CN102816452B - Benzothiazole dye monomeric compound and disperse dye - Google Patents

Abstract

The invention provides a benzothiazole dye monomer compound suitable for dyeing hydrophobic fiber materials, the structure of which is shown in formula (I). The disperse dye prepared by using the dye monomer compound of the present invention has good dyeing depth and wide dyeing pH range when applied to fabric dyeing, and is especially suitable for printing and dyeing of hydrophobic textile materials, including semi-synthetic or synthetic hydrophobic fiber blended textiles. Dyeing and printing of materials, especially suitable for dyeing polyester materials, can obtain red dyed fabrics with uniform color tone, excellent wash resistance and excellent ironing sublimation resistance.

Description

A kind of benzothiazole dye monomer compound and disperse dye

(1) Technical field

The invention relates to a benzothiazole dye monomer compound suitable for dyeing hydrophobic fiber materials and a disperse dye prepared from it.

(2) Background technology

In recent years, with the increase in the demand and consumption of polyester fabrics, disperse dyes have become one of the most active dyes in the world dye market. The fastness of polyester fabrics dyed with disperse dyes is an important indicator of its quality. On the one hand, products with poor color fastness will fade during wearing, which will affect other clothes worn on the body, or contaminate other clothes when washed with other clothes, affecting the appearance; on the other hand, there is a direct relationship between good and bad color fastness To the health and safety of the human body, the dye molecules on products with poor color fastness may be absorbed by the human body through the skin and endanger the skin and even harm the health of the body.

The color fastness of the dye mainly depends on the bonding force between the dye and the fiber. If the bonding bond between the two is not strong, no amount of external force can make them bond firmly, even if the auxiliary agent or other accelerator is used to make the dye fast. The color fastness is increased by about 0.5 grades, and it cannot withstand the damage of external factors such as ironing, washing, and friction. Therefore, it is particularly important to strive to improve the color fastness of the product itself.

In recent years, the demand for heterocyclic intermediates in the market has grown rapidly. The introduction of heterocyclic rings into dye molecules is an active field of research and development for disperse dyes. Although the existing literature CN101522816 and GB909843 provide a new dye compound, it can Fastness and sublimation fastness have performed well, but there is still room for further improvement.

(3) Contents of the invention

The object of the present invention is to: provide a class of disperse dye monomer compounds with nitrobenzothiazole heterocyclic amine as the diazo component, which have high color yield, good level dyeing property and wide dyeing pH range when applied to fabric dyeing , Excellent ironing sublimation fastness and washing fastness.

The technical scheme adopted in the present invention is:

A benzothiazole dye monomer compound, the structure of which is shown in formula (I):

In formula (I):

R ₁ and R ₂ are each independently -CH ₂ CH ₂ COOH, -CH ₂ CH=CH ₂ , benzyl or -CH ₂ CH ₂ COOCH ₂ COR ₄ , and R ₄ is methyl or phenyl;

R ₃ is -OH, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or -NHCOCH ₃ .

Preferably, R ₁ and R ₂ are both -CH ₂ CH ₂ COOH or -CH ₂ CH ₂ COOCH ₂ COR ₄ , and R ₃ is -OH, -CH ₃ , -OCH ₃ or -NHCOCH ₃ .

More preferably, the benzothiazole dye monomer compound is one of the following:

The azo disperse dyes described in the present invention can be prepared by conventional methods in the industry, such as: diazotizing the 2-amino-6-nitrobenzothiazole compound of formula (II), and then combining the diazonium salt of the compound with the formula The components of (Ⅲ) are coupled to prepare the target product.

In the above structural formulas (II) and (III), the definitions of R ₁ , R ₂ and R ₃ are the same as those in formula (I).

The diazotization of 2-amino-6-nitrobenzothiazole of formula (II) is carried out by its known method, such as using sodium nitrite or nitrosyl Sulfuric acid is used as a diazotization reagent, and the temperature range for diazotization is -10°C~10°C.

Likewise, the diazotized compound of formula (II) can be coupled with the compound of formula (III) according to known methods. The reaction is suitably carried out in an acidic medium at a temperature ranging from -10°C to 10°C.

The diazo components of formula (II) are known compounds or can be prepared by known methods. Coupling components of formula (III) can also be prepared by known methods.

