阅读说明：本技术 一种具有高水洗牢度的偶氮染料化合物、制备方法及应用 (Azo dye compound with high washing fastness, preparation method and application ) 是由 李海玉 卞真俊 沙英华 赵闯 宋域灿 于 2021-07-27 设计创作，主要内容包括：本发明属于纺织染料技术领域,具体涉及一种具有高水洗牢度的偶氮染料化合物、制备方法及应用。所述偶氮染料化合物的结构如下式(1)所示。所述偶氮染料化合物作为分散染料应用于聚酯/聚酰胺纤维织物的染色和印花,得到相应色光从橙色到蓝色(具体包括黄色、橙色、红色、紫色和蓝色)。本发明的偶氮染料化合物既保持分散红343的色光鲜艳(非常接近分散红60)、染色固着率高、生产过程对环境友好的优点,又具备水洗牢度十分优秀的分散染料。(The invention belongs to the technical field of textile dyes, and particularly relates to an azo dye compound with high washing fastness, a preparation method and application thereof. The structure of the azo dye compound is shown as the following formula (1). The azo dye compound is applied to dyeing and printing of polyester/polyamide fiber fabrics as a disperse dye, and corresponding color light from orange to blue (specifically including yellow, orange, red, purple and blue) is obtained. The azo dye compound of the invention not only keeps bright color light of disperse red 343 (very close to disperse red 60), but also has high dyeing fixation rate and environmental friendliness in the production processFriendly and has very excellent washing fastness.)

1. An azo dye compound having high washing fastness, characterized in that: the structure of the azo dye compound is shown as the following formula (1):

in the formula:

R₁is hydrogen, C_1-4Alkoxy or halogen;

R₂is hydrogen, C_1-6Alkyl, allyl, benzyl, phenethyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₃is hydrogen, C_1-6Alkyl, allyl, benzyl, phenethyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₄is hydrogen, methyl, ethyl, hydroxy, C_1-4Alkylsulfonylamino group, C_1-4Alkylamido or halogen;

R₅is acetyl, sulfonamide, aminocarbonyl or- (CH)₂)_pCOOR₈Wherein p is 0-4, R₈Is hydrogen, C_1-8Straight chain alkyl, C_1-8Isomers of straight chain alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl methyl, benzyl or benzyl derivatives;

R₆is hydrogen, chlorine, bromine or cyano;

R₇is chlorine, bromine or cyano.

2. The azo dye compound having high washing fastness according to claim 1, wherein R is₅Is sulfonamide, aminocarbonyl, acetyl or- (CH)₂)_pCOOR₈Wherein p is 0-2.

3. The azo dye compound having high washing fastness according to claim 2, wherein- (CH)₂)_pCOOR₈In R₈Is a methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, tetrahydrofuryl methyl, benzyl or benzyl derivative.

4. The azo dye compound having high washing fastness according to claim 1, wherein R is₁Is hydrogen, methoxy or chlorine.

5. The azo dye compound having high washing fastness according to claim 1, wherein R is₂Is C_1-4Alkyl, benzyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-3, n is 0-3; said C is_1-4Alkyl is methyl, ethyl or propyl.

6. The azo dye compound having high washing fastness according to claim 1, wherein R is₃Is C_1-4Alkyl, benzyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-3, n is 0-3; said C is_1-4Alkyl is methyl, ethyl or propyl.

7. The azo dye compound having high washing fastness according to claim 1, wherein R is₄Is hydrogen, methyl, hydroxyl, methylsulfonamido or acetamido.

8. A method for producing an azo dye compound according to any one of claims 1 to 7, comprising the steps of:

s1 diazotization reaction: under the condition that the temperature is 0-10 ℃, nitrosyl sulfuric acid is dripped into the sulfuric acid solution of the compound A, and the reaction is continued for 1-5 hours after the dripping is finished, so as to obtain diazo liquid;

the compound A is

S2 preparation of coupling liquid: dispersing the compound B in an acidic aqueous medium at the temperature of 5-10 ℃ to obtain a coupling solution; the compound B is

S3 synthesis of the azo dye compound: under the condition of stirring, dropwise adding the diazo liquid prepared in S1 into the coupling liquid, filtering and washing with water to be neutral after the reaction is finished, and finally obtaining the azo dye compound X₁(ii) a The azo dye compound X₁In R₆Is hydrogen, chlorine or bromine, R₇Is chlorine or bromine; the azo dye compound X₁Is composed of

9. The method of claim 8, wherein R is₆And/or R₇When the cyano group is formed, the preparation method further comprises the following steps:

s4 cyanation reaction: the azo dye compound X₁Dissolving in DMF, adding cuprous cyanide or zinc cyanide in batches for cyaniding, cooling, filtering, washing with alcohol and washing with water after the reaction is finished, and finally obtaining the azo dye compound X₂The azo dye compound X₂The structural formula is as follows:

10. the use of the azo dye compound according to any of claims 1 to 7 as a disperse dye for dyeing or printing polyester/polyamide fiber fabrics to obtain corresponding shades including yellow, orange, red, violet and blue.

