CN102250491B - Disazo reactive dye - Google Patents
Disazo reactive dye Download PDFInfo
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- CN102250491B CN102250491B CN 201010175509 CN201010175509A CN102250491B CN 102250491 B CN102250491 B CN 102250491B CN 201010175509 CN201010175509 CN 201010175509 CN 201010175509 A CN201010175509 A CN 201010175509A CN 102250491 B CN102250491 B CN 102250491B
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- dye
- dyestuff
- oso
- formula
- active dye
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Abstract
The invention discloses a disazo reactive dye with a novel structure as shown in general formula (I), wherein the definition of each group in the formula is described in the description. After cellulose fibers such as cotton and ramie are dyed by the dye, different colors such as bright red, purple, blue and the like are displayed; the dye has a good colorizing rate, a good color-fixation rate, fastness to wet processing such as washing, sweat and the like, and fastness to sunlight, and is also applicable to direct textile printing of cellulose fibers.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to a kind of bi-azo active dye.
Background technology
Usually synthesized derivative reactive dyestuffs tetrazo compound by H acid, had following general structure:
The dark dyes such as that the color of this type of dyestuff is generally is dark blue, black.Such as navy reactive black KN-B, be take H acid as coupling component, para-ester is that diazo component carries out the bilateral coupling and gets dyestuff.The structure of reactive black KN-B dyestuff is as follows:
Fabric can be dyed black under the dark concentration of this dyestuff, but its degree of fixation being lower, only is 61-66%.The mode of many these dyestuffs of employing and other color reactive dyestuffs blending improves degree of fixation and other application performances of dyestuff at present.
Summary of the invention
The object of the invention is to develop the bi-azo active dye of class formation novelty, excellent performance.
Have now found that, when adopting 1,8-diaminonaphthalene-3, the 6-disulfonic acid is during as coupling component, although only a substituting group is different from H acid (8 is hydroxyl), but carry out the bi-azo active dye compound of the resulting class new texture of bilateral coupling with itself and identical diazo component, color and performance after comparing, dye with known dye have than big difference.For example, with 1,8-diaminonaphthalene 3, the 6-disulfonic acid is that coupling component, para-ester are that the color that diazo component gets dyestuff when carrying out the bilateral coupling is purple, and preferably enhancing is arranged, and degree of fixation can reach 80.59%.And the color of using the reactive black KN-B that H acid makes for coupling component instead is navy, and degree of fixation only is 61-66%.Accordingly, the applicant is with 1,8-diaminonaphthalene-3, and the 6-disulfonic acid is developed the bi-azo active dye of class formation novelty, excellent performance as coupling component, thereby has realized the purpose of invention.
Technical scheme of the present invention is as follows:
Bi-azo active dye with following general structure (I):
In the formula:
R
1, R
2Can be identical or different, be selected from respectively H, C
1-C
2Alkyl, C
1-C
2Alkoxyl group or-SO
3M;
Y is selected from-SO
2CH
2CH
2OSO
3M ,-SO
2CH=CH
2,-CONH (CH
2)
nSO
2C
2H
4OSO
3M ,-NHCOCH (Ha
1) CH
2(Ha
1) or-NHCOC (Ha
1)=CH
2, Ha wherein
1Represent halogen;
M is selected from H, Na, K or Li;
N is 1 to 6 integer.
The present invention more preferably technical scheme is, in the bi-azo active dye of general formula (I):
R
1, R
2Can be identical or different, be selected from respectively H ,-CH
3,-OCH
3Or-SO
3M;
Y is selected from-SO
2CH
2CH
2OSO
3M ,-CONH (CH
2)
nSO
2C
2H
4OSO
3M or-NHCOCH (Ha
1) CH
2-Ha
1, Ha wherein
1Represent halogen;
M is selected from H or Na;
N is 1 to 4 integer.
Further preferred technical scheme is, the bi-azo active dye that structural formula is following, and M is selected from H or Na in the formula.
