1. A reactive dye compound which is a compound having a structure represented by the following formula (I) or an alkali metal salt thereof (preferably sodium salt or potassium salt):

in formula (I):

D¹、D²each independently of the otherIs a group represented by the following formula (a), formula (b) or formula (c), and D¹、D²Not both being a group represented by the following formula (a), formula (b) or formula (c):

in the above formulas (a) to (c):

R¹～R⁵each independently is H, C₁～C₄Straight or branched alkyl, C₁～C₄Alkoxy or sulfonic acid groups;

X¹、X²、X³are independent of each other H, C₁～C₄Straight or branched alkyl, C₁～C₄Alkoxy, -SO₂Y¹、-NHCO(CH₂)_pSO₂Y²or-CONH (CH)₂)_qSO₂Y³And D is¹、D²At least one of which contains fibre-reactive groups, i.e. -SO₂Y¹、-NHCO(CH₂)_pSO₂Y²or-CONH (CH)₂)_qSO₂Y³Wherein Y is¹～Y³Each independently is-CH ═ CH₂、-C₂H₄OSO₃H or-CH₂CH₂Cl，p＝1-3，q＝1-3。

2. A reactive dye compound according to claim 1, wherein: d¹Selected from the group consisting of the groups represented by the formula (a) or the formula (b), D²Selected from the group represented by formula (c), wherein the reactive dye compound has a structure represented by formula (Ia) or formula (Ib):

the substituents in the formula (Ia) and the formula (Ib) are as defined in the formula (I).

3. A reactive dye compound according to claim 1 or 2, characterized in that: the formula (a) is selected from one of the following groups:

4. a reactive dye compound according to claim 1 or 2, characterized in that: the formula (b) is selected from one of the following groups:

5. a reactive dye compound according to claim 1 or 2, characterized in that: the formula (c) is selected from one of the following groups:

6. a reactive dye compound according to claim 1, wherein: the reactive dye compound is selected from one of compounds shown in the following formulas (I-1) to (I-63) and alkali metal salts thereof:

7. a reactive dye compound according to claim 1, wherein: the compound shown in the formula (I) contains a quinone hydrazone structure shown in the following formula (ie) and/or (if) and/or (Ig) and/or (ih),

the substituents in the formulae (ie) to (ih) are as defined for formula (I).

8. A process for the preparation of a compound of formula (i) as claimed in claim 1, which comprises:

(1) diazotization:

diazotizing the arylamine compounds shown in the formula (IIa), the formula (IIb) and/or the formula (IIc) respectively to obtain respective diazonium salts according to requirements;

(2) coupling reaction:

adding water into 3, 5-dihydroxy benzoic acid, pulping, performing primary coupling on the pulped solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb) and the diazonium salt of the formula (IIc) in the step (1), and performing secondary coupling on the solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb) and the diazonium salt of the formula (IIc), wherein the diazonium salts adopted in the primary coupling and the secondary coupling cannot be the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb) or the diazonium salt of the formula (IIc), so as to obtain the compound (I);

the substituents in the above formulae (IIa) to (IIc) are as defined for formula (I).

9. A reactive dye preparation comprising the reactive dye compound of claim 1.

10. Use of a reactive dye preparation according to claim 9 in the printing of cellulose fibres, polyamide fibres or fabrics thereof.

(II) background of the invention

The improvement of the fastness to washing of the fabric dyed by the reactive dye is always a key point and a difficult point in the printing and dyeing production. The covalent bond between part of the reactive dye and the cotton fiber is affected by external conditions, and the bond breakage and hydrolysis are easy to occur, so that the color fastness of the dyed fabric is deteriorated, and particularly the color fastness to washing and staining cannot well meet the production requirement. In order to solve the above problems, the present inventors have developed a novel reactive dye structure, using 3, 5-dihydroxybenzoic acid as a coupling component, and have conducted intensive studies on the compound, and have obtained yellow to orange dyes with excellent color fastness properties on the basis of a large number of experiments.

Disclosure of the invention

The invention aims to provide a reactive dye compound with novel structure and excellent performance, a preparation method thereof and application thereof in printing and dyeing of cellulose fibers, polyamide fibers and fabrics thereof.

The technical solution adopted by the present invention is specifically explained below.