Technical Field

The invention belongs to the technical field of textile dyes, and particularly relates to an azo dye compound with high washing fastness, a preparation method and application thereof.

Background

In the disperse dye red variety, disperse red 60 has the greatest influence: the color light is bright (bright blue light red), the level dyeing property and the light fastness are good, the dye is popular with users, and the market consumption is large. However, disperse red 60 itself has some serious drawbacks: the lifting power is low, and the dyeing process is not suitable for deep color dyeing; the sublimation fastness is poor; the washing fastness is poor; the crude dye has low color development intensity and small molar extinction coefficient (about 14346 mol)^-1cm^-1) (ii) a The biggest problem is that: disperse red 60 belongs to anthraquinone dyes, and has large discharge amount of three wastes, high concentration of toxic and harmful substances and very difficult treatment in the production and manufacturing process, so that the production of the dyes is stopped from the last 80 th century in western developed countries and dye companies in Japan and Korea. At present, the product in the domestic and foreign markets is from China. In order to solve the problem of serious environmental hazard in the production process, researchers in dye industries at home and abroad are making hard research, development and exploration for nearly 50 years. In the last 80 th century, disperse Red 343 was introduced by Desida for the purpose of replacing disperse Red 60. Disperse red 343 with bright color (color is very close to disperse red 60) and high color development intensity (molar extinction coefficient of about 46390 mol)^-1cm^-1About 3 times as much as disperse red 60) is very popular with the dye industry. However, disperse red 343 has poor water washing fastness and is an important flaw.

Disclosure of Invention

In order to solve the problems, the invention provides an azo dye compound with high washing fastness, a preparation method and application thereof. The azo dye compound is an azo disperse dye which has high vividness and high washing fastness and is environment-friendly in the production process.

The invention is realized by the following technical scheme:

an azo dye compound having high washing fastness, the structure of which is shown in the following formula (1):

in the formula:

R₁is hydrogen, C_1-4Alkoxy or halogen;

R₂is hydrogen, C_1-6Alkyl, allyl, benzyl, phenethyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、

-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₃is hydrogen, C_1-6Alkyl, allyl, benzyl, phenethyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₄is hydrogen, methyl, ethyl, hydroxy, C_1-4Alkylsulfonylamino group, C_1-4Alkylamido or halogen;

R₅is acetyl, sulfonamide, aminocarbonyl or- (CH)₂)_pCOOR₈Wherein p is 0-4, R₈Is hydrogen, C_1-8Straight chain alkyl, C_1-8Isomers of straight chain alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl methyl, benzyl or benzyl derivatives;

R₆is hydrogen, chlorine, bromine or cyano;

R₇is chlorine, bromine or cyano.

Further, said R₅Is sulfonamide, aminocarbonyl, acetyl or- (CH)₂)_pCOOR₈Wherein p is 0-2; - (CH)₂)_pCOOR₈In R₈Is C_1-6Straight chain alkyl (including methyl, ethyl, propyl, butyl, pentyl and hexyl), C_1-6Isomers of straight chain alkyl groups (including isopropyl, isobutyl and tert-butyl), cyclopentyl, cyclohexyl, tetrahydrofuryl methyl, benzyl or benzyl derivatives.

Further, the benzyl derivative is C-containing_1-4Alkyl of (C)_1-4Alkoxy, chlorine, bromine, cyano, hydroxy, nitro or C_1-4SO₂-benzyl derivatives of substituents.

Further, the benzyl derivative is 4-methylbenzyl, 4-methoxybenzyl, 4-chlorobenzyl, 4-cyanobenzyl or 4-nitrobenzyl.

Further, said R₁Is hydrogen, methoxy or chlorine.

Go toStep (a), the R₂Is C_1-4Alkyl, benzyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-3, n is 0-3; said C is_1-4Alkyl is methyl, ethyl or propyl.

Further, said R₃Is C_1-4Alkyl, benzyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-3, n is 0-3; said C is_1-4Alkyl is methyl, ethyl or propyl.

Further, said R₄Is hydrogen, methyl, hydroxy, C_1-4Alkylsulfonylamino or C_1-4An alkylamido group; said C is_1-4The alkylsulfonylamino group is a methylsulfonylamino group; said C is_1-4The alkylamido group is an acetamido group.