Bi-azo active dye shown in the general formula of the present invention (I) can adopt the ordinary method preparation.For example, with 1,8-diaminonaphthalene-3, the 6-disulfonic acid makes by diazotization, coupled reaction as coupling component, the diazo component required with preparing the target dyestuff.Do not adopt in the preparation process and saltout product convection drying, three-waste free discharge.1,8-diaminonaphthalene-3,6-disulfonic acid are by 1,8-dinitronaphthalene-3, and the reduction of 6-disulfonic acid prepares, and other raw materials have commercially available.
Bi-azo active dye shown in the general formula (I) is a kind of environmental protection type dye of novel structure without carcinogenic toxicity.
Bi-azo active dye of the present invention can be used for dyeing and the stamp of cellulosic fibre material, such as the cellulosic fibre such as cotton, numb.Also can be applicable to dyeing and the stamp of the fiber blending fabric of hydroxyl fiber.Therefore, the present invention comprises that also the bi-azo active dye shown in the general formula (I) is used for the dyeing of cellulosic fibre material and the purposes of stamp.
Bi-azo active dye of the present invention presents the different colours such as bright-coloured redness, purple, blueness after the cellulosic fibre dyeing such as cotton, numb, wet treatment fastness and the sunlight fastness such as dye uptake, degree of fixation and washable, sweat proof are arranged preferably.
Dyestuff of the present invention can adopt various staining method fixation on fiber, particularly with water soluble dyestuffs solution and printing and dyeing paste form.And the present invention can adopt the variety of ways such as dip-dye, continuous knot dyeing, cold rolling heap or printing and dyeing to dye and stamp.
Embodiment
Following examples are used for further specifying the present invention.The umber that wherein relates to is parts by weight, except the solution of indicating specially concentration, all is converted to the sterling metering; Concentration unit is concentration expressed in percentage by weight.The method that adopts for every application performance test of dyestuff is as well known to those skilled in the art public.
Preparation of dyestuff embodiment
Embodiment 1
The preparation of dyestuff (1)
With 24.0 part 1,8-dinitrobenzene-3,6-naphthalene disulfonic acid are dissolved in 120 parts of water, together add autoclave with 0.2 part of 5% Pt/C catalyzer.The sealing autoclave is successively used nitrogen, hydrogen exchange gas reactor each four times, and the interior hydrogen pressure of still this moment is 0.5MPa.Under high-speed stirring, be warming up to 90～100 ℃, pass into hydrogen and keep that hydrogen pressure is 1.2～1.4MPa in the still, react 1 hour reduction reaction and finish.Leach catalyzer under the room temperature, the filtrate evaporate to dryness obtains product 1,8-diaminonaphthalene-3,6-disulfonic acid, liquid-phase chromatographic analysis product content 98.47%, yield 91.7%.
Get 32.3 part 1,8-diaminonaphthalene-3,6-disulfonic acid are scattered in 200 parts the water, and transferring to pH value of solution with 10% sodium carbonate solution is 5.5～6, makes it entirely molten, stand-by.
Get in the water that 56.2 parts of (4-beta-hydroxyethyl sulfone sulfate) aniline are scattered in 100 parts, pulled an oar 1 hour, then add 30 part 30% hydrochloric acid soln, be cooled to 0～5 ℃, add fast 14 parts of Sodium Nitrites, control temperature between 0～5 ℃, diazotization reaction 2 hours.Eliminate excessive nitrous acid, in 1 hour, splash into above-mentioned dissolving good 1,8-diaminonaphthalene-3,6-disulfonic acid solution, the control temperature was 5～10 ℃ of lower reactions 2 hours.With 10% sodium carbonate solution adjustment and to keep reaction medium pH be 6～6.5, the control temperature is 10～15 ℃ of lower reactions again, and detecting the diazonium salt disappearance with H acid is reaction end, convection drying must as shown in the formula 123.5 parts of purple dyes, its maximum absorption wavelength is λ
Max=580nm.Dye cotton or linen and be bright-coloured purple, have good lifting force, high dye uptake, high degree of fixation and good fastness.
Embodiment 2-10
The preparation of dyestuff (2)-dyestuff (10)
Select (the 4-beta-hydroxyethyl sulfone sulfate) aniline among different diazo component (seeing Table 1) the replacement embodiment 1, the preparation method is with embodiment 1, obtain dyestuff (2)-dyestuff (10), its concrete structure, maximum absorption wavelength and color see Table 2.