In a first aspect, the present invention provides a reactive dye compound which is a compound having a structure represented by the following formula (i):

in formula (I):

D¹、D²each independently is a group of formula (a), formula (b) or formula (c), and D¹、D²Not both being a group represented by the following formula (a), formula (b) or formula (c):

in the above formulas (a) to (c):

R¹～R⁵each independently is H, C₁～C₄Straight or branched alkyl, C₁～C₄Alkoxy or sulfonic acid groups;

X¹、X²、X³are independent of each other H, C₁～C₄Straight or branched alkyl, C₁～C₄Alkoxy, -SO₂Y¹、-NHCO(CH₂)_pSO₂Y²or-CONH (CH)₂)_qSO₂Y³And D is¹、D²At least one of which contains fibre-reactive groups, i.e. -SO₂Y¹、-NHCO(CH₂)_pSO₂Y²or-CONH (CH)₂)_qSO₂Y³Wherein Y is¹～Y³Each independently is-CH ═ CH₂、-C₂H₄OSO₃H or-CH₂CH₂Cl，p＝1-3，q＝1-3。

In the present invention, said C₁～C₄The straight or branched alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; said C₁～C₄The alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.; said C₁～C₄The alkanoylamino group of (a) may be formylamino, acetylamino, n-propionylamino, isopropionylamino, n-butyrylamino, isobutyrylamino, t-butyrylamino and the like.

Further, in the formulae (a) to (c):

R¹～R⁵each independently is H, methyl, methoxy or sulfonic group;

X¹、X²、X³independently of one another are-SO₂Y¹、-NHCO(CH₂)_pSO₂Y²or-CONH (CH)₂)_qSO₂Y³Wherein Y is¹～Y³Each independently is-CH ═ CH₂、-CH₂CH₂Cl or-C₂H₄OSO₃H，p＝1-3，q＝1-3。

Further, D¹Preferably a group of the formula (a) or (b), D²Preferably a group of formula (c), said reactive dye compound having a structure of formula (Ia) or (Ib):

the substituents in the formula (Ia) and the formula (Ib) are as defined in the formula (I).

Further, in the reactive dye compound, the formula (a) is preferably selected from one of the following groups:

further, in the reactive dye compound, the formula (b) is preferably selected from one of the following groups:

further, in the reactive dye compound, the formula (c) is preferably selected from one of the following groups:

the invention specifically recommends that the reactive dye compound is selected from one of the compounds shown in the following formulas (I-1) to (I-63) and alkali metal salts thereof:

further, in the present invention, it is preferable that the reactive dye compound is one selected from the group consisting of compounds represented by formulae (I-1) to (I-40) and alkali metal salts thereof.

Further, in the present invention, it is preferable that the reactive dye compound is one selected from the group consisting of compounds represented by formulae (I-1) to (I-8), formulae (I-11) to (I-26), and alkali metal salts thereof.

It should be emphasized that the dye compounds (I) according to the invention, the dyes coupled in the ortho position to the phenolic hydroxyl group, often exist in the form of quinone hydrazone compounds, i.e. the dye mixtures of the general formula (I) contain quinone hydrazone structures represented by the following formulae (ie) and/or (if) and/or (ig) and/or (ih), and in view of the writing habits of the skilled person, the writing forms of azo compounds are still used in the summary and the examples section, which does not affect the essence of the invention:

the substituents in the formulae (ie) to (ih) are as defined for formula (I).

In a second aspect, the present invention provides a process for the preparation of a compound of formula (i) comprising:

(1) diazotization:

diazotizing the arylamine compounds shown in the formula (IIa), the formula (IIb) and/or the formula (IIc) respectively to obtain respective diazonium salts according to requirements;

(2) coupling reaction:

adding water into 3, 5-dihydroxy benzoic acid, pulping, performing primary coupling on the pulped solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb) and the diazonium salt of the formula (IIc) in the step (1), and performing secondary coupling on the solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb) and the diazonium salt of the formula (IIc), wherein the diazonium salts adopted in the primary coupling and the secondary coupling cannot be the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb) or the diazonium salt of the formula (IIc), so as to obtain the compound (I);

the substituents in the above formulae (IIa) to (IIc) are as defined for formula (I).

