CN115960472A - Azo type dye compound and synthesis process and application thereof - Google Patents
Azo type dye compound and synthesis process and application thereof Download PDFInfo
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- CN115960472A CN115960472A CN202211665076.7A CN202211665076A CN115960472A CN 115960472 A CN115960472 A CN 115960472A CN 202211665076 A CN202211665076 A CN 202211665076A CN 115960472 A CN115960472 A CN 115960472A
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 50
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 50
- 239000000975 dye Substances 0.000 claims abstract description 71
- 239000012954 diazonium Substances 0.000 claims abstract description 44
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 44
- 239000000987 azo dye Substances 0.000 claims abstract description 34
- 238000005859 coupling reaction Methods 0.000 claims abstract description 22
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 17
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 36
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- 239000000203 mixture Substances 0.000 claims description 32
- 235000019233 fast yellow AB Nutrition 0.000 claims description 30
- -1 azo acid yellow Chemical compound 0.000 claims description 29
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- 238000002360 preparation method Methods 0.000 claims description 5
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- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
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- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
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- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
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Abstract
The application relates to the technical field of fine chemicals, in particular to an azo type dye compound and a synthesis process and application thereof. An azo dye compound has a structure shown in a formula I; in formula I: r1 is selected from-H, C1-C4 alkyl or-CH 2 CH 2 SO 3 M; n and p are respectively and independently integers of 1-4; r2 is selected from- (CH 2) nSO 3 M or-SO 3 M and n are integers from 0 to 4; r3 is selected from-H, C1-C4 alkyl or C2-C6 alkyl interrupted by oxygen; m is selected from-H or a metal cation; the synthesis process comprises the following steps: carrying out diazotization reaction on the compound shown in the formula II to obtain diazonium salt; carrying out coupling reaction on the diazonium salt and the compound shown as the formula III to obtain the compound shown as the formula IA compound is provided. The azo dye compound does not contain heavy metal, and has the characteristics of safety, environmental protection, less three-waste discharge, simple synthesis process and low cost.
Description
Technical Field
The application relates to the technical field of fine chemicals, in particular to an azo type dye compound and a synthesis process and application thereof.
Background
The acid dye is a water-soluble molecular compound which contains an acid gene such as sulfonic acid group, carboxyl group and the like, can be combined with amino groups in protein fiber molecules by ionic bonds and is used under acidic, weak acid or neutral conditions. The acid dye has color and can make other substances obtain bright and firm color in molecular state or dispersed state.
Acid dyes are classified into strongly acidic dyes, weakly acidic dyes, mordant acidic dyes, complex acidic dyes, and the like according to their chemical structures and dyeing conditions. At present, because the acid complex dye contains metal atoms, a metal complex can be formed on the fabric during dyeing, so that the dyed fabric has good dyeing fastness.
However, most of the metal atoms in the acid complex dye are heavy metals such as chromium, cobalt and the like, and are very difficult to biodegrade. If the aqueous solution or waste containing the heavy metal-containing acidic complex dye is directly discharged into the environment, there is a problem of environmental pollution.
Disclosure of Invention
In order to improve the environmental protection performance and the dyeing fastness of the dye, the application provides various azo type dye compounds, and a synthesis process and application thereof.
In a first aspect, the present application provides an azo-type dye compound, which adopts the following technical scheme:
an azo dye compound has a structure shown in formula I:
in the formula I:
r1 is selected from-H, C1-C4 alkyl, - (CH) 2 ) n OH、-(CH 2 ) p OCH 3 or-CH 2 CH 2 SO 3 M; n and p are respectively independent integers from 1 to 4;
r2 is selected from- (CH) 2 )nSO 3 M、-SO 3 M，-CONH 2 or-COOM, n is an integer of 0-4;
r3 is selected from-H, C1-C4 alkyl or C2-C6 alkyl interrupted by oxygen;
m is selected from-H or a metal cation.