The diazo component of table 1 preparation dyestuff (2)-dyestuff (10)
| The dyestuff numbering | Diazo component |
| 2 | (3-beta-hydroxyethyl sulfone sulfate) aniline |
| 3 | 4-[2-(β-ethyl sulfonyl sulfate)-ethyl] formamido-aniline |
| 4 | 3-[2-(β-ethyl sulfonyl sulfate)-ethyl] formamido-aniline |
| 5 | (4-beta-hydroxyethyl sulfone sulfate) aniline-2-sulfonic acid |
| 6 | (5-beta-hydroxyethyl sulfone sulfate) aniline-2-sulfonic acid |
| 7 | (4-beta-hydroxyethyl sulfone sulfate) aniline-2-methoxyl group-5-methyl |
| 8 | (4-beta-hydroxyethyl sulfone sulfate) aniline-2, the 5-dimethoxy |
| 9 | (4-beta-hydroxyethyl sulfone sulfate) aniline-2-methoxyl group |
| 10 | (5-beta-hydroxyethyl sulfone sulfate) aniline-2-methoxyl group |
The reactive dyestuffs of the different diazo component preparations of table 2
| The dyestuff numbering | R 1 | Y | R 2 | M | λ max (nm) | Color |
| 2 | H | 3-SO 2C 2H 4OSO 3Na | H | Na | 565 | Rhodo |
| 3 | H | 4-CONHC 2H 4SO 2C 2H 4OSO 3Na | H | Na | 515 | Rhodo |
| 4 | H | 3-CONHC 2H 4SO 2C 2H 4OSO 3Na | H | Na | 555 | Rhodo |
| 5 | H | 4-SO 2C 2H 4OSO 3Na | 2-SO 3Na | Na | 615 | Dark blue |
| 6 | H | 5-SO 2C 2H 4OSO 3Na | 2-SO 3Na | Na | 610 | Blue |
| 7 | 5-CH 3 | 4-SO 2C 2H 4OSO 3Na | 2-OCH 3 | Na | 550 | Dark reddish purple |
| 8 | 5-OCH 3 | 4-SO 2C 2H 4OSO 3Na | 2-OCH 3 | Na | 565 | Dark blue |
| 9 | H | 4-SO 2C 2H 4OSO 3Na | 2-OCH 3 | Na | 529 | Rhodo |
| 10 | H | 5-SO 2C 2H 4OSO 3Na | 2-OCH 3 | Na | 525 | Rhodo |
Application embodiment
Embodiment 11
Dyestuff (1) is pressed 1%o.w.f (fabric is heavy relatively) consumption, and bath raio 1: 40 under the 50g/L Sodium sulfate anhydrous.min(99) is urged to dye, is dyed the cotton fabric that boiled in advance, and is lower to 15g/L yellow soda ash fixation, washing, soap boiling, drying at 60 ℃.Present bright-coloured purple at cotton.Dye uptake is 94.90%, and degree of fixation is 80.59%, has good lifting force and fastness.
The performance test data of dyestuff (1) sees Table 3, table 4, table 5, and the Integ value namely records the integrated value of each wavelength of K/S in the table 3 at spectrometer.
Table 3 dyestuff (1) lifting force test result
| Dye level (%) | 1 | 2 | 4 | 6 | 8 | 10 |
| The Integ value | 10.12 | 17.25 | 24.10 | 31.15 | 35.83 | 36.99 |
Table 4 dyestuff (1) dye uptake and degree of fixation test result
| Time (dividing) | 5 | 15 | 30 | 35 | 45 | 60 | 90 | |
| Dye uptake (%) | 0 | 48.32 | 48.69 | 58.40 | 85.11 | 92.70 | 93.53 | 94.90 |
| Degree of fixation (%) | 63.81 | 72.33 | 75.01 | 80.59 |
Table 5 dyestuff (1) fastness test result (dye level 3%)
Dyestuff (2)-dyestuff (10) carries out the tint applications performance test by the method for embodiment 11, and the result shows, has equally high colour-fast rate, good lifting force and fastness.