Further, the compound (i) is preferably synthesized by the following steps:

(1) diazotization:

according to the requirement, pulping the compounds shown in the formula (IIa), the formula (IIb) and/or the formula (IIc) together with water and ice for 1-2 h, adding a certain amount of hydrochloric acid after pulping, then adding a sodium nitrite solution within 20-30min, controlling the pH to be 0.5-3.0 (preferably 0.5-2.0) and the temperature T to be 0-30 ℃ (preferably 0-20 ℃) to carry out diazotization reaction, and detecting the end point (namely, no discoloration within 5 s) by using an ethanol solution of 4-dimethylaminobenzaldehyde; after the diazotization end point is reached, sulfamic acid is used for eliminating excessive sodium nitrite to respectively obtain diazo liquid of the formula (IIa), the formula (IIb) or the formula (IIc) for storage and standby; wherein the molar ratio of the compound of formula (IIa), the compound of formula (IIb) or the compound of formula (IIc) to the hydrochloric acid and the sodium nitrite is 1 (1-3) to (1-1.1), preferably 1 (1-1.8) to (1-1.02);

(2) coupling reaction:

adding water into 3, 5-dihydroxy benzoic acid, pulping and dispersing, and controlling the temperature to be 15-25 ℃. Adding the dispersed 3, 5-dihydroxybenzoic acid into the diazo liquid of the formula (IIa), the diazo liquid of the formula (IIb) or the diazo liquid of the formula (IIc) prepared in the step (1), controlling the pH to be 2.0-5.0 and the temperature to be 0-30 ℃ (preferably 0-20 ℃) by using liquid alkali or sodium bicarbonate to carry out coupling reaction, testing diazo by using an H acid test solution, and obtaining a coupling product 1 when the diazo is colorless at a ring penetration position, namely the diazo has completely reacted to the end point;

adding the diazo liquid of the formula (IIa), the diazo liquid of the formula (IIb) or the diazo liquid of the formula (IIc) obtained in the step (1) into the coupling product 1, controlling the pH value to be 5.0-8.0 by using liquid alkali or baking soda, controlling the temperature to be 0-30 ℃ (preferably 0-20 ℃) to carry out coupling reaction, testing diazo by using H acid test solution, and obtaining the compound of the formula (I) after the diazo has reacted completely to the end point and being colorless at the position of a seepage ring;

the diazo liquid used in the above two coupling reactions can not be all of the diazo liquid of formula (IIa), the diazo liquid of formula (IIb) or the diazo liquid of formula (IIc); wherein the molar ratio of the compound of formula (IIa), the compound of formula (IIb) and the compound of formula (IIc) to the 3, 5-dihydroxybenzoic acid is (0.95-1.2): 1, preferably (0.98-1.08): 1.

it is well known in the art that in the compounds of formula (I) according to the invention, when Y is¹～Y³is-C₂H₄OSO₃H or-CH₂CH₂Cl, (-SO) beta-hydroxyethyl sulfone sulfate in typical reactive dye dyeing applications₂C₂H₄OSO₃H) Or beta-chloroethylsulfone (-SO)₂C₂H₄Cl) in alkaline medium to generate vinylsulfonyl (-SO) through elimination reaction₂CH＝CH₂) And then carrying out nucleophilic addition reaction with the cellulose fiber to form a covalent bond.

The compounds (i) according to the invention, during their preparation, also allow the presence of by-products in amounts not exceeding 30%, which can be used without isolation, directly in the processing of commercial dyes, including, without limitation, compounds or mixtures of the following structure:

in the above by-products, the substituents are as defined in the above formula (I).

The reactive dye compounds of the invention, formula (I) being embodied in the form of the free acid, are generally prepared and isolated in the actual synthesis process in the form of their alkali metal salts, preferably sodium or potassium salts, particularly preferably sodium salts, and are also used for dyeing in the form of their salts, as is also known to the person skilled in the art, i.e. the carboxyl and sulfonic acid groups in formula (I) can be present in the form of sodium carboxylates or sodium sulfonates.

The reactive dye compounds according to the invention may be present in the form of powders, granules, aqueous solutions or synthesis solutions, and the isolation of the dye compounds according to the invention from the synthesis solutions may be carried out by generally known methods, for example by salting out the dye from the reaction medium with an electrolyte, such as sodium chloride or potassium chloride, or by evaporating and spray-drying the solution, and the dye compounds therefore generally comprise the electrolyte salts customary for reactive dyes, such as sodium chloride, sodium sulfate, etc.

