Reactive dye compound and preparation method and application thereof

Abstract

A reactive dye compound and preparation method and application for printing and dyeing of cellulosic fibers, polyamide fibers and fabrics thereof. Formula (I) is the dye compound structure where D.sup.1 and D.sup.2 are each independently the group of the following formula (a) or (b) or (c), and D.sup.1 and D.sup.2 are not simultaneously selected from the following formula (a). R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are each independently H, linear or branched C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkoxy or sulfo; m=0-3. Each R.sup.3 is independently selected from amino, sulfo, ureido, C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkanoylamino or C.sub.1˜C.sub.4 alkoxy, n=0-3, and each R.sup.6 is independently selected from hydroxyl, amino and sulfo. X.sup.1, X.sup.2 and X.sup.3 are each independently H, C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkoxy, —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, and at least one of D.sup.1 and D.sup.2 contains a fiber-reactive group. Y.sup.1˜Y.sup.3 are each independently —CH═CH.sub.2, —C.sub.2H.sub.4OSO.sub.3H or —CH.sub.2CH.sub.2Cl, p=1-3, and q=1-3. ##STR00001##

Claims

1. A reactive dye compound of the following formula (I) or a quinohydrazone tautomer thereof: ##STR00089## in formula (I) D.sup.1 and D.sup.2 are each independently a group of the following formula (a) or (b) or (c), where D.sup.1 and D.sup.2 are not simultaneously selected from the following formula (a): ##STR00090## in the above formulae (a)˜(c): R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are each independently H, linear or branched C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkoxy or sulfo; m=0-3, each R.sup.3 is independently selected from amino, sulfo, ureido, C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkanoylamino and C.sub.1˜C.sub.4 alkoxy; n=0-3, each R.sup.6 is independently selected from hydroxyl, amino and sulfo; and X.sup.1, X.sup.2 and X.sup.3 are each independently H, linear or branched C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkoxy, —SO.sub.2Y.sup.1, —NHCO(CH.sub.2).sub.pSO.sub.2Y.sub.2 or —CONH(CH.sub.2).sub.qSO.sub.2Y.sup.3, and at least one of D.sup.1 and D.sup.2 contains a fiber-reactive group which is —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, wherein Y.sup.1˜Y.sup.3 are each independently —CH═CH.sub.2, —C.sub.2H.sub.4OSO.sub.3H or —CH.sub.2CH.sub.2Cl, p=1-3, and q=1-3, or an alkali metal salt thereof.

2. The reactive dye compound as claimed in claim 1, wherein the reactive dye compound has the structure shown as the following formula (I): ##STR00091## in formula (I): D.sup.1 and D.sup.2 are each independently a group of the following formula (a) or (b) or (c), where D.sup.1 and D.sup.2 are not simultaneously selected from the following formula (a): ##STR00092## in the above formulae (a), (b) and (c): R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are each independently H, linear or branched C.sub.1˜C.sub.4 alkyl, C.sub.1˜C.sub.4 alkoxy or sulfo; m=0-3, each R.sup.3 is independently selected from sulfo, ureido, and C.sub.1˜C.sub.4 alkanoylamino; n=0-3, each R.sup.6 is independently selected from hydroxyl and sulfo; and X.sup.1, X.sup.2 and X.sup.3 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, wherein Y.sup.1˜Y.sup.3 are each independently —CH═CH.sub.2, —C.sub.2H.sub.4OSO.sub.3H or —CH.sub.2CH.sub.2Cl, p=1-3, and q=1-3.

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

4. The reactive dye compound as claimed in claim 1, wherein R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are each independently selected from H, methyl, methoxy and sulfo; in the group represented by formula (b), m is 1 or 2, and each R.sup.3 is independently selected from sulfo, ureido, acetylamino and methyl.

5. The reactive dye compound as claimed claim 1, wherein D.sup.1 is selected from the group consisting of the following groups: ##STR00093## ##STR00094##

6. The reactive dye compound as claimed in claim 1, wherein D.sup.2 is selected from the group consisting of the following groups: ##STR00095## ##STR00096## ##STR00097##

7. The reactive dye compound as claimed in claim 1, wherein the reactive dye compound is selected from the group consisting of the following structures: ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108##

8. The reactive dye compound as claimed in claim 7, wherein the reactive dye compound of formula (I) is selected from the group consisting of the compounds represented by formulae (I-1)˜(I-33), (I-52), and (I-53).

