CN104312202A - Low-alkaline or alkali-free active dark red dye and preparation method thereof - Google Patents
Low-alkaline or alkali-free active dark red dye and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of active dyes in a new material technology and in particular relates to a low-alkaline or alkali-free active dark red dye shown in a formula (I) in the specification, wherein M is hydrogen or alkali metal. The low-alkaline or alkali-free active dark red dye can be crosslinked and fixed with cotton fibers by only adding 1-3g/L of an alkaline agent during dyeing and even can be crosslinked and fixed with the cotton fibers under the condition that pH value of a dye bath is equal to 7 without adding the alkaline agent; the new material technology is a new technology completely different from the traditional technology and is especially applicable to dyeing of various blended mixture fabrics; the low-alkaline or alkali-free active dark red dye and the cotton fibers form covalent bond combination, so that stable and relatively good dry and wet fastness, light fastness, washing fastness are realized; and uncoupled pyridine carboxylic acid is a vitamin, so that less environmental influence is produced.
Description
Technical field
The present invention relates to the reactive dyestuff field in new material technology, particularly a kind of low alkali or the active deep red dye well its preparation method of non-alkali.
Background technology
Traditional reactive dyeing all needs to be cross-linked set with alkaline agent and cotton fibre, and the alkaline agent generally added is soda ash, and consumption is at 20g/l, and the levels such as dry wet fastness, light fastness, washing fastness are lower.
Chlorine on active group " chlorotriazine " in traditional KE type or HE type reactive dyestuffs is open existence, and the dyeing of traditional blended union is for washing/cotton two one-bath two-step process, brocade/cotton two one-bath two-step process etc., and energy consumption is large, and waste water is many, and manpower consumption is also large.
Summary of the invention
The object of the invention is to solve the problem, the invention provides the levels such as a kind of dry wet fastness, light fastness, washing fastness better, energy consumption is low, one group of low alkali or non-alkali reactive dyestuffs and preparation method thereof that waste discharge is few.
Low alkali or the active deep red dyestuff of non-alkali shown in formula (1)
Wherein, M is hydrogen or basic metal.
Preferably, described low alkali or the active deep red dyestuff of non-alkali are the one of following formula (1-1) or formula (1-2) compound or the mixing of formula (1-1) and formula (1-2) compound:
In addition, present invention also offers the preparation method of a kind of low alkali or the active deep red dyestuff of non-alkali.
The preparation method of low alkali or the active deep red dyestuff of non-alkali, comprises the steps:
A, a contracting reaction
Cyanuric chloride adds water, trash ice, dispersion agent are pulled an oar 1 hour in about 0 DEG C; 1-amino-8-naphthol-3,6-disulphonic acid being added slowly cyanuric chloride suspends in material, control temperature 0-10 DEG C between charge period, pH≤3; After adding, protect pH=1-2 with sodium bicarbonate, temperature 0-3 DEG C of reaction to terminal;
B, two contracting reactions
Joined by Ursol D in an above-mentioned contracting liquid, be warming up to 30-50 DEG C immediately, when PH≤3.0, add sodium bicarbonate slowly and adjust pH=5-7, insulation protects pH value reaction to terminal;
C, doazo reaction
1.5-disulfonic acid-2-naphthylamines adds water, trash ice, dispersion agent making beating 1-2 hour, adds hydrochloric acid, trash ice, adds sodium nitrite solution slowly, control temperature 0-15 DEG C between charge period, and keep congo-red test paper to show avy blue; Sodium nitrite solution adds complete, is incubated 0-15 DEG C of reaction 1 hour, adds thionamic acid and to disappear unnecessary Sodium Nitrite;
D, coupled reaction
1.5-disulfonic acid-2-naphthylamines diazonium salt is joined in above-mentioned two contracting liquid, insulation 5-10 DEG C, add sodium bicarbonate adjustment pH=5-7, react to diazonium salt and disappear;
E, three contracting reactions
Nicotinic acid or γ-picolinic acid dry powder directly add in coupling solution, stir after 10 minutes, are directly warming up to 80-95 DEG C, and keep pH=4-7 with sodium bicarbonate; Control reaction to terminal;
F, steam drying
Terminal directly obtains formula (1) dyestuff with steam drying after arriving.
The present invention also provides low alkali or the active deep red dye composite of non-alkali, comprise the low alkali shown in formula (1) or the active deep red dyestuff of non-alkali and auxiliary agent, described auxiliary agent is: the one in Sodium sulfate anhydrous.min(99), Sodium hexametaphosphate 99, condensation compound of methyl naphthalene sulfonic acid and formaldehyde, naphthalene sulfonic acidformaldehyde condensation product or its mixture.Preferably, auxiliary agent is Sodium sulfate anhydrous.min(99).