By adopting the technical scheme, the water-soluble group in the dye compound can improve the water solubility of the dye compound, can also improve the permeability of the dye compound to fibers, promotes the combination of the dye compound and the fibers, and improves the acting force of the combination of the dye compound and the fibers, thereby improving the color fastness of the dye compound. Meanwhile, the dye compound does not contain heavy metal, is nontoxic and carcinogenic, has sensitization, and has the advantages of high dyeing fastness, safety, environmental protection, less discharge of three wastes, low manufacturing cost and suitability for industrial production.
Preferably, R1 in the formula I is-H or C1-C4 alkyl; r2 is- (CH) 2 )nSO 3 M or-SO 3 M and n are 0 or 1, M is-H, na or K.
By adopting the technical scheme, the water-soluble group in the dye compound is optimized, the obtained dye compound not only has good water solubility in water, but also can be hydrolyzed for use after being dissolved in water, and the dyeing fastness and the pH tolerance of the obtained dye compound are improved.
Preferably, the compound shown in the formula I comprises any one of formula I-1, formula I-2, formula I-3, formula I-4, formula I-5, formula I-6, formula I-7 and formula I-8;
by adopting the technical scheme, the six azo type dye compounds are adopted to dye the fabric, and the dyed fabric has good soaping color fastness and sublimation fastness.
In a second aspect, the present application provides a synthesis process of an azo-type dye compound, which adopts the following technical scheme: a synthesis process of an azo dye compound comprises the following preparation steps:
s1: carrying out diazotization reaction on the compound shown in the formula II to obtain diazonium salt;
s2: carrying out coupling reaction on the diazonium salt and a compound shown in a formula III to obtain a compound shown in a formula I;
the reaction route of the steps is as follows:
by adopting the technical scheme, the synthesis process of the dye compound has the advantages of few synthesis steps, simple synthesis process, greenness and environmental protection, and is beneficial to large-scale production.
Preferably, the synthesis process of the azo dye compound comprises the following preparation steps:
s1: adding hydrochloric acid into an aqueous solution of a compound shown in a formula II, stirring and mixing for 0.3-0.5h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization for 2-4h under the condition that the pH value is 0.5-3 to obtain diazonium salt;
s2: firstly, stirring and mixing the compound of the formula III in water with the pH value of 7-8, then adding diazonium salt, carrying out coupling reaction for 2-3h at the temperature of 5-10 ℃ and the pH value of 5-8, filtering and drying to obtain the compound of the formula I.
By adopting the technical scheme, on one hand, nitrous acid generated by the reaction of the sodium nitrite solution and hydrochloric acid is relatively stable at 0-5 ℃, so that the nitrous acid is favorable for reacting with a compound of a formula II dissolved in a hydrochloric acid aqueous solution to generate diazonium salt, and the yield of the diazonium salt is improved; on the other hand, in the reaction environment with the pH value of 0.5-3, the nitrous acid and the compound of the formula II completely react, and the obtained diazonium salt has strong activity and is not easy to decompose, so that the yield of the diazonium salt can be further improved, the coupling efficiency of the diazonium salt with strong activity and the compound of the formula III can be improved, and the yield of the compound of the formula I can be improved. Meanwhile, when the compound of the formula III dissolved by beating is subjected to coupling reaction with the diazonium salt, the influence of the reaction temperature on the stability of the diazonium salt is small, and the condition that the pH value is 5-8 can improve the concentration of free amine in the reaction liquid, thereby being beneficial to further improving the coupling efficiency of the diazonium salt and the compound of the formula III and improving the yield of the compound of the formula I.
Preferably, in S1, the mass ratio of the compound of the formula II, hydrochloric acid and sodium nitrite is 1 (4-6) to 1-1.2.
By adopting the technical scheme, the yield and the stability of the diazonium salt are improved by optimizing the adding amount of the compound shown in the formula II, the hydrochloric acid and the sodium nitrite, so that the coupling efficiency of the diazonium salt and the compound shown in the formula III is improved, and the yield of the compound shown in the formula I is improved.
Preferably, in the S2, the mass ratio of the compound of the formula II to the compound of the formula III is 1 (2-2.2).
