CN100543086C - A kind of bi-azo active dye, preparation method and composition thereof - Google Patents
A kind of bi-azo active dye, preparation method and composition thereof Download PDFInfo
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- CN100543086C CN100543086C CNB2006100496426A CN200610049642A CN100543086C CN 100543086 C CN100543086 C CN 100543086C CN B2006100496426 A CNB2006100496426 A CN B2006100496426A CN 200610049642 A CN200610049642 A CN 200610049642A CN 100543086 C CN100543086 C CN 100543086C
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- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000975 dye Substances 0.000 claims abstract description 81
- 239000012954 diazonium Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000005859 coupling reaction Methods 0