Wherein, M is hydrogen or basic metal.
Preferably, described low alkali or the active deep red dyestuff of non-alkali are the one of following formula (1-1) or formula (1-2) compound or the mixing of formula (1-1) and formula (1-2) compound:
Only need to add 1-3g/l alkaline agent during the reactive dyeing that the present invention relates to and just can be cross-linked set with cotton fibre, even do not add alkaline agent, under the condition of dye bath pH=7, the active deep red dyestuff of this invention and cotton fibre just can be made to be cross-linked set.This is a kind of and the diverse novel process of traditional technology, new technology, is specially adapted to various union dyeing.These group reactive dyestuffs become covalent bonds with cotton fibre, therefore stablize and have the dry levels such as fastness, light fastness, washing fastness that wet preferably.The pyridine carboxylic acid thrown off is a kind of VITAMIN, less on environmental protection impact.
Infect KE type or HE type reactive dyestuffs in active group " chlorotriazine " on chlorine be open existence, and the chlorine on active group " chlorotriazine " in reactive dyestuffs of the present invention by nicotinic acid or γ-picolinic acid replace, so the percent hydrolysis of dyestuff also can decrease during dyeing, dye structure is more stable, can the hot conditions of resistance to 140 DEG C.Neutral fixation, the characteristic condition such as high temperature resistant other dyeings just can be given play to, thus the dyeing technique of applicable blended union, the blend dyeing novel process of existing market maturation mainly can be used for washing/cotton one-bath one-step dyeing, brocade/cotton one-bath one-step dyeing, wash/cotton one-bath two-step process, brocade/cotton one-bath two-step process etc., and the dyeing of traditional blended union is for washing/cotton two one-bath two-step process, brocade/cotton two one-bath two-step process etc.The appearance energy efficient greatly of this patent product, reduces discharge of wastewater, decreases manpower consumption etc.
Through testing and verification, due to the relation of dye structure, the cotton of the active deep red dyestuff of this invention, nylon, terylene staining are very good.This advantage adopts the printing and dyeing novel process such as bath one step or bath two steps when being also more applicable for the dyeing of blended union.
Various starting material used in the method for the invention can commercially obtain.
The preparation process of compound prepared by the present invention and use procedure are all safety, environmental protection, energy-conservation.
Embodiment
The explanation of the following examples just to technical scheme of the present invention, does not form any restriction to technical scheme of the present invention and protection domain.
Embodiment 1: the preparation that formula (1-1) is active deep red.
A, a contracting reaction
12g cyanuric chloride adds water 50g, trash ice 150g, dispersion agent 1g in about 0 DEG C making beating 1 hour.1-amino-8-naphthol-3,6-disulphonic acid (configure in advance: 26g+ water 80g adds sodium bicarbonate 6g and adjusts pH=6-7, stir molten clear) is added cyanuric chloride slowly to suspend in material, control temperature 0-10 DEG C between charge period, pH≤3.After adding, protect pH=1-2, temperature 0-3 DEG C of reaction to terminal (1-2 hour) with 5g sodium bicarbonate.
B, two contracting reactions
Joined by 3.5g Ursol D in an above-mentioned contracting liquid, be warming up to 30-50 DEG C immediately, when PH≤3.0, add 5g sodium bicarbonate slowly and adjust pH=5-7, insulation protects pH value reaction to terminal (2-3 hour).
C, doazo reaction
Add water 80g, trash ice 100g, dispersion agent 1g of 50g1.5-disulfonic acid-2-naphthylamines pulls an oar 1 hour, add 15g hydrochloric acid (content 30%), 50g trash ice, slowly sodium nitrite solution (configuring in advance: 10g Sodium Nitrite+30g water stirs molten clear) is added, control temperature 0-15 DEG C between charge period, and keep congo-red test paper to show avy blue.Sodium nitrite solution adds complete, is incubated 0-15 DEG C of reaction 1 hour, adds 0.5g thionamic acid and to disappear unnecessary Sodium Nitrite.
D, coupled reaction
1.5-disulfonic acid-2-naphthylamines diazonium salt is joined in above-mentioned two contracting liquid, insulation 5-10 DEG C, add 15g sodium bicarbonate adjustment pH=5-7, react to diazonium salt disappearance (2-3 hour).
E, three contracting reactions
8g nicotinic acid dry powder directly adds in coupling solution, stirs after 10 minutes, is directly warming up to 80-95 DEG C, and keeps pH=4-7 with 13g sodium bicarbonate.Control reaction (reaction 8-10 hour) to terminal.
F, steam drying
Terminal directly obtains 132g formula (1-1) active deep red dyestuff with steam drying after arriving.
The structural formula that G, raw materials are corresponding with it is as shown in table 1
Table 1
Embodiment 2: the preparation that formula (1-2) is active deep red.