Claims (4)
1. bi-azo active dye, structure is shown in general formula (I):
In the formula:
R
1, R
2Can be identical or different, be selected from respectively H, C
1-C
2Alkyl, C
1-C
2Alkoxyl group or-SO
3M;
Y is selected from-SO
2CH
2CH
2OSO
3M ,-SO
2CH=CH
2,-CONH (CH
2)
nSO
2C
2H
4OSO
3M ,-NHCOCH (Ha
1) CH
2(Ha
1) or-NHCOC (Ha
1)=CH
2, Ha wherein
1Represent halogen;
M is selected from H, Na, K or Li;
N is 1 to 6 integer.
2. according to bi-azo active dye claimed in claim 1, in the general formula (I):
R
1, R
2Can be identical or different, be selected from respectively H ,-CH
3,-OCH
3Or-SO
3M;
Y is selected from-SO
2CH
2CH
2OSO
3M ,-CONH (CH
2)
nSO
2C
2H
4OSO
3M or-NHCOCH (Ha
1) CH
2-Ha
1, Ha wherein
1Represent halogen;
M is selected from H or Na;
N is 1 to 4 integer.
3. according to bi-azo active dye claimed in claim 2, structural formula is as follows, and M is selected from H or Na in the formula:
4. one kind is used for the dyeing of cellulosic fibre material and the purposes of stamp according to the bi-azo active dye shown in claim 1 formula of (I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010175509 CN102250491B (en) | 2010-05-17 | 2010-05-17 | Disazo reactive dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010175509 CN102250491B (en) | 2010-05-17 | 2010-05-17 | Disazo reactive dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102250491A CN102250491A (en) | 2011-11-23 |
| CN102250491B true CN102250491B (en) | 2013-04-10 |
Family
ID=44978073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010175509 Expired - Fee Related CN102250491B (en) | 2010-05-17 | 2010-05-17 | Disazo reactive dye |
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| Country | Link |
|---|---|
| CN (1) | CN102250491B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074229A (en) * | 1991-12-20 | 1993-07-14 | 山道士有限公司 | Fibre-reactive disazo compounds |
| EP0795586A2 (en) * | 1996-03-13 | 1997-09-17 | Basf Aktiengesellschaft | Mixtures of reactive disazo dyes |
| US5831040A (en) * | 1996-06-14 | 1998-11-03 | Ciba Specialty Chemicals Corporation | Disazo reactive dyes, their preparation and use |
| CN1422907A (en) * | 2001-12-01 | 2003-06-11 | 德意志戴斯达纺织品及染料两合公司 | Fiber active diazo-dye mixture and use thereof |
| CN1643079A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and use |
| CN1659241A (en) * | 2002-06-13 | 2005-08-24 | 克莱里安特财务(Bvi)有限公司 | Disazo dyes having adapted affinity |
| CN1687243A (en) * | 2005-04-21 | 2005-10-26 | 赵卫国 | Super black WNN of active azo dye and preparation thereof |
-
2010
- 2010-05-17 CN CN 201010175509 patent/CN102250491B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074229A (en) * | 1991-12-20 | 1993-07-14 | 山道士有限公司 | Fibre-reactive disazo compounds |
| EP0795586A2 (en) * | 1996-03-13 | 1997-09-17 | Basf Aktiengesellschaft | Mixtures of reactive disazo dyes |
| US5831040A (en) * | 1996-06-14 | 1998-11-03 | Ciba Specialty Chemicals Corporation | Disazo reactive dyes, their preparation and use |
| CN1422907A (en) * | 2001-12-01 | 2003-06-11 | 德意志戴斯达纺织品及染料两合公司 | Fiber active diazo-dye mixture and use thereof |
| CN1643079A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and use |
| CN1659241A (en) * | 2002-06-13 | 2005-08-24 | 克莱里安特财务(Bvi)有限公司 | Disazo dyes having adapted affinity |
| CN1687243A (en) * | 2005-04-21 | 2005-10-26 | 赵卫国 | Super black WNN of active azo dye and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴祖望等.深色活性染料的近期进展.《化工进展》.2009,第28卷(第5期),874-881. * |
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|---|---|
| CN102250491A (en) | 2011-11-23 |
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Granted publication date: 20130410 Termination date: 20160517 |