Another object of the present invention is to provide a method for preparing the above azo dye compound, comprising the steps of:

s1 diazotization reaction: under the condition that the temperature is 0-10 ℃, nitrosyl sulfuric acid is dripped into the sulfuric acid solution of the compound A, and the reaction is continued for 1-5 hours after the dripping is finished, so as to obtain diazo liquid;

the compound A is

The sulfuric acid solution of the compound A is prepared by dissolving the compound A in sulfuric acid and cooling to-5-20 ℃;

the chemical reaction equation related to S1 includes:

s2 preparation of coupling liquid: dispersing the compound B in an acidic aqueous medium at the temperature of 5-10 ℃ to obtain a coupling solution; the compound B is

S3 synthesis of the azo dye compound: dropwise adding the diazo liquid prepared in S1 into the coupling liquid under the stirring condition; after the reaction is finished, filtering and washing with water to be neutral to finally obtain the azo dye compound X₁(ii) a The azo dye compound X₁In R₆Is hydrogen, chlorine or bromine, R₇Is chlorine or bromine; the azo dye compound X₁Is composed of

The chemical reaction involved in S3 includes:

further, R in the azo dye compound₆And/or R₇When the cyano group is formed, the preparation method further comprises the following steps:

s4 cyanation reaction: the azo dye compound X₁Dissolving in DMF, and adding cuprous cyanide in portionsOr zinc cyanide is added for 1 to 3 hours, and after the reaction is finished, the azo dye compound X is finally obtained through cooling, filtering, alcohol washing and water washing₂The azo dye compound X₂The structural formula is as follows:

the chemical reaction involved in S4 includes:

further, the mole ratio of the compound a to the nitrosyl sulfuric acid in S1 is: 1: 1.0-1.1; the preferred molar ratio is: 1:1.0-1.02.

Further, the PH value in the acidic medium in S2 is in the range of: 1-5.

Further, in the preparation method, the molar ratio of the compound A to the compound B is 1: 1.0-1.1; preferably in a molar ratio of 1:1.01 to 1.03.

Further, the azo dye compound X₁The molar ratio of the cuprous cyanide to the cuprous cyanide is 1:2.0-2.2, preferably 1: 2.0-2.1.

Further, the azo dye compound X₁The molar ratio of the zinc cyanide to the zinc cyanide is 1: 1-1.2; preferably 1: 1.0-1.05.

It is a further object of the present invention to provide a use of the above azo dye compound as a disperse dye for dyeing and printing polyester/polyamide fiber fabrics to give corresponding shades from orange to blue (specifically including yellow, orange, red, violet and blue).

Further, the azo dye compound is processed as a disperse dye according to a general process method of disperse dye dispersion processing or according to other process methods of disperse dye dispersion processing.

Further, the azo dye compound is used as a disperse dye for hydrophobic fiber materials, especially for dyeing or printing of polyester fibers, and polyamide textile dyeing requirements. Before the disperse dye shown in the formula (1) is used, the disperse dye is mixed with a dispersing auxiliary agent and suspended in a liquid medium, and then sanding, microparticulation and drying are carried out to obtain the disperse dye; the dispersing auxiliary agent is an anionic dispersing agent and/or a nonionic auxiliary agent.

Further, the anionic dispersant is one or more than two of naphthalene sulfonic acid formaldehyde condensate, alkyl naphthalene sulfonic acid formaldehyde condensate, benzyl naphthalene sulfonic acid formaldehyde condensate and lignosulfonate.

Further, the nonionic auxiliary agent is fatty alcohol-polyoxyethylene ether or fatty acid-polyoxyethylene ester.

Further, the azo dye compound and the dispersing auxiliary agent account for 10-50% by weight, and the dispersing auxiliary agent accounts for 50-90% by weight.

Further, when the azo dye compound is prepared into a disperse dye, the disperse dye can be a single structure or a mixture of a plurality of dyes, and the composite dye can be a compound of a plurality of single dyes or can be directly synthesized into a mixed dye for commercial processing.

The azo dye compound with high washing fastness, the preparation method and the application of the azo dye compound at least have the following beneficial technical effects:

(1) the azo dye compound of the invention can be widely used for dyeing polyester fiber or amine fiber blended fabric as disperse dye. The dyeing process has the characteristics of good washing fastness, high lifting power, high dyeing degree and the like, and can reach 4-5 grades.

(2) The azo dye series compound has bright color light and wide color spectrum, and covers yellow, orange, yellow, blue, purple and blue. And the synthesis process is simple, environment-friendly, relatively less in the amount of three wastes and easy to treat.

(3) The azo dye compound not only keeps the advantages of bright color light of disperse red 343 (very close to disperse red 60), high dyeing fixation rate and environment-friendly production process, but also has the disperse dye with very excellent washing fastness.

Drawings

FIG. 1 is a chart of the H spectrum of the azo dye compound prepared in example 27 of the present invention.