The invention also relates to the application of the benzothiazole dye monomer compound in the preparation of disperse dyes for dyeing hydrophobic fiber materials. The dye monomer compound of the present invention is almost insoluble in water. Before use, the dye monomer compound can be conveniently converted into a dye formulation, such as in the presence of auxiliary agents, water or other wetting agents, the dye of the present invention The monomer compound is ground to an average particle size of 0.1-10 microns, and then vacuum-dried or spray-dried.

The invention also relates to a disperse dye used for dyeing hydrophobic fiber materials, which is composed of more than one dye monomer compound of formula (I) and an auxiliary agent, and the mass ratio of the dye monomer compound to the auxiliary agent is 1:0.8~5 .

The auxiliary agent is a commonly used dispersant, diffusing agent, etc. when compounding disperse dyes, and can be one of the following or a mixture of two or more of them: naphthalenesulfonic acid formaldehyde condensate, alkylnaphthalenesulfonic acid formaldehyde condensate, benzyl Anionic dispersants such as naphthalenesulfonic acid formaldehyde condensate and lignosulfonate. Specifically, naphthalenesulfonic acid formaldehyde condensate such as diffusant NNO, alkylnaphthalenesulfonic acid formaldehyde condensate such as dispersant MF (methylnaphthalenesulfonic acid formaldehyde condensate), benzylnaphthalenesulfonic acid formaldehyde condensate such as diffusing agent CNF, etc. , lignosulfonate such as sodium lignosulfonate (such as commercially available dispersants Reax 83A, Reax 85A), etc.

Preferably, the composition is composed of more than one benzothiazole dye monomer compound in formulas (I-1) to (I-20) and auxiliary agents.

The disperse dyes made from the nitrobenzothiazole disperse dye monomer compound of the present invention are especially suitable for the printing and dyeing of hydrophobic textile materials, including the dyeing and printing of semi-synthetic or synthetic hydrophobic fiber textile materials. The material may be dyed in any form including fibres, yarns or non-woven or woven or knitted fabrics. Especially for dyeing polyester materials, it can obtain red dyed fabrics with uniform color tone, washability and excellent sublimation fastness to ironing.

The disperse dyes prepared according to the present invention can be dyed by common exhaust dyeing method and pad dyeing method, and can also be used for direct printing. Among them, the ordinary exhaust dyeing method is such as pretreating the polyester fabric, putting it into the dyeing vat for dip dyeing, after dyeing, washing in cold water to neutrality, wringing, and then performing reduction cleaning and drying; direct printing is like performing pre-dyeing treatment on the fabric. , drying, setting, printing disperse dye color paste on the printing machine, and then steaming, using steaming to fix the dye on the fabric, finally washing, tentering and setting.

In addition, the dye monomer compound can be conveniently compounded with other disperse dye monomer compounds to obtain various hues. Of course, the dye monomer compounds of the above general formula can also form a mixture with each other.

The beneficial effects of the present invention are mainly embodied in that: a novel nitrobenzothiazole dye monomer compound and its application are provided, and a disperse dye composition composed of the nitrobenzothiazole dye monomer compound is provided. The disperse dye prepared by using the dye monomer compound of the present invention has good dyeing depth and wide dyeing pH range when applied to fabric dyeing, and is especially suitable for printing and dyeing of hydrophobic textile materials, including semi-synthetic or synthetic hydrophobic fiber blended textiles. Dyeing and printing of materials, especially suitable for dyeing polyester materials, can obtain red dyed fabrics with uniform color tone, excellent wash resistance and excellent ironing sublimation resistance.

(4) Specific implementation methods

The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:

Example 1:

Put 21.8g (0.2mol) of m-aminophenol, 72g (1mol) of acrylic acid, 100g of water into a 500ml container, heat up to 90°C, keep it warm for 10h, cool down, add 200g of methanol at the same time, keep stirring at 0-5°C for 12h, and crystallize Filter and wash with 50 g of methanol. After washing, dry to obtain the dicarboxylic acid product a.

Put 68.5g (0.5mol) of bromoacetone, 11.6g of soda ash, and dicarboxylic acid product a (100.3g, 0.1mol) into a 500ml container, raise the temperature to 80°C, put in 5gKI, and keep warm for 12h. Cool down to 40°C, add 200g of water, crystallize and filter to obtain coupling component A.

Diazotization: Add 50g of 98% concentrated sulfuric acid, 80g of 85% phosphoric acid, 35g (0.11mol) of 40% nitrosyl sulfuric acid into a 250ml container, cool down to 0~5℃, control 3~4h to finish adding 19.5 g (0.1mol) 2-amino-6-nitrobenzothiazole, after adding, keep warm at 0~5℃ for 3h.

