepared:

##STR00095##

Application Example 1

[0062] The dried reactive dyes obtained in examples 1-66 and comparative examples 1-3 were respectively dissolved in water and added with sodium sulfate powder with a final concentration of 50 g/L to prepare a dyeing solution. The dyeing concentration (dye to cloth weight) was set at 4%, the bath ratio (gram weight of cloth to milliliter volume of dyeing solution) was set at 1:20, cotton was placed in the bath for adsorption at 60° C. for 30 minutes, alkali (sodium carbonate 20 g/L) was added for dye fixation for 45 minutes, the dyed fabric was washed with water, soaped, and dried to obtain a yellow to orange dyed fabric. Tests of fastnesses to washing and rubbing were carried out according to methods in ISO 105 C10-2006 and ISO 105 X12. The results are shown in table 2:

TABLE-US-00002 TABLE 2 Fastness to washing (ISO 105 C10-2006), grade Fastness to 95° C. × 30 min rubbing, grade Examples Acetate Cotton Nylon Polyester Acrylic Wool Dry Wet 1 4-5 4 4 5 4-5 4 4-5 3-4 2 4-5 4 4 5 4-5 4 4-5 3-4 3 4-5 4 4 5 4-5 4 4-5 3-4 4 4-5 4 4 5 4-5 4 4-5 3-4 5 4-5 4 4 5 4-5 4 4-5 3-4 6 4-5 4-5 4 5 4-5 4 4-5 3-4 7 4-5 4-5 4 5 4-5 4 4-5 3-4 8 4-5 4-5 4 5 4-5 4 4-5 3-4 9 4-5 4 4 5 4-5 4 4-5 3-4 10 4-5 4 4 5 4-5 4 4-5 3-4 11 4-5 4 4 5 4-5 4 4-5 3-4 12 4-5 4 4 5 4-5 4 4-5 3-4 13 4-5 4 4 5 4-5 4 4-5 3-4 14 4-5 4 4 5 4-5 4 4-5 3-4 15 4-5 4 4 5 4-5 4 4-5 3-4 16 4-5 4 4 5 4-5 4 4-5 3-4 17 4-5 4 4 5 4-5 4 4-5 3-4 18 4-5 4-5 4 5 4-5 4 4-5 3-4 19 4-5 4-5 4 5 4-5 4 4-5 3-4 20 4-5 4 4 5 4-5 4 4-5 3-4 21 4-5 4 4 5 4-5 4 4-5 3-4 22 4-5 4 4 5 4-5 4 4-5 3-4 23 4-5 4 4 5 4-5 4 4-5 3-4 24 4-5 4 4 5 4-5 4 4-5 3-4 25 4-5 4-5 4 5 4-5 4 4-5 3-4 26 4-5 4-5 4 5 4-5 4 4-5 3-4 27 4-5 4-5 4 5 4-5 4 4-5 3-4 28 4-5 4-5 4 5 4-5 4 4-5 3-4 29 4 4 4 4-5 4-5 4 4-5 3-4 30 4 4 4 4-5 4-5 4 4-5 3-4 31 4 4 4 4-5 4-5 4 4-5 3-4 32 4 4 4 4-5 4-5 4 4-5 3-4 33 4 4 4 4-5 4-5 4 4-5 3-4 34 4 4 4 4-5 4-5 4 4-5 3-4 35 4 4 4 4-5 4-5 4 4-5 3-4 36 4 4 4 4-5 4-5 4 4-5 3-4 37 4 4 4 4-5 4-5 4 4-5 3-4 38 4 4 4 4-5 4-5 4 4-5 3-4 39 4 4 4 4-5 4-5 4 4-5 3-4 40 4 4 4 4-5 4-5 4 4-5 3-4 41 4 4 4 4-5 4-5 4 4-5 3-4 42 4 4 4 4-5 4-5 4 4-5 3-4 43 4 4 4 4-5 4-5 4 4-5 3-4 44 4 4 4 4-5 4-5 4 4-5 3-4 45 4 4 4 4-5 4-5 4 4-5 3-4 46 4 4 4 4-5 4-5 4 4-5 3-4 47 4 4 4 4-5 4-5 4 4-5 3-4 48 4-5 4-5 4 5 4-5 4 4-5 3-4 49 4-5 4-5 4 5 4-5 4 4-5 3-4 50 4-5 4-5 4 5 4-5 4 4-5 3-4 51 4-5 4-5 4 5 4-5 4 4-5 3-4 52 4-5 4-5 4 5 4-5 4 4-5 3-4 53 4-5 4-5 4 5 4-5 4 4-5 3-4 54 4-5 4-5 4 5 4-5 4 4-5 3-4 55 4-5 4-5 4 5 4-5 4 4-5 3-4 56 4 4 4 4-5 4-5 4 4-5 3-4 57 4 4 4 4-5 4-5 4 4-5 3-4 58 4 4 4 4-5 4-5 4 4-5 3-4 59 4 4 4 4-5 4-5 4 4-5 3-4 60 4 4 4 4-5 4-5 4 4-5 3-4 61 4 4 4 4-5 4-5 4 4-5 3-4 62 4 4 4 4-5 4-5 4 4-5 3-4 63 4 4 4 4-5 4-5 4 4-5 3-4 64 4 4 4 4-5 4-5 4 4-5 3-4 65 4 4 4 4-5 4-5 4 4-5 3-4 66 4 4 4 4-5 4-5 4 4-5 3-4 Comparative 4 3-4 3-4 4 4 3 4-5 3 example 1 Comparative 4 3-4 3-4 4 4 3 4-5 3-4 example 2 Comparative 4 4 3-4 4 4 3-4 4 3 example 3

[0063] From table 2, we can see that the reactive dyes of the present invention are significantly superior to those of the prior art in fastness to washing and rubbing.