FIG. 2 is a spectrum C of an azo dye compound prepared in example 27 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.

The following examples serve to illustrate the invention. In the examples, parts are by weight, percentages are by weight and temperatures are in degrees celsius unless otherwise indicated. The relationship between parts by weight and parts by volume is the same as the relationship between grams and cubic centimeters.

Examples 1 to 9 below are for the azo dye compounds X₁In some of the examples given, the azo dye compound X₁The structural formula of (A) is as follows:

wherein:

R₁is hydrogen or methoxy;

R₂is hydrogen, C_1-6Alkyl, allyl, benzyl, phenethyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₃is hydrogen, C_1-6Alkyl, allyl, benzyl, phenethyl, cyanoethyl,Or- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₄is hydrogen, methyl, hydroxy, methylsulfonamido or acetamido;

R₅is acetyl, sulfonamide, aminocarbonyl or of the formula: - (CH)₂)_pCOOR₈Wherein p is 0-4, R₈Is hydrogen, C_1-8Straight chain alkyl, C_1-8Isomers of straight chain alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl methyl, benzyl or benzyl derivatives.

Example 1

180G sulfuric acid and 56G nitrosyl sulfuric acid were added to a 250ml three-necked flask, cooled to 0-5 ℃ in an ice bath with stirring, and 58.6G compound (A-1) was added in portions for 1 hour, and then stirred at that temperature for 3 hours.

After the reaction is finished, obtaining a diazo liquid; dripping the diazo liquid into a mixture containing 50ML sulfuric acid, 800G ice water and 56.48G compound (B-1) within 1 hour at the temperature of 5-9 ℃, stirring for 3 hours, filtering, washing with water to be neutral, and drying to obtain the azo dye compound (X)₁-1)111.15G。

The dye is used for dyeing polyester fibers to obtain red, orange and yellow light. λ max (nm) 445 nm.

Example 2:

synthesis of dye (X) according to the preparation of example 1₁-2) the dye is used for dyeing polyester fiber to obtain red orange. λ max (nm) 449.1 nm.

Example 3:

synthesis of dye (X) according to the preparation of example 1₁-3) for dyeing polyester fibres to a golden yellow colour. λ max (nm) 445 nm.

Example 4:

synthesis of dye (X) according to the procedure of example 1₁4) the dye is used for dyeing the polyester fiber to golden yellow. λ max (nm) ═ 438 nm.

Example 5:

synthesis of dye (X) according to the procedure of example 1₁-5) for dyeing polyester fibers to obtain red orange. λ max (nm) 451 nm.

Example 6:

synthesis of dye (X) according to the procedure of example 1₁-6) for dyeing polyester fibres to a yellowish brown colour. λ max (nm) 430.8 nm.

Example 7:

synthesis of dye (X) according to the procedure of example 1₁7) for dyeing polyester fibres to a yellow-red colour. λ max (nm) 449.5 nm.

Example 8:

synthesis of dye (X) according to the procedure of example 1₁-8) for dyeing polyester fibers to obtain red orange. λ max (nm) 442.2 nm.

Example 9:

synthesis of dye (X) according to the procedure of example 1₁-9) for dyeing polyester fibres to a red colour. λ max (nm) 466 nm.

Examples 10-12 below are some examples according to formula (1), the structural formula of formula (1) being as follows:

in the formula:

R₁is hydrogen or methoxy;

R₂is composed ofOr- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₃is composed ofOr- (CH)₂)_mCOOM, M being-CH₂CH₂OCH₃、-CH₂CH₂OCH₂CH₃、-(CH₂)_nCH₃、-(CH₂)_nCH₃Isomers of (A) or (B)Wherein m is 0-4, n is 0-5;

R₄is hydrogen, methyl, hydroxy, methylsulfonamido or acetamido;

R₅is acetyl, sulfonamide, aminocarbonyl or of the formula: - (CH)₂)_pCOOR₈Wherein p is 0-4, R₈Is hydrogen, C_1-8Straight chain alkyl, C_1-8Isomers of straight chain alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl methyl, benzyl or benzyl derivatives;

R₆is cyano;

r7 is cyano.

Example 10:

adding 180G sulfuric acid and 56G nitrosyl sulfuric acid into 250ml three-neck flask, cooling to 0-5 deg.C with ice bath under stirring, adding 45.8G compound (A-2) for 1 hr, and stirring at the temperature for 2 hr.