Coupling: Put 1000g of water, 10g of 98% concentrated sulfuric acid, 0.1mol of coupling component A into a 2L container, and beat for half an hour. Add the above-mentioned diazo component dropwise into the beating liquid of the coupling component within 1~2h.

Control the temperature at 0~5°C and fully react for 5~6h. Responses were detected using a percolation ring assay. After the end point is reached, heat the material to 75°C, keep it warm for 3 hours, filter it with suction, and wash it to neutral to obtain the finished dye Ⅰ-1, λ _max (DMF) = 555nm, dyed polyester fabric by high temperature and high pressure method is red, fastness Good performance, washing fastness up to grade 5, sublimation fastness to ironing up to grade 4~5 or above.

The polyester fiber dyeing method is as follows: the obtained dry dye monomer is mixed with an auxiliary agent, and the weight ratio is: dry dye monomer (100 percent): dispersant MF: sodium lignosulfonate: water = 1: 1:1:5, fully ground, dried to obtain commercial dyes. Add 200ml of water and 0.1 gram of commercial dye to the dye vat. After the dye is completely dissolved, control the pH value to 3~9, add 4 grams of polyester fabric, seal the dye vat, put it into the proofer, heat it to 40°C, keep it warm for 15 minutes, and then slowly Heat up to 130°C and keep warm for 45 minutes, take out the dyed fabric after cooling down, soap, wash, and dry.

Example 2:

Similar to the preparation method of the coupling raw material described in Example 1, the coupling component B can be prepared by replacing bromoacetone with an equimolar amount of 2-bromoacetophenone.

According to the synthesis method of the dye in Example 1, the above-mentioned coupling component B is coupled with the diazo solution of 2-amino-6-nitrobenzothiazole to obtain the finished dye I-2, λ _max (DMF )=550nm, the polyester fabric dyed by high temperature and high pressure method is red, the fastness performance is good, the washing fastness reaches 5 grades, and the ironing sublimation fastness reaches 4~5 grades or above.

Embodiment 3~12:

According to the preparation methods of Examples 1-2, different coupling raw materials are used to prepare dyes with excellent color fastness properties of the structures shown in Table 1 below (polyester dyeing method is the same as Example 1).

Table 1

Example 13:

Put 0.5mol of m-aminophenol, 0.5mol of acrylic acid, 100g of water into a 500ml container, heat up to 90°C, keep it warm for 30h, cool down, add 200g of methanol at the same time, keep stirring at 0-5°C for 12h, crystallize and filter, wash with 50g of methanol . After washing, a carboxylic acid product c1 is obtained.

Put 50g of DMF, 11.6g of soda ash, 0.1mol of monocarboxylic acid product c1, 31.5g of chloropropene into a 500ml container, raise the temperature to 80°C, put in 2g of KI, keep warm and reflux for 24h. Cool down, add 400g methanol at the same time, keep stirring at 0-5°C for 12h, filter the crystals, and wash with 50g methanol. After washing, it is dried to obtain intermediate c2.

Put 100g of DMF, 11.6g of soda ash, 0.1mol of intermediate c2, and 18.2g of bromoacetone into a 500ml container, raise the temperature to 60°C, put in 1g of KI, and keep warm for 12h. Cool down to 40°C, add 200g of water, crystallize and filter to obtain Intermediate C.

According to the synthesis method of the dye in Example 1, the above-mentioned coupling component C is coupled with the diazo solution of 2-amino-6-nitrobenzothiazole to obtain the finished dye I-4, λ _max (DMF )=538nm, the polyester fabric dyed by high temperature and high pressure method is red, and the fastness to washing and ironing is above grade 4~5.

Example 14:

Put 0.4mol of m-aminophenol, 0.4mol of acrylic acid, 100g of water into a 500ml container, heat up to 90°C, keep it warm for 30h, cool down, add 200g of methanol at the same time, keep stirring at 0-5°C for 12h, crystallize and filter, wash with 50g of methanol . After washing, a carboxylic acid product d1 is obtained.

Put 150g of water, 11.6g of soda ash, 0.1mol of monocarboxylic acid product d1, 20.5g of benzyl chloride into a 500ml container, raise the temperature to 80°C, put in 2g of KI, and keep warm for 12h. Cool down, add 400g of methanol at the same time, keep stirring at 0-5°C for 12h, filter the crystals, and wash with 50g of methanol. After washing, it was dried to obtain the intermediate d2.