A, a contracting reaction
12g cyanuric chloride adds water 50g, trash ice 150g, dispersion agent 1g in about 0 DEG C making beating 1 hour.1-amino-8-naphthol-3,6-disulphonic acid (configure in advance: 26g+ water 80g adds sodium bicarbonate 6g and adjusts pH=6-7, stir molten clear) is added cyanuric chloride slowly to suspend in material, control temperature 0-10 DEG C between charge period, pH≤3.After adding, protect pH=1-2, temperature 0-3 DEG C of reaction to terminal (1-2 hour) with 5g sodium bicarbonate.
B, two contracting reactions
Joined by 3.5g Ursol D in an above-mentioned contracting liquid, be warming up to 30-50 DEG C immediately, when PH≤3.0, add 5g sodium bicarbonate slowly and adjust pH=5-7, insulation protects pH value reaction to terminal (2-3 hour).
C, doazo reaction
Add water 80g, trash ice 100g, dispersion agent 1g of 50g1.5-disulfonic acid-2-naphthylamines pulls an oar 1 hour, add 15g hydrochloric acid (content 30%), 50g trash ice, slowly sodium nitrite solution (configuring in advance: 10g Sodium Nitrite+30g water stirs molten clear) is added, control temperature 0-15 DEG C between charge period, and keep congo-red test paper to show avy blue.Sodium nitrite solution adds complete, is incubated 0-15 DEG C of reaction 1 hour, adds 0.5g thionamic acid and to disappear unnecessary Sodium Nitrite.
D, coupled reaction
1.5-disulfonic acid-2-naphthylamines diazonium salt is joined in above-mentioned two contracting liquid, insulation 5-10 DEG C, add 15g sodium bicarbonate adjustment pH=5-7, react to diazonium salt disappearance (2-3 hour).
E, three contracting reactions
8g γ-picolinic acid dry powder directly adds in coupling solution, stirs after 10 minutes, is directly warming up to 80-95 DEG C, and keeps pH=4-7 with 13g sodium bicarbonate.Control reaction (reaction 8-10 hour) to terminal.
F, steam drying
Terminal directly obtains 132g formula (1-2) active deep red dyestuff with steam drying after arriving.
The structural formula that G, raw materials are corresponding with it is as shown in table 2
Table 2
Embodiment 3: filter out several formula, in table 3 according to features such as superior application performances.Its application performance of reactive dyestuffs prepared by the embodiment of the present invention is as shown in following table 4 and table 5.
Table 3
| Sequence number | Color | Formula rate |
| Formula (1-1) | Scarlet | Formula (1-1) 60g, Sodium sulfate anhydrous.min(99) 40g |
| Formula (1-2) | Scarlet | Formula (1-2) 80g, Sodium sulfate anhydrous.min(99) 20g |
| Formula (1-1)+formula (1-2) | Scarlet | Formula (1-1) 30g, formula (1-2) 50g, Sodium sulfate anhydrous.min(99) 20g |
In above-mentioned table 1, each reactive dye compositions carries out dry powder blend in tempering tank, or spraying dry after common dissolving.Also have other reactive dye compositions not enumerating, but comprise in the present invention.
Embodiment 2:100g cotton, the low alkali of the one obtained by embodiment 1 or the active deep red dyestuff of non-alkali, weigh 2% by fabric, is being in the dye bath of 20:1 containing 60g/l Sodium sulfate anhydrous.min(99), bath raio, adsorb 30min at 60 DEG C, add soda ash (consumption 15-20g/l) fixation 45min.DYED FABRICS is through washing, soap boiling, drying.The dyed cotton fabric obtained has Exposure to Sunlight and the moisture resistant fastness of homogeneous color and satisfaction.Specific performance is in table 4.
Table 4
Table 5
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (5)
1. low alkali shown in formula (1) or the active deep red dyestuff of non-alkali
Wherein, M is hydrogen or basic metal.