After the reaction is finished, obtaining a diazo liquid; dripping the diazo liquid into a mixture containing 50ML sulfuric acid, 800G ice water and 56.4G compound (B-1) within 1 hour at the temperature of 6-10 ℃, stirring for 3 hours, filtering, washing with water to be neutral, and drying to obtain the azo dye compound (X)₁-10)97.9G。

400G of DMF and 3G of sodium bromide were added to a 1000ml three-necked flask, and 97.9G of (X) was stirred₁-10) slowly adding the mixture, heating to 80-90 ℃, stirring for 1 hour to completely dissolve the materials, adding 17G cuprous cyanide in batches, reacting at 90-100 ℃ for 2 hours, heating to 110-;

cooling to 55 deg.C, adding 300G methanol for 1 hr, cooling to 30 deg.C, adding 1.5G sodium thiosulfate, stirring for 2 hr, filtering, washing with methanol to colorless, collecting mother liquor, washing with water, and draining to obtain dye compound (X)₂-1)82.2G, which dye is used for dyeing polyester fibers orange. λ max (nm) 509 nm.

Example 11:

synthesis of dye (X) according to the procedure of example 10₂-2) for dyeing polyester fibres to orange. λ max (nm) 466 nm.

Example 12:

synthesis of dye (X) according to the procedure of example 10₂-3) for dyeing polyester fibres to a yellow-red colour. λ max (nm) 509 nm.

Examples 13 to 32 which follow are some examples according to formula (1), in which

In the formula:

R₁is hydrogen;

R₂is ethyl, propyl, butyl, cyanoethyl, CH₂CH₂COOCH₃、-CH₂COOCH₃、Or

R₃Is ethyl, propyl, butyl, cyanoethyl, CH₂CH₂COOCH₃、-CH₂COOCH₃、Or

R₄Is a hydroxyl group;

R₅is acetyl or of the general formula: -COOR₈，R₈Is hydrogen, C_1-8Straight chain alkyl, C_1-8Isomers of straight chain alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl methyl, benzyl or benzyl derivatives;

R₆is cyano;

R₇is cyano.

Example 13:

180G sulfuric acid and 56G nitrosyl sulfuric acid were added to a 250ml three-necked flask, the temperature was lowered to 0 to 5 ℃ in an ice bath with stirring, and 58.6G compound (A-3) was added in portions for 1 hour, and after the addition, the mixture was stirred at that temperature for 2 hours.

After the reaction is finished, obtaining a diazo liquid; dripping the diazo solution into a mixture containing 50ML sulfuric acid, 800G ice water and 50.9G compound (B-2) at 6-9 deg.C within 1 hr, stirring for 3 hr, filtering, washing with water to neutrality, and oven drying to obtain compound (X)₁-11)103.6G。

In a 1000ml three-necked flask, 416G of DMF and 3G of sodium bromide are added, and 103.6G of (X) are stirred₁-11) slowly adding the mixture, heating to 80-90 ℃, stirring for 1 hour to completely dissolve the materials, adding 33.3G cuprous cyanide in batches, carrying out heat preservation reaction at 70-80 ℃ for 2 hours, heating to 105-;

cooling to 55 deg.C, adding 336G methanol for 1 hr, cooling to 30 deg.C, adding 3G sodium thiosulfate, stirring for 2 hr, filtering, washing with methanol to colorless, collecting mother liquor, washing with water, and draining to obtain dye compound (X)₂-4)77.7G, theThe dye is used for dyeing the polyester fiber to obtain blue light red. λ max (nm) 542 nm.

Example 14:

synthesis of dye (X) according to the procedure of example 13₂-5) for dyeing polyester fibres to a red color λ max (nm) 526nm

Example 15:

synthesis of dye (X) according to the procedure of example 13₂-6) for dyeing polyester fibres to a red colour. λ max (nm) ═ 523 nm. IR (cm)^-1)：3075cm^-1(Ar-H)，2954cm^-1(-CH₂-)，2234cm^-1(-CN)，1717cm^-1(-C＝O)，1591cm^-1，1524cm^-1(benzene ring C ═ C), 1434cm^-1(-N＝N-)，1291cm^-1，1147cm^-1(C-O)，808cm^-1，768cm^-1((aromatic ring C-H).

Example 16:

synthesis of dye (X) according to the procedure of example 13₂7) for dyeing polyester fibres to a red colour. λ max (nm) 521 nm. IR (cm)^-1)：3069cm^-1(Ar-H)，2955cm^-1(-CH₂-)，2229cm^-1(-CN)，1713cm^-1(-C＝O)，1591cm^-1，1524cm^-1(benzene ring C ═ C), 1440cm^-1(-N＝N-)，1331cm^-1(aryl C-N), 1291cm^-1，1166cm^-1(C-O)，806cm^-1，768cm^-1((aromatic ring C-H).