By adopting the technical scheme, the addition of the compound shown in the formula II and the compound shown in the formula III is optimized, so that the utilization rate of the compound shown in the formula III during coupling reaction is improved, the residue of the compound shown in the formula III is reduced, and the production cost of the compound shown in the formula I is saved.
In a third aspect, the present application provides an azo acid yellow dye composition, which adopts the following technical scheme:
an azo acid yellow dye composition comprising the azo dye compound.
By adopting the technical scheme, the dye compound has good water solubility, can be directly hydrolyzed in water, permeates into fibers, is combined with the fibers, and is favorable for improving the dyeing fastness and the pH tolerance of the dye composition.
Preferably, the azo acid yellow dye composition comprises the azo dye compound and a dyeing assistant; the dyeing auxiliary comprises one or more of calcium chloride, anhydrous sodium sulfate and sodium bicarbonate;
the weight ratio of the azo dye compound to the dyeing auxiliary agent is 1 (0.2-5).
By adopting the technical scheme, the dye compound and the dyeing auxiliary agent are mixed according to the weight ratio and then are used for dyeing the fiber, the improvement of the affinity of the dye compound to the fiber is facilitated, and the obtained fiber has good dyeing fastness.
In summary, the present application has the following beneficial effects:
the water-soluble group in the dye compound can improve the water solubility of the dye compound, improve the permeability and the binding force of the dye compound on fibers, and the dye compound can be directly hydrolyzed in water and has wider pH tolerance, so that the obtained dye compound has good dyeing fastness and pH tolerance; meanwhile, the dye compound does not contain heavy metal, is nontoxic and carcinogenic, has sensitization, and has the advantages of high dyeing fastness, safety, environmental protection, less discharge of three wastes, low manufacturing cost and suitability for industrial production.
Drawings
FIG. 1 is a diagram of dyeing process in the dyeing performance test of the present application.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
Example 1
An azo type dye compound has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials and the feeding amount thereof used in the synthesis process are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-1 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-1; the diazonium salt is added to an aqueous solution of formula III-1 at pH 5 at 5-10 ℃ for a coupling reaction time of 2h, filtered, dried and triturated to a particle size of 178 μm to give formula I-1 (yellow powder, 305g, 92.5% purity, 96% yield).
The results of the elemental analysis of formula I-1 are shown in the following Table.
Example 2
An azo dye compound, which has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials and the feeding amount thereof used in the synthesis process are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the compound shown in the formula II-1 with water to obtain an aqueous solution of the compound shown in the formula II; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-2 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-2; the diazonium salt is added to an aqueous solution of formula III-2 at 5-10 ℃ and pH 5 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-2 (yellow powder, 297g, 93.1% purity, 95.4% yield).
The results of the elemental analysis of formula I-2 are shown in the following Table.
Example 3
An azo type dye compound has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials and the feeding amount thereof used in the synthesis process are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-3 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-3; the diazonium salt is added to an aqueous solution of formula III-3 at 5-10 ℃ and pH 5 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-3 (yellow powder, 319.2g, 92.1% purity, 94.7% yield).
The results of the elemental analysis of formula I-3 are shown in the following table.
Example 4
An azo type dye compound has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials and the feeding amount thereof used in the synthesis process are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-4 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-4; the diazonium salt is added to an aqueous solution of formula III-4 at 5-10 ℃ and pH 5 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-4 (yellow powder, 342g, 96.5% purity, 95.2% yield).
The results of the elemental analysis of formula I-4 are shown in the following table.
Example 5
An azo type dye compound has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials and the feeding amount thereof used in the synthesis process are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-5 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-5; the diazonium salt is added to an aqueous solution of formula III-5 at 5-10 ℃ and pH 5 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-5 (yellow powder, 305g, 95.8% purity, 97.3% yield).
The results of the elemental analysis of formula I-5 are shown in the following table.