2. the low alkali according to claims 1 or the active deep red dyestuff of non-alkali, structural formula is the one of following formula (1-1) or formula (1-2) compound or the mixing of formula (1-1) and formula (1-2) compound:
3. the preparation method of the low alkali described in claim 1 or 2 or the active deep red dyestuff of non-alkali, is characterized in that: comprise the steps:
A, a contracting reaction
Cyanuric chloride adds water, trash ice, dispersion agent are pulled an oar 1 hour in about 0 DEG C; 1-amino-8-naphthol-3,6-disulphonic acid being added slowly cyanuric chloride suspends in material, control temperature 0-10 DEG C between charge period, pH≤3; After adding, protect pH=1-2 with sodium bicarbonate, temperature 0-3 DEG C of reaction to terminal;
B, two contracting reactions
Joined by Ursol D in an above-mentioned contracting liquid, be warming up to 30-50 DEG C immediately, when PH≤3.0, add sodium bicarbonate slowly and adjust pH=5-7, insulation protects pH value reaction to terminal;
C, doazo reaction
1.5-disulfonic acid-2-naphthylamines adds water, trash ice, dispersion agent making beating 1-2 hour, adds hydrochloric acid, trash ice, adds sodium nitrite solution slowly, control temperature 0-15 DEG C between charge period, and keep congo-red test paper to show avy blue; Sodium nitrite solution adds complete, is incubated 0-15 DEG C of reaction 1 hour, adds thionamic acid and to disappear unnecessary Sodium Nitrite;
D, coupled reaction
1.5-disulfonic acid-2-naphthylamines diazonium salt is joined in above-mentioned two contracting liquid, insulation 5-10 DEG C, add sodium bicarbonate adjustment pH=5-7, react to diazonium salt and disappear;
E, three contracting reactions
Nicotinic acid or γ-picolinic acid dry powder directly add in coupling solution, stir after 10 minutes, are directly warming up to 80-95 DEG C, and keep pH=4-7 with sodium bicarbonate; Control reaction to terminal;
F, steam drying
Terminal directly obtains formula (1) dyestuff with steam drying after arriving.
4. low alkali or the active deep red dye composite of non-alkali, comprise low alkali described in claim 1 or 2 or the active deep red dyestuff of non-alkali and auxiliary agent, described auxiliary agent is: the one in Sodium sulfate anhydrous.min(99), Sodium hexametaphosphate 99, condensation compound of methyl naphthalene sulfonic acid and formaldehyde, naphthalene sulfonic acidformaldehyde condensation product or its mixture.
5. low alkali according to claim 4 or the active deep red dye composite of non-alkali, is characterized in that: described auxiliary agent is Sodium sulfate anhydrous.min(99).
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|---|---|---|---|
| CN201410512778.0A CN104312202A (en) | 2014-09-29 | 2014-09-29 | Low-alkaline or alkali-free active dark red dye and preparation method thereof |
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| CN201410512778.0A CN104312202A (en) | 2014-09-29 | 2014-09-29 | Low-alkaline or alkali-free active dark red dye and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100478A (en) * | 2019-12-30 | 2020-05-05 | 浙江劲光实业股份有限公司 | Preparation method and application of blue dye with three active groups |
| CN114133764A (en) * | 2021-12-10 | 2022-03-04 | 上海雅运新材料有限公司 | Red dye composition and application and dyeing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0420949B2 (en) * | 1983-10-19 | 1992-04-07 | Nippon Kayaku Kk | |
| JP2001214087A (en) * | 2000-02-04 | 2001-08-07 | Sumitomo Chem Co Ltd | Reactive dye composition and dyeing method using the same |
| EP1712677A1 (en) * | 2005-04-08 | 2006-10-18 | Clariant International Ltd. | Aqueous solutions of optical brighteners |
| KR20120058140A (en) * | 2010-11-29 | 2012-06-07 | (재)한국섬유소재연구소 | Dyeing method of rayon-polyester union cloth |
| CN103243576A (en) * | 2013-05-02 | 2013-08-14 | 浙江亿得化工有限公司 | Reactive dye printing paste for flat net or rotary screen printing and preparation method of reactive dye printing paste |
-
2014
- 2014-09-29 CN CN201410512778.0A patent/CN104312202A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0420949B2 (en) * | 1983-10-19 | 1992-04-07 | Nippon Kayaku Kk | |
| JP2001214087A (en) * | 2000-02-04 | 2001-08-07 | Sumitomo Chem Co Ltd | Reactive dye composition and dyeing method using the same |
| EP1712677A1 (en) * | 2005-04-08 | 2006-10-18 | Clariant International Ltd. | Aqueous solutions of optical brighteners |
| KR20120058140A (en) * | 2010-11-29 | 2012-06-07 | (재)한국섬유소재연구소 | Dyeing method of rayon-polyester union cloth |
| CN103243576A (en) * | 2013-05-02 | 2013-08-14 | 浙江亿得化工有限公司 | Reactive dye printing paste for flat net or rotary screen printing and preparation method of reactive dye printing paste |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100478A (en) * | 2019-12-30 | 2020-05-05 | 浙江劲光实业股份有限公司 | Preparation method and application of blue dye with three active groups |
| CN111100478B (en) * | 2019-12-30 | 2021-03-05 | 浙江劲光实业股份有限公司 | Preparation method and application of blue dye with three active groups |
| CN114133764A (en) * | 2021-12-10 | 2022-03-04 | 上海雅运新材料有限公司 | Red dye composition and application and dyeing method thereof |
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