Example 17:

synthesis of dye (X) according to the procedure of example 13₂-8) for dyeing polyester fibres to obtain a red λ max (nm) 523nm

Example 18:

synthesis of dye (X) according to the procedure of example 13₂-9) for dyeing polyester fibres to a red color λ max (nm) 524nm

Example 19:

synthesis of dye (X) according to the procedure of example 13₂10) for dyeing polyester fibres to blue red, λ max (nm) 539.7nm

Example 20:

synthesis of dye (X) according to the procedure of example 13₂11) for dyeing polyester fibres to a red color λ max (nm) 525nm

Example 21:

synthesis of dye (X) according to the procedure of example 13₂12) for dyeing polyester fibres in red, with a colour λ max (nm) 497 nm.

Example 22:

180G sulfuric acid and 56G nitrosyl sulfuric acid were added to a 250ml three-necked flask, the temperature was lowered to 0 to 5 ℃ in an ice bath with stirring, 61.8G of the compound (A-4) was added in 1 hour portion, and after the addition, the mixture was stirred at that temperature for 2 hours.

After the reaction is finished, obtaining a diazo liquid; dripping the diazo liquid into a mixture containing 50ML sulfuric acid, 800G ice water and 56.4G compound (B-1) within 1 hour at the temperature of 5-9 ℃, stirring for 3 hours, filtering, washing with water to be neutral, and drying to obtain the azo dye compound (X)₁-12)110.6G。

A1000 ml three-necked flask was charged with 445G of DMF and 3G of sodium bromide, and 110.6G of (X) was stirred₁-12) slowly adding the mixture, heating to 80-90 ℃, stirring for 1 hour to completely dissolve the materials, adding 32.9G cuprous cyanide in batches, carrying out heat preservation reaction at 90-95 ℃ for 2 hours, heating to 115 ℃ and carrying out heat preservation reaction at 120 ℃ for 3 hours;

cooling to 55 deg.C, adding 340G methanol for 1 hr, cooling to 30 deg.C, adding 3G sodium thiosulfate, stirring for 2 hr, filtering, washing with methanol to colorless, collecting mother liquor, washing with water, and draining to obtain dye compound (X)₂13)92.1G, which is used for dyeing polyester fibers to obtain blue light red. λ max (nm) 542 nm.

Example 23:

synthesis of dye (X) according to the procedure of example 22₂14) for dyeing polyester fibres to a blue red color. λ max (nm) 545 nm.

Example 24:

synthesis of dye (X) according to the procedure of example 22₂15) for dyeing polyester fibres to a blue red color. λ max (nm) 542 nm. IR (cm)^-1)：2951cm^-1(-CH₂-)，2230cm^-1(-CN)，1715cm^-1(-C＝O)，1436cm^-1(N＝N)，1620cm^-1，1588cm^-1(benzene ring C ═ C), 1337cm^-1(aryl C-N), 1226cm^-1，1171cm^-1(C-O)，795cm^-1，761cm^-1(aromatic ring C-H).

Example 25:

synthesis of dye (X) according to the procedure of example 22₂-16) for dyeing polyester fibres to a blue red color. λ max (nm) 543 nm.

Example 26:

synthesis of dye (X) according to the procedure of example 22₂17) for dyeing polyester fibres to a blue red color. λ max (nm) 543 nm.

Example 27:

as shown in FIGS. 1 and 2, this example synthesizes a dye (X) according to the preparation method of example 22₂18) for dyeing polyester fibres to a blue red color. λ max (nm) 543 nm. IR (cm)^-1):2946cm^-1(-CH₂-)，2225cm^-1(-CN)，1718cm^-1(-C＝O)，1434cm^-1(-N＝N-)，1626cm^-1，1591cm^-1(benzene ring C ═ C), 1352cm^-1(aryl C-N),1273m^-1，1155cm^-1((C-O)，794cm^-1，764cm^-1(benzene ring C-H).

Example 28:

synthesis of dye (X) according to the procedure of example 22₂19) for dyeing polyester fibres to a blue red color. λ max (nm) 540 nm.

Example 29:

synthesis of dye (X) according to the procedure of example 22₂-20) for dyeing polyester fibres to a blue red color. λ max (nm) ═ 537.8 nm. IR (cm)^-1)：2930cm^-1，2954cm^-1(-CH₂-)，2227cm^-1(-CN)，1724cm^-1(-C＝O)，1590cm^-1，1524cm^-1(benzene ring C ═ C), 1269cm^-1，1154cm^-1(C-O)，816cm^-1，762cm^-1((aromatic ring C-H).

Example 30:

synthesis of dye (X) according to the procedure of example 22₂21) for dyeing polyester fibres to a blue red color. λ max (nm) 538 nm.

Example 31:

synthesis of dye (X) according to the procedure of example 22₂22) for dyeing polyester fibres to a blue red color. λ max (nm) 543.5 nm.

Example 32:

synthesis of dye (X) according to the procedure of example 22₂23) for dyeing polyester fibres to a blue red color. λ max (nm) 543 nm.