Example 6
An azo type dye compound has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials and the feeding amount thereof used in the synthesis process are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the formula II-2 with water to obtain an aqueous solution of the formula II-2; adding hydrochloric acid into the aqueous solution of the formula II-2, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-1 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-1; the diazonium salt is added to an aqueous solution of formula III-1 at 5-10 ℃ and pH 5 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-6 (yellow powder, 312g, 95.6% purity, 96.8% yield).
The results of the elemental analyses of formula I-6 are shown in the following table.
Example 7
An azo type dye compound has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials used in the synthesis process and the feeding amount thereof are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the formula II-3 with water to obtain an aqueous solution of the formula II-3; adding hydrochloric acid into the aqueous solution of the formula II-3, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-6 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-6; the diazonium salt is added to an aqueous solution of formula III-6 at 5-10 ℃ and pH 5 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-7 (yellow powder, 293g, 95.5% purity, 96.8% yield).
The results of the elemental analyses of formula I-7 are shown in the following Table.
Example 8
An azo type dye compound has a specific structural formula as follows:
the reaction equation of the synthesis step of the synthesis process of the azo dye compound is as follows:
the raw materials and the feeding amount thereof used in the synthesis process are shown in the following table:
the synthesis process of the azo dye compound comprises the following steps:
s1: mixing the formula II-4 with water to obtain an aqueous solution of the formula II-4; adding hydrochloric acid into the aqueous solution of the formula II-4, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-7 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-7; the diazonium salt is added to an aqueous solution of formula III-7 at 5-10 ℃ and pH 5 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-8 (yellow powder, 319g, 95.8% purity, 96.9% yield).
The results of the elemental analysis of formula I-8 are shown in the following Table.
Example 9
An azo-type dye compound, which is different from example 5 in that the process for synthesizing the azo-type dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.4h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 3h under the condition that the pH value is 2 to obtain diazonium salt;
s2: adding the formula III-5 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-5; the diazonium salt is added to an aqueous solution of formula III-5 at 5-10 ℃ and pH 7 for a coupling reaction for 2.5h, filtered, dried and milled to a particle size of 178 μm to give formula I-5 (yellow powder, 310g, 96.3% purity, 98.1% yield).
Example 10
An azo-type dye compound, which is different from example 5 in that the process for synthesizing the azo-type dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.5h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization for 4h under the condition that the pH value is 3 to obtain diazonium salt;
s2: adding the formula III-5 into water, and then adjusting the pH value to 8 to obtain an aqueous solution of the formula III-5; the diazonium salt is added to an aqueous solution of formula III-5 at 5-10 ℃ and pH 8 for a coupling reaction for 3h, filtered, dried and milled to a particle size of 178 μm to give formula I-5 (yellow powder, 308g, 96.0% purity, 98.3% yield).
Example 11
An azo-type dye compound, which is different from example 5 in that the synthesis process of the azo-type dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.3h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 4 to obtain diazonium salt;
s2: adding the formula III-5 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-5; the diazonium salt is added to an aqueous solution of formula III-5 at 5-10 ℃ and pH 9 for a coupling reaction for 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-5 (yellow powder, 303g, 93.5% purity, 95.8% yield).
Example 12
An azo-type dye compound, which is different from example 5 in that the process for synthesizing the azo-type dye compound comprises the following steps:
s1: mixing the formula II-1 with water to obtain an aqueous solution of the formula II-1; adding hydrochloric acid into the aqueous solution of the formula II-1, stirring and mixing for 0.3h, adding a sodium nitrite solution at 5-10 ℃, and carrying out diazotization reaction for 2h under the condition that the pH value is 0.5 to obtain diazonium salt;
s2: adding the formula III-5 into water, and then adjusting the pH value to 7 to obtain an aqueous solution of the formula III-5; the diazonium salt is added to an aqueous solution of formula III-5 at pH 4 at 5-10 ℃ for a coupling reaction time of 2h, filtered, dried and milled to a particle size of 178 μm to give formula I-5 (yellow powder, 300g, 92.0% purity, 94.5% yield).