9. The reactive dye compound as claimed in claim 7, wherein the reactive dye compound is selected from the group consisting of the compounds represented by formulae (I-1), (I-7), (I-17), (I-18), (I-21), (I-22), (I-24) and (I-25).

10. The reactive dye compound as claimed in claim 1, wherein the reactive dye compound contains a quinohydrazone structure of the following formula (Ib), (Ic), (Id), (Ie), ##STR00109## wherein each substituent of formula (Ib), (Ic), (Id) and/or (Ie) has the same definition as that of formula (I).

11. The reactive dye compound as claimed in claim 1, wherein the dye compound is prepared and isolated in the form of alkali metal salt in the actual synthesis process for dyeing in the form of alkali metal salt.

12. The reactive dye compound as claimed in claim 11, wherein the alkali metal salt is sodium or potassium salt.

13. The reactive dye compound as claimed in claim 12, wherein the alkali metal salt is sodium salt.

14. A preparation method of the reactive dye compound as claimed in claim 1, comprising: (1) diazotization, which is carried out according to the following steps A and B and/or C: A: the arylamine compounds represented by formula (IIa), formula (IIb) and/or formula (IIc) are respectively diazotized to obtain respective diazonium salts; B: coupling a diazonium salt of a compound of formula (IIb) with an aromatic amine of formula (IIIa) to obtain a compound of formula (IVa), which is subjected to diazotization to obtain a diazonium salt; C: coupling a diazonium salt of a compound of formula (IIc) with an aromatic amine of formula (IIIb) to obtain a compound of formula (IVb), which is subjected to diazotization to obtain a diazonium salt; (2) coupling reaction, in which 3,5-dihydroxybenzoic acid is added with water and stirred, the resulting solution is first-coupled with a diazonium salt of a compound of formula (IIa), formula (IVa), or formula (IVb) obtained in the step (1), then second-coupled with a diazonium salt of a compound of formula (IIa), formula (IVa), formula (IVb), or the diazonium salts used in the first-coupling and the second-coupling cannot both be the diazonium salt of a compound of formula (IIa), and thus the reactive dye compound (I) is obtained; ##STR00110## each substituent of formulae (IIa), (IIb), (IIc), (IIIa), (IIIb), (IVa) and (IVb) has the same definition as that of formula (I).

15. A reactive dye product comprising the reactive dye compound as claimed in claim 1 and an auxiliary.

16. The reactive dye product as claimed in claim 15, which contains the reactive dye compound of formula (I) and an auxiliary, wherein the weight of the auxiliary does not exceed 45% of the weight of the reactive dye product.

17. The reactive dye product as claimed in claim 15, wherein the auxiliary is selected from one or more of the following auxiliaries: a naphthalene sulfonic acid formaldehyde condensate, a methylnaphthalenesulfonic acid formaldehyde condensate, a diffusing agent CNF, Yuanming powder, lignosulfonate, sodium acetate, sodium hydrogencarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and thickener.

18. A method of dying or printing of cellulosic fibers, polyamide fibers or fabrics thereof, the method comprising contacting the reactive dye compound as claimed in claim 1 with the cellulosic fibers, polyamide fibers and fabrics thereof.

19. A method of dying or printing of cellulosic fibers, polyamide fibers or fabrics thereof, the method comprising contacting the reactive dye product as claimed in claim 15 with the cellulosic fibers, polyamide fibers and fabrics thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the 1HNMR spectrum of the compound (I-1) obtained in example 1;

(2) FIG. 2 is the 13C NMR spectrum of the compound (I-1) obtained in example 1;

(3) FIG. 3 is the 1H NMR spectrum of the chromophore 2 obtained in example 1;

(4) FIG. 4 is the 13C NMR spectrum of the chromophore 2 obtained in example 1;

(5) FIG. 5 is the build-up curve.

SPECIFIC EMBODIMENTS

(6) The present invention will be further described in conjunction with the specific examples, but the scope of the present invention is not limited thereto:

(7) For convenience of writing, all the chemical formulae in the examples are embodied by the form of free acid, and their substantial dyeing properties are equivalent to the form of alkali metal salts (such as sodium salts, potassium salts, etc.).