Put 100g of DMF, 11.6g of soda ash, 0.1mol of intermediate d2, and 14.2g of bromoacetone into a 500ml container, raise the temperature to 60°C, put in 1g of KI, and keep it warm for 12h. Cool down to 40°C, add 200g of water, crystallize and filter to obtain intermediate D.

According to the synthesis method of the dye in Example 1, the above-mentioned coupling component D is coupled with the diazo solution of 2-amino-6-nitrobenzothiazole to obtain the finished dye I-5, λ _max (DMF )=535nm, the polyester fabric dyed by high temperature and high pressure method is red, and the fastness to washing and ironing is above grade 4~5.

Embodiment 15~20:

According to the preparation methods of Examples 13-14, different coupling raw materials are used to prepare dyes with excellent color fastness properties as shown in Table 2 below (polyester dyeing method is the same as Example 1).

Table 2

Examples 21~28

The dye monomer compound of the present invention can be blended in any ratio of two or more kinds, mixed with additives (commercially available), fully ground, dried to obtain commercial dyes, and applied to dyeing according to the method described in Example 1. , the red dyed fabric with excellent color fastness can be obtained, and the mixing components and proportions are shown in Table 3:

table 3

Comparative example 1

According to the method described in above-mentioned embodiment 1, carry out the commercialization of dyestuff and dyeing polyester fiber, the following formula (I-6) among the present invention, (I-9) dye compound and the following formula in patent CN101522816 (Ⅳ-1) compound dyeing comparison, the color fastness to washing is 0.5 higher, the sublimation fastness to ironing is 0.5~1.0 higher, and the dyeing rate is increased by 2~3%.

Comparative example 2:

According to the method described in above-mentioned Example 1, carry out the commercialization of dyestuff and dyeing polyester fiber, the following formula (I-10) among the present invention, (I-15) dye compound and the following formula in patent CN101522816 (Ⅳ-2) compound dyeing comparison, its color fastness to washing and sublimation fastness to ironing are higher than 0.5 grade.

Comparative example 3:

According to the method described in above-mentioned Example 1, carry out the commercialization of dyestuff and dyeing polyester fiber, the following formula (I-10) among the present invention, (I-15) dye compound and the following formula in patent CN101522816 The compound (Ⅳ-3) was dyed and compared, its color fastness to washing was 0.5 grade higher, and its ironing sublimation fastness was 0.5~1.0 grade higher.

Comparative example 4:

According to the method described in above-mentioned embodiment 1, carry out the commercialization of dyestuff and dyeing polyester fiber, the dyestuff compound of following formula (I-13) among the present invention and the following formula (IV-4) in patent GB896232 Comparing the dyeing of the compound, the sublimation fastness to ironing is 0.5~1 grade higher.

Comparative example 5:

According to the method described in above-mentioned embodiment 1, carry out the commercialization of dyestuff and dyeing polyester fiber, the dyestuff compound of following formula (I-8) among the present invention and the following formula (IV-5) in patent GB896232 Compound dyeing comparison, its color fastness to washing and ironing sublimation fastness are higher than 0.5 grade.

Claims (5)

1. a benzothiazoles dye monomer compound, its structure is as shown in formula I:

In formula I:

R ₁, R ₂be-CH simultaneously ₂cH ₂cOOCH ₂cOR ₄, R ₄for methyl or phenyl;

R ₃for-OH ,-OCH ₃or-NHCOCH ₃.

2. benzothiazoles dye monomer compound as claimed in claim 1, is characterized in that described benzothiazoles dye monomer compound is one of following:

3. the application of benzothiazoles dye monomer compound in the dispersed dye dyeed for the preparation of hydrophobic fiber material as claimed in claim 1.

4., for dispersed dye for hydrophobic fiber material dyeing, be made up of more than one formula I dye monomer compounds and auxiliary agent, dye monomer compound and auxiliary agent mass ratio are 1:0.8 ~ 5;

In formula I:

R ₁, R ₂-CH ₂cH ₂cOOCH ₂cOR ₄, R ₄for methyl or phenyl;

R ₃for-OH ,-OCH ₃or-NHCOCH ₃.

5. dispersed dye as claimed in claim 4, is characterized in that described auxiliary agent is one of following or wherein two or more mixture: naphthalene sulfonic acidformaldehyde condensation product, alkyl naphthalene sulfonic acid formaldehyde condensation products, benzyl naphthalene sulfonic formaldehyde condensation compound, sulfonated lignin.