Example 13
An azo dye compound, which is different from example 5 in the following points in the raw materials and the amounts thereof used in the synthesis process, is shown in the following table:
detection gave formula I-5 (yellow powder, 306g, 94.8% purity, 96.5% yield).
Example 14
An azo dye compound, which is different from example 5 in the following points in the raw materials and the amounts thereof used in the synthesis process, is shown in the following table:
detection gave formula I-5 (yellow powder, 312g, purity 95.4%, yield 97.0%).
Performance testing
The azo acid yellow dye compositions obtained in the application examples 1-8 of the present application were subjected to a dyeing property test, a pH tolerance test, a soaping color fastness test, a sublimation fastness test, nylon-ammonia homochromatic properties, and a nylon-cotton bath dyeing test, by the following methods: 1. and (3) testing dyeing performance: five nylon base materials are selected: nylon knitted fabric, nylon, taslon, oxford, and crepe fabric were dyed according to the dyeing process shown in fig. 1, wherein the dyeing depth was 2% o.w.f (dye to fabric weight) and the pH was 4.0. And then observing the uniformity of the color of the cloth surfaces of the five nylon base materials in a standard lamp box under the conditions of constant temperature and constant humidity, and scoring by 0-5 minutes according to the uniformity degree of the color of the cloth surfaces, wherein the uniformity of the color of the cloth surfaces is very good at 5 minutes.
2. Testing pH tolerance: on nylon knitted fabric, dyeing was performed according to the dyeing process of fig. 1 under the conditions of pH values of 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 8.0, and 9.0, respectively. And then testing the color difference CIEDE and the force wgt of the sample by using a Datacolor color measuring instrument under the conditions of constant temperature and constant humidity, and recording.
3. Soaping color fastness test: nylon knitted fabric was first dyed according to the dyeing process in figure 1, wherein the dyeing depth was 2% o.w.f (dye to fabric weight) and the pH was 4.0. Then the sample is shaped for 45S at 180 ℃ and finally determined according to the international standard ISO105C 10-2006C.
4. Testing sublimation fastness: nylon cloth was first dyed according to the dyeing process in figure 1, with a depth of dyeing of 2% o.w.f (dye to fabric weight) and a pH of 4.0. Then the sample is shaped for 45S at 180 ℃ and finally measured according to the international standard ISO 105-P01.
5. Polyamide-ammonia homochromatism test: nylon yarn and spandex yarn were mixed at a ratio of 92/8, and dyed according to the dyeing process of fig. 1, wherein the dyeing depth was 2% o.w.f (dye to fabric weight) and the pH was 4.0. And after dyeing is finished, comparing the color proximity degrees of the nylon yarn and the spandex yarn in a standard lamp box under the conditions of constant temperature and constant humidity, and scoring for 0-5 points according to the color proximity degrees, wherein the color is very close to 5 points.
6. Brocade cotton-bath dyeing test: on brocade cotton knitted fabric, dyeing was carried out according to the dyeing process of fig. 1, wherein the dyeing depth was 2% o.w.f (dye to fabric weight) and the pH was 4.0. And after dyeing is finished, observing the color obtaining uniformity of the nylon/cotton fabrics in a standard lamp box under the conditions of constant temperature and constant humidity, and grading by 0-5 minutes according to the color obtaining uniformity degree of the nylon/cotton fabrics, wherein the color obtaining uniformity of the nylon/cotton fabrics is very good at 5 minutes.
Application examples
Application example 1
The azo acid yellow dye composition comprises the following components in parts by weight.
The preparation method of the azo acid yellow dye composition comprises the following steps: adding the dyeing auxiliary agent into the azo dye compound, and grinding the mixture to obtain the azo acid yellow dye composition, wherein the particle size of the mixture is 1-3 mu m.
In the application examples of the present application, azo type dye compounds were prepared from example 1.
Application examples 2 to 6
An azo acid yellow dye composition is different from application example 1 in that the azo type dye compound is different.
In application examples 2 to 6, azo type dye compounds were synthesized by the following examples.