Example 33:

synthesis of dye (X) according to the procedure of example 22₂-24) for dyeing polyester fibres to a blue red color. λ max (nm) 544 nm.

Examples 34 to 43 which follow are some examples according to formula (1), in which

In the formula:

R₁is hydrogen or methoxy;

R₂is ethyl, propyl, butyl, cyanoethyl, -CH₂CH₂COOCH₃、-CH₂COOCH₃、Or

R₃Is ethyl, propyl, butyl, cyanoethyl, -CH₂CH₂COOCH₃、-CH₂COOCH₃、

Or

R₄Is methyl, acetamido or methylsulfonamido;

R₅is acetyl or of the general formula: -COOR₈，R₈Is hydrogen, C_1-8Straight chain alkyl, C_1-8Isomers of straight chain alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl methyl, benzyl or benzyl derivatives;

R₆is cyano;

R₇is cyano.

Example 34:

180G sulfuric acid and 56G nitrosyl sulfuric acid were added to a 250ml three-necked flask, the temperature was lowered to 0 to 5 ℃ in an ice bath with stirring, 61.8G of the compound (A-4) was added in 1 hour portion, and after the addition, the mixture was stirred at that temperature for 3 hours.

After the reaction is finished, obtaining a diazo liquid; dripping the diazo solution into a mixture containing 50ML sulfuric acid, 800G ice water and 56G compound (B-1) at 5-8 deg.C within 1 hr, stirring for 3 hr, filtering, washing with water to neutrality, and oven drying to obtain compound (X)₁-13)109G。

Into a 1000ml three-necked flask were charged 436G of DMF and 3G of sodium bromide, and 109G of (X) was added under stirring₁-13) slowly adding the mixture, heating to 80-90 ℃, stirring for 1 hour to completely dissolve the materials, adding 32.6G cuprous cyanide in batches, carrying out heat preservation reaction at 80-90 ℃ for 2 hours, heating to 115-120 ℃ and carrying out heat preservation reaction for 1 hour;

cooling to 55 deg.C, adding 330G methanol for 1 hr, cooling to 30 deg.C, adding 3G sodium thiosulfate, stirring for 2 hr, filtering, washing with methanol to colorless, collecting mother liquor, washing with water, and draining to obtain dye compound (X)₂-24)75.9G, which is used for dyeing polyester fibers to obtain a red-violet color. λ max (nm) 546 nm.

Example 35:

synthesis of dye (X) according to the procedure of example 33₂26) used for dyeing polyester fibers to obtain red purple. λ max (nm) 520 nm.

Example 36:

synthesis of dye (X) according to the procedure of example 33₂27) for dyeing polyester fibers to a blue violet color. λ max (nm) 549 nm.

Example 37:

synthesis of dye (X) according to the procedure of example 33₂-28) for polyester fibresThe blue light purple is obtained after dyeing. λ max (nm) 565 nm. IR (cm)^-1)：3356cm^-1(N-H)，2955cm^-1(-CH₂-)，2218cm^-1(-CN)，1720cm^-1(-C＝O)，1549cm^-1,1524cm^-1(C-phenyl ring), 1460cm^-1(-N＝N-)，1336cm^-1(aryl C-N), 1262cm^-1，1162cm^-1，1119cm^-1(C-O)，859cm^-1，798cm^-1，765cm^-1(Ar-H)。

Example 38:

synthesis of dye (X) according to the procedure of example 33₂29) used for dyeing polyester fibers to obtain blue purple. λ max (nm) ═ 563 nm.

Example 39:

synthesis of dye (X) according to the procedure of example 33₂30) for dyeing polyester fibers to obtain a red-violet color. λ max (nm) 551 nm. IR (cm)^-1)：3282cm^-1(N-H)，929cm^-1(-CH₂-)，2232cm^-1(-CN)，1726cm^-1(-C＝O)，1682cm^-1，1605cm^-1(benzene ring C ═ C), 1434cm^-1(-N＝N-)，1339cm^-1(aryl C-N),1280cm^-1，1169cm^-1，1135cm^-1(C-O)，815cm^-1(Ar-H)。

Example 40:

synthesis of dye (X) according to the procedure of example 33₂31) for dyeing polyester fibers to a blue-violet color. λ max (nm) 565 nm. IR (cm)^-1)：3342cm^-1(N-H)，2957cm^-1(-CH₂-)，2230cm^-1(-CN)，1708cm^-1(-C＝O)，1587cm^-1，1524cm^-1(benzene ring C ═ C), 1430cm^-1(-N＝N-)，1379cm^-1(aryl C-N), 1266cm^-1，1118cm^-1(C-O),795cm^-1，768cm^-1(Ar-H)。

Example 41:

synthesis of dye (X) according to the procedure of example 33₂32) for dyeing polyester fibres to a blue violet colour. λ max (nm) 586.7 nm.