Example 1

(8) 1) Diazotization:

(9) 28.1 g (0.1 mol) of para-ester (p-β-hydroxyethyl sulfone sulfate aniline) were added into 100 g of water and 100 g of ice, the mixture was beaten for about 1 h, added with 20 g of 31% hydrochloric acid (containing 0.17 mol of HCl), and then added with 24 g of a 30% sodium nitrite solution (containing 0.104 mol of sodium nitrite) within 20-30 min. The diazotization reaction was carried out for 1 hour to 2 hours by controlling pH at between 0.5 and 2.0 and temperature T at 0° C. to 20° C., and the end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (i.e., no color change within 5 s). After the diazotization, the excess sodium nitrite was eliminated with sulfamic acid, and the obtained diazo solution of para-ester was stored for use.

(10) 36.1 g (0.1 mol) of sulfonated para-ester (2-sulfonic acid-4-β-hydroxyethylsulfone sulfate aniline) were added into 100 g of water and 100 g of ice, the mixture was beaten for about 1 h, added with 20 g of 31% hydrochloric acid (containing 0.17 mol of HCl), and then added with 24 g of a 30% sodium nitrite solution (containing 0.104 mol of sodium nitrite) within 20-30 min. The diazotization reaction was carried out for 1 hour to 2 hours by controlling pH at between 0.5 and 2.0 and temperature T at 0° C. to 20° C., and the end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (i.e., no color change within 5 s). After the diazotization, the excess sodium nitrite was eliminated with sulfamic acid, and the obtained diazo solution of sulfonated para-ester was stored for use.

(11) The above diazo solution of 0.1 mol of sulfonated para-ester was added to 15.1 g (0.1 mol) of 3-aminophenylurea, the coupling reaction was carried out for 0.5 h to 2 h by controlling pH at between 4.0 and 6.0 with 30% liquid alkali and temperature T at 0° C. to 20° C. The diazo was tested with H-acid test solution, if the bleed circle was colorless, it meant that the diazo had been reacted completely to the end point (if not, the reaction continued to the end point), thereby obtaining chromophore 1. Chromophore 1 was added with 20 g of 31% hydrochloric acid (containing 0.17 mol of HCl), and then added with 24 g of a 30% sodium nitrite solution (containing 0.104 mol of sodium nitrite) within 20-30 min. The diazotization reaction was carried out for 1 hour to 2 hours by controlling pH at between 0.5 and 2.0 and temperature T at 0° C. to 20° C., and the end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (i.e., no color change within 5 s). After the diazotization, the excess sodium nitrite was eliminated with sulfamic acid, and the obtained diazo solution of chromophore 1 was stored for use.

(12) 2) Coupling:

(13) Firstly, 154 g (0.1 mol) of 3,5-dihydroxybenzoic acid were added to 200 g of water for beating, the pH was adjusted to 8.0-9.0 with soda ash, the temperature was controlled at 20° C. to 25° C., and the beaten 3,5-dihydroxybenzoic acid solution was added to the diazo solution of 0.1 mol para-ester obtained in step 1), the reaction was carried out for 0.5 hour to 2.5 hours by controlling pH at 4.0 with 30% liquid alkali and temperature at 0° C. to 20° C., when the content of the free 3,5-dihydroxybenzoic acid was detected to be below 3% by HPLC the reaction was ended, and chromophore 2 represented by the following formula (A) was obtained and characterized by H1-NHR spectra[.sup.1HNMR (DMSO-d6) [3.68-3.71 ppm 2H(t), 3.98-4.01 ppm 2H(t), 6.42 ppm 1H(s), 6.62 ppm 1H(s), 7.96-7.97 ppm 2H (d), 8.05-8.07 ppm 2H (d)]. The spectra of chromophore 2 were shown as FIGS. 3 and 4.