In the third aspect, when the reactive dye compound of the present invention is sold as a commercial product, no auxiliary agent may be added, or conventional auxiliary agents in commercial dyes, such as a cosolvent, a dispersant, an alkali-resistant auxiliary agent, a dust-proofing agent, a surfactant, a buffer, an accelerating agent, etc., may be added. Therefore, the invention also provides a reactive dye product which contains the reactive dye compound. Preferably, the reactive dye product contains the reactive dye compound and an auxiliary agent, wherein the weight of the auxiliary agent is not more than 45% of the weight of the reactive dye compound, and preferably not more than 40%. The auxiliary agent is preferably one or the combination of any several of the following components: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), dispersant CNF (benzylnaphthalenesulfonate formaldehyde condensate), sodium sulfate (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium hydrogen carbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener, and the like. The auxiliary agents are all conventional types sold in the market.

In a fourth aspect, the invention provides the use of the reactive dye product in printing and dyeing of cellulose fibers, polyamide fibers or fabrics thereof. The cellulose fiber is preferably cotton fiber or regenerated fiber, but may also include other plant fiber, such as hemp fiber or fabric; the polyamide fiber is preferably an animal fiber material including a sheath, a wool or a silk, and a synthetic fiber material such as nylon 6 and nylon 66. When the fiber material is printed and dyed by using the reactive dye compound or the reactive dye product, the dyeing can be carried out according to a known reactive dye dyeing method, such as a common reactive dye dip dyeing method and a pad dyeing method, wherein the dip dyeing method is a method of dipping the fabric into a dye solution to gradually dye the fabric, and the procedures of dyeing, fixing color, washing, soaping, washing, dewatering, drying and the like are usually required.

The pad dyeing is a dyeing method that a fabric is soaked in a dye solution, then the fabric passes through a roller, the dye solution is uniformly rolled into the fabric, and then the fabric is steamed or hot-melted and the like, and generally the procedures of pad dyeing, drying- (pad fixing solution), steaming or baking, washing, soaping, washing, drying and the like are needed.

Generally, the dye usage amount is different due to different dyeing requirements on fabrics, when a dip dyeing method is used for dyeing, the dyeing depth (owf) is generally 0.1-10% (the dye accounts for the weight percent of the fabrics), the bath ratio is 1: 2-1: 60 (the weight ratio of the fabrics to the dye liquor is preferably 1: 10-1: 30), the initial dyeing temperature is controlled to be 30-60 ℃, the dyeing time is 10-30 minutes, the soaping temperature is 85-95 ℃, the soaping time is 10-15 minutes, the color fixing temperature is 60-100 ℃, the color fixing time is 10-50 minutes, and the color fixing pH value is 9-11. When the pad dyeing method is used for dyeing, the pad retention rate of the cellulose fiber is generally 60-80%, the steaming temperature is 100-103 ℃, and the steaming time is 1-3 minutes. In the pad dyeing method, a cold pad-batch dyeing method is frequently used at present, and a dye and an alkaline substance are introduced into a pad dyeing machine, coiled and stacked at room temperature for 2-30 hours for color fixation, and then thoroughly rinsed.

The invention has the beneficial effects that: the reactive dye compound has a novel structure, excellent color fastness, especially outstanding washing fastness and rubbing fastness, and good combination stability with fibers, and is suitable for dyeing and printing fibers such as cotton, artificial cotton, silk, wool and the like.

(IV) description of the drawings

FIG. 1 is a UV-Vis spectrum of a reactive dye compound prepared in example 3;

FIG. 2 is a mass spectrum of the reactive dye compound prepared in example 3, wherein m/Z-432.96 is a target molecule double charge ionization peak. .

(V) detailed description of the preferred embodiments

The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:

the dye compound prepared in the embodiment of the invention is sodium salt and is applied in the form of sodium salt, but for the convenience of writing, all structural formulas in the embodiment are embodied in the form of free acid, and the substantial dyeing performance of the free acid and the sodium salt is known to be equivalent by persons skilled in the art.

Example 1

(1) Diazotization:

a diazotization reaction was carried out for 1 to 2 hours by adding 41.1g (0.1mol) of 2-amino-6-hydroxyethyl sulfone sulfate ester-1-naphthalenesulfonic acid into 100g of water and 100g of ice and beating for about 1 hour, adding 20g of 31% hydrochloric acid (containing 0.17mol of HCl), adding 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) within 20 to 30 minutes, controlling pH at 0.5 to 2.0 and temperature T at 0 to 20 ℃, and detecting the end point (i.e., no discoloration within 5 seconds) with an ethanol solution of 4-dimethylaminobenzaldehyde. After the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained 2-amino-6-hydroxyethyl sulfone sulfate ester-1-naphthalenesulfonic acid diazotization solution for later use.