Example 42:

synthesis of dye (X) according to the procedure of example 33₂33) for dyeing polyester fibers to a blue violet color. λ max (nm) 560.4 nm.

Example 43:

synthesis of dye (X) according to the procedure of example 33₂-34) for dyeing polyester fibres in purple. λ max (nm) 544.6 nm. IR (cm)^-1)：2912cm^-1,2968cm^-1(-CH₂-)，2231cm^-1(-CN)，1715cm^-1(-C＝O),1588cm^-1,1509cm^-1(benzene ring C ═ C), 1328cm^-1(aryl C-N), 1248cm^-1，1167cm^-1(C-O),1131cm^-1，1095cm^-1(aminoalkyl C-N), 851cm^-1，807cm^-1，762cm^-1(aromatic ring C-H).

Examples 44 to 51 which follow are some examples according to formula (1), in which

In the formula:

R₁refers to methoxy.

R₂Is ethyl, propyl, butyl, cyanoethyl, -CH₂CH₂COOCH₃、-CH₂COOCH₃、Or

R₃Is ethyl, propyl, butyl, cyanoethyl, -CH₂CH₂COOCH₃、-CH₂COOCH₃、

Or

R₄Is an acetylamino group;

R₅is acetyl or of the general formula: -COOR₈，R₈Is hydrogen, C_1-8Straight chain alkyl, C_1-8Isomers of straight chain alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl methyl, benzyl or benzyl derivatives;

R₆is cyano;

R₇is cyano.

Example 44:

synthesis of dye (X) according to the procedure of example 33₂35) for dyeing polyester fibers to obtain a red blue color. λ max (nm) ═ 590 nm.

Example 45:

synthesis of dye (X) according to the procedure of example 33₂36) for dyeing polyester fibres blue. λ max (nm) ═ 590 nm.

Example 46:

synthesis of dye (X) according to the procedure of example 33₂-37) for dyeing polyester fibres blue. λ max (nm) 605 nm.

Example 47:

synthesis of dye (X) according to the procedure of example 33₂38) for dyeing polyester fibres blue. λ max (nm) 600 nm.

Example 48:

synthesis of dye (X) according to the procedure of example 33₂39) for dyeing polyester fibres blue. λ max (nm) ═ 590 nm.

Example 49:

synthesis of dye (X) according to the procedure of example 33₂40) for dyeing polyester fibres blue. λ max (nm) 608 nm. IR (cm)^-1)：3064cm^-1(Ar-H)，2230cm^-1(-CN)，1709cm^-1(-C＝O)，1605cm^-1，1504cm^-1(benzene ring C ═ C), 1349cm^-1(aryl C-N), 1210cm^-1，1141cm^-1(C-O)，872cm^-1，770cm^-1((aromatic ring C-H).

Example 50:

synthesis of dye (X) according to the procedure of example 33₂41) for dyeing polyester fibres blue. λ max (nm) 620.8 nm.

Example 51:

synthesis of dye (X) according to the procedure of example 33₂42) for dyeing polyester fibres to a green blue colour. λ max (nm) 615.9 nm.

The dye compounds prepared in examples 52-69 are shown in Table one.

The dyes described below are likewise suitable for dyeing polyester fiber materials. They are prepared analogously to the examples:

table one:

dyeing application and performance test:

and (3) measuring the solid content of the dye filter cake obtained according to the embodiment, calculating the folding dry amount, adding a dispersing agent MF (shown in the following table 2) and a proper amount of water, performing sand grinding dispersion in a sand mill, filtering out dye dispersion slurry after sampling and inspection are qualified, and performing quick drying to obtain corresponding dye commercial powder.

Table 2:

taking 0.1 g of each disperse dye finished product, placing the disperse dyes finished product in 100ml of water for uniform dispersion, transferring 25ml of a transfer pipette, placing the transfer pipette in a dye vat of a high-temperature high-pressure dyeing machine, adding 74ml of water, adjusting the pH value of a dye bath to be 5 by using a sodium acetate buffer solution, adding 5g of superfine polyester fiber standard cloth, closing the dye vat, and starting dyeing: heating from 60 ℃ to 130 ℃ within 45 minutes, keeping the temperature at 130 ℃ for dyeing for 60 minutes, stopping heat preservation, cooling to below 90 ℃, taking out the dyed sample, carrying out cold water washing and reduction washing, and drying. The color fastness to washing is respectively measured by adopting the national standard GB/T3921-1997. The test results are shown in Table 3.

Table 3:

as shown in the table, when the novel high-washing-fastness azo dye compound is applied to dyeing of polyester fiber or spandex blended fabric, dyed fabric with high vividness and good washing fastness can be obtained.