(14) ##STR00027##

(15) The diazo solution of chromophore 1 obtained in step (1) was added to the chromophore 2, the coupling reaction was further carried out for 0.5 h to 10 h by controlling pH at between 5.0 and 8.0 with 30% liquid alkali and temperature at 0° C. to 20° C. The diazo was tested with H-acid test solution, if the bleed circle was colorless, it meant that the diazo had been reacted completely to the end point, thereby obtaining the orange reactive dye compound (I-1). In aqueous solution its λmax=485 nm, the mass spectrum (ESI-MS) m/z (−): 325.84 ([M−3H].sup.3−/3), 488.96 ([M−2H].sup.2−/2), 978.89 ([M−H].sup.−1). The dye (in terms of free sulfonic acid) had the molecular weight M of 980.0, and was characterized by H1-NHR spectra [.sup.1HNMR (DMSO-d6) [3.61-3.74 ppm 4H(m), 3.96-4.04 ppm 4H(m), 6.22 ppm 1H(s), 7.48-8.20 ppm 8H(m), 8.40 ppm 1H(s), 9.02 ppm 1H (s), 11.1 ppm 1H (s)]. The spectra of the compound (I-1) were shown as FIGS. 1 and 2.

(16) ##STR00028##

Examples 2˜58

(17) Referring to the preparation method of the azo dye described in example 1, using intermediate materials well known in the art, the dye compounds of the formulae shown in the following tables 1 were respectively prepared by stepwise diazotization and coupling reaction.

(18) TABLE-US-00001 TABLE 1 Ex- am- λmax ples Reactive dye compounds (nm)  2 480  3 0 485  4 490  5 495  6 490  7 465  8 470  9 465 10 465 11 480 12 480 13 0 475 14 470 15 470 16 485 17 520 18 510 19 510 20 525 21 500 22 510 23 0 470 24 510 25 520 26 510 27 500 28 510 29 535 30 535 31 485 32 485 33 0 485 34 500 35 510 36 515 37 475 38 480 39 485 40 485 41 480 42 480 43 0 490 44 485 45 480 46 480 47 475 48 500 49 505 50 510 51 470 52 485 53 0 475 54 480 55 495 56 490 57 500 58 470

Comparative Example 1

(19) According to example 38 in patent CN1266869, the reactive dye compound represented by the following formula was prepared:

(20) ##STR00086##

Comparative Example 2

(21) According to example 9 in patent CN1283054, the reactive dye compound represented by the following formula was prepared:

(22) ##STR00087##

Comparative Example 3

(23) According to example 11 in patent CN101283054, the reactive dye compound represented by the following formula was prepared:

(24) ##STR00088##

Application Example 1

(25) The reactive dyes obtained in examples 1˜58 and comparative examples 1˜3 were respectively dissolved in water, and Yuanming powder was added to prepare dyeing solutions with a final concentration of 50 g/L. The dyeing concentration (dye to cloth weight) was set at 4% and 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 fabrics were washed with water, soaped, and dried to obtain a orange to reddish brown dyed fabric. The staining fastness to washing test and rubbing fastness test were carried out according to the methods of ISO 105 C10-2006 and ISO 105×12, respectively. The results were shown in table 2:

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

(27) As can be seen from table 2, the reactive dye compounds of the present invention were more prominent in the overall performance of washing fastness and rubbing fastness than the existing dyes.

Application Example 2

(28) The degree of fixation of the compounds in the examples of the present invention and the reactive dyes in comparative examples 1˜3 were tested according to the method of GB/T2391-2014 standard. The results were shown in table 3:

(29) TABLE-US-00003 TABLE 3 Compounds Comparative Comparative Comparative example example example Properties I-1 I-2 I-7 1 2 3 Degree of 78.2% 79.1% 77.8% 70.9% 69.2% 70.4% fixation

(30) As can be seen from table 3, compared with the existing dyes, the reactive dye compounds of the present invention had significant improvement in staining fastness to washing and degree of fixation, and could be more widely used for printing and dyeing of cotton and blended fabrics thereof because of their good staining fastness. And the compounds had high degree of fixation, clear remanent dyeing liquor, and reduced residue of organics, and were more ecological and environmentally friendly.

Application Example 3

(31) The build-up property of the reactive dyes of examples 1, 52, 17, 21, 22 and 25 of the present invention and comparative examples 1˜3, was tested according to the method of GB/T 21875-2016 standard. The results were shown in FIG. 5, wherein S1˜S6 represented the build-up curve of examples 1, 52, 17, 21, 22 and 25 respectively, and D1˜D3 represented the build-up curve of comparative examples 1˜3 respectively.

(32) As can be seen from FIG. 5, compared with the existing dyes, the reactive dye compounds of the present invention had a remarkable increase in the apparent color depth on the cloth surface as the dyeing depth was increased, while the dyes of the comparative examples 1˜3 in the late period had an almost saturated color depth as the dyeing concentration was increased.