The azo acid yellow dye compositions obtained in application examples 1 to 8 of the present application were subjected to a dyeing property test, a pH tolerance test, a soaping color fastness test, a sublimation fastness test, nylon/ammonia homochromatic properties, and a nylon/cotton bath dyeing test, and the test results are shown in the following table.
1. Dyeing performance test results
From the above table, it is known that the azo acid yellow dye composition obtained in the application examples 1 to 8 of the present application can be used for dyeing nylon knitted fabric, nylon, taslon, oxford fabric and brocade crepe, and the uniformity of color of the five fiber fabrics is very good. Therefore, the azo acid yellow dye composition obtained in the application examples 1 to 8 can dye nylon fabrics of different materials, and has good applicability.
2. Results of pH tolerance test
2.1 color difference CIEDE test data
2.2 parts by force wgt test data
From the above table, it can be seen that the azo acid yellow dye compositions obtained in application examples 1 to 8 of the present application have a low color difference CIEDE value and a small change in the weight wgt value when dyed at a pH of 3.0 to 8.0. Therefore, the azo acid yellow dye composition obtained in application examples 1-8 can be dyed at a pH value of 3.0-8.0, and has good pH tolerance.
3. Color fastness to soaping test results
From the above table, it can be seen that the azo acid yellow dye compositions obtained in the application examples 1-8 have good color fastness to acetate, cotton, nylon, polyester, acrylic and wool.
4. Sublimation fastness test results
From the above table, it can be seen that the fabrics dyed with the azo acid yellow dye compositions obtained in application examples 1 to 8 have high staining grade at 180 ℃ and 210 ℃ and good sublimation fastness.
5. Brocade ammonia homochromatism test result
From the above table, it can be seen that, when the azo acid yellow dye composition obtained in application examples 1 to 8 of the present application is used to dye nylon yarn and spandex yarn, the color proximity degree is as high as 5 minutes, the two fibers have similar cloth surface colors and good homochromatism. Therefore, the azo acid yellow dye composition obtained in the application examples 1-8 can achieve excellent level dyeing effect on nylon/spandex fabrics.
6. Brocade cotton-bath dyeing test results
From the above table, it can be seen that the uniformity score of the color of the brocade and cotton fabric using the azo acid yellow dye composition obtained in the application examples 1-8 of the present application is as high as 5. Therefore, the azo acid yellow dye composition obtained in the application examples 1-8 can obtain uniform color of the cloth surface after the brocade cotton is dyed in a bath, the problem of color flower in the brocade cotton dyeing in the bath can be effectively reduced, and the production efficiency is improved.
Comparative example
Comparative example 1
An azo acid yellow dye composition is different from application example 1 in that an equal weight of c.i. acid yellow 59 is used instead of the azo type dye compound.
Comparative example 2
An azo acid yellow dye composition is different from application example 1 in that an equal weight of c.i. acid yellow 79 is used instead of the azo type dye compound.
Comparative example 3
An azo acid yellow dye composition is different from application example 1 in that an equal weight of c.i. acid yellow 199 is used instead of the azo type dye compound.
The azo acid yellow dye compositions obtained in comparative examples 1 to 3 of the present application were subjected to a dyeing property test, a soaping fastness test, a sublimation fastness test, a brocade ammonia homochromy test, and a brocade cotton-bath dyeing test, and the test results are shown in the following table.