36.1g (0.1mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethyl sulfone sulfate aniline) is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at the pH value of 0.5-2.0 and the temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, the end point is not discolored within 5 s). And (4) after the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained sulfonated para-ester diazotization liquid for later use.

(2) Coupling:

firstly, 154g (0.1mol) of 3, 5-dihydroxybenzoic acid is added into 200g of water for pulping, the temperature is controlled to be 20-25 ℃, the pulped 3, 5-dihydroxybenzoic acid solution is added into the diazo liquid of 2-amino-6-hydroxyethyl sulfone sulfate-based-1-naphthalenesulfonic acid obtained in the step (1), the pH is controlled to be 2.0-4.0 by 30% liquid alkali, the temperature is controlled to be 0-20 ℃, the reaction is carried out for 15-20h, and the free 3, 5-dihydroxybenzoic acid is controlled to be below 3% by HPLC to obtain the end point, thus obtaining the chromophore 1 shown in the following formula (A).

And (2) adding the sulfonated para-ester diazo solution prepared in the step (1) into a chromophore 1, controlling the pH to be 5.0-8.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further performing coupling reaction for 5-10H, testing diazo by using an H acid test solution, and obtaining an orange reactive dye compound (I-1) when the diazo reaction is completely finished, wherein the lambda max in an aqueous solution is 440 nm.

Example 2

(1) Diazotization:

40.0g (0.1mol) of 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) aniline is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at a pH of 0.5-2.0 and a temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no discoloration occurs within 5 s). After the diazotization end point is reached, sulfamic acid is used for eliminating excessive sodium nitrite to obtain 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) aniline diazo liquid for storage and standby.

36.1g (0.1mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethyl sulfone sulfate aniline) is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at the pH value of 0.5-2.0 and the temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, the end point is not discolored within 5 s). And (4) after the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained sulfonated para-ester diazotization liquid for later use.

(2) Coupling:

firstly, 154g (0.1mol) of 3, 5-dihydroxybenzoic acid is added into 200g of water for pulping, the temperature is controlled to be 20-25 ℃, the pulped 3, 5-dihydroxybenzoic acid solution is added into the 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) phenylamine obtained in the step (1), the pH is controlled to be 2.0-4.0 by 30 percent liquid alkali, the temperature is controlled to be 0-20 ℃, the reaction is carried out for 15-20h, and the free 3, 5-dihydroxybenzoic acid is controlled to be below 3 percent by HPLC to obtain the end point, thus obtaining the chromophore 2 shown in the following formula (B).

And (2) adding the sulfonated para-ester diazo solution prepared in the step (1) into a chromophore 2, controlling the pH to be 5.0-8.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further performing coupling reaction for 5-10H, testing diazo by using an H acid test solution, and obtaining an orange reactive dye compound (I-11) when the diazo reaction is completely finished, wherein the lambda max in an aqueous solution is 420 nm.

Examples 3 to 63:

dye compounds having the structures shown in Table 1 below were prepared by stepwise diazotization and coupling reactions using intermediate raw materials well known in the art according to the azo dye preparation methods described in example 1 or example 2, respectively.

TABLE 1

Application example 1

The reactive dyes prepared in the embodiments 1-63 of the invention are respectively dissolved in water, and 50g/L of anhydrous sodium sulphate is added to prepare dye liquor. The dyeing concentration is 4 percent (dye to cloth weight), the bath ratio is 1:20 (cloth weight grams to volume milliliters of dyeing liquid), the fabric is placed into cotton cloth for adsorption for 30 minutes at the temperature of 60 ℃, and alkali (20 g/L of sodium carbonate) is added for fixation for 45 minutes. And washing, soaping and drying the dyed fabric to obtain yellow to orange dyed fabric. The wash fastness and rubbing fastness tests were carried out according to the methods in ISO 105C 10-2006, ISO 105X12, and the results are shown in Table 2:

TABLE 2

As can be seen from Table 2, the reactive dye compound of the present invention is excellent in washing fastness and rubbing fastness.