1. Dyeing performance test results
2. Soaping resistance color fastness test result
3. Sublimation fastness test results
4. Brocade ammonia homochromatism test result
5. Brocade cotton-bath dyeing test results
By analyzing the data in the above table, the azo acid yellow dye composition of application example 1 and the azo acid yellow dye compositions of comparative examples 1 to 3 have good dyeing performance, polyamide-amine homochromy performance and polyamide-cotton bath dyeing performance. Meanwhile, the azo acid yellow dye composition of application example 1 has better fastness to soaping and sublimation fastness than the azo acid yellow dye compositions of comparative examples 1 to 3. Therefore, the azo dye compound has the same color fastness as the acid complex dye, does not contain heavy metal, and cannot crack sensitized carcinogenic aromatic amine. Therefore, the azo dye compound has the advantages of high dyeing fastness, safety, environmental protection, less three-waste discharge, low cost and suitability for industrial production.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. An azo-type dye compound is characterized in that the structure is shown as formula I:
in formula I:
r1 is selected from-H, C1-C4 alkyl, - (CH) 2 ) n OH、-(CH 2 ) p OCH 3 or-CH 2 CH 2 SO 3 M; n and p are respectively and independently integers of 1-4;
r2 is selected from- (CH) 2 )nSO 3 M、-SO 3 M，-CONH 2 or-COOM, n is an integer of 0-4;
r3 is selected from-H, C1-C4 alkyl or C2-C6 alkyl interrupted by oxygen;
m is selected from-H or a metal cation.
2. The azo-type dye compound according to claim 1, wherein R1 in formula-i is-H or C1-C4 alkyl; r2 is- (CH) 2 )nSO 3 M or-SO 3 M and n are 0 or 1, M is-H, na or K.
3. The azo-type dye compound according to claim 1, wherein the compound represented by formula i comprises any one of formula i-1, formula i-2, formula i-3, formula i-4, formula i-5, formula i-6, formula i-7 and formula i-8;
4. a process for the synthesis of azo dye compounds according to any of claims 1 to 3, characterized in that it comprises the following preparation steps:
s1: carrying out diazotization reaction on the compound shown in the formula II to obtain diazonium salt;
s2: carrying out coupling reaction on the diazonium salt and a compound shown in a formula III to obtain a compound shown in a formula I;
the reaction route of the steps is as follows:
5. the process for the synthesis of azo dye compounds according to claim 4, comprising the following preparation steps:
s1: adding hydrochloric acid into an aqueous solution of a compound of a formula II, stirring and mixing for 0.3-0.5h, adding a sodium nitrite solution at 0-5 ℃, and carrying out diazotization reaction for 2-4h under the condition that the pH value is 0.5-3 to obtain diazonium salt;
s2: firstly, stirring and mixing the compound of the formula III in water with the pH value of 7-8, then adding diazonium salt, carrying out coupling reaction for 2-3h at the temperature of 5-10 ℃ and the pH value of 5-8, filtering and drying to obtain the compound of the formula I.
6. The process for synthesizing an azo-type dye compound according to claim 4, wherein the mass ratio of the compound of formula II, hydrochloric acid and sodium nitrite in S1 is 1 (2-3) to (1-1.2).
7. The process according to claim 4, wherein the amount of the compound of formula II to the compound of formula III in S2 is 1 (2-2.2).
8. An azo acid yellow dye composition comprising the azo dye compound according to any one of claims 1 to 3.
9. The azo acid yellow dye composition according to claim 8, comprising the azo type dye compound and a dyeing assistant; the dyeing auxiliary comprises one or more of calcium chloride, anhydrous sodium sulfate and sodium bicarbonate;
the weight ratio of the azo dye compound to the dyeing auxiliary agent is 1 (0.2-5).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193153A (en) * | 1987-02-06 | 1988-08-10 | Nippon Kayaku Co Ltd | Electrophotographic sensitive body |
| JPS63305363A (en) * | 1987-06-05 | 1988-12-13 | Fuji Electric Co Ltd | Electrophotographic sensitive body |
| US4988594A (en) * | 1989-07-26 | 1991-01-29 | Fuji Electric, Co. Ltd. | Diazo photoconductor for electrophotography |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193153A (en) * | 1987-02-06 | 1988-08-10 | Nippon Kayaku Co Ltd | Electrophotographic sensitive body |
| JPS63305363A (en) * | 1987-06-05 | 1988-12-13 | Fuji Electric Co Ltd | Electrophotographic sensitive body |
| US4988594A (en) * | 1989-07-26 | 1991-01-29 | Fuji Electric, Co. Ltd. | Diazo photoconductor for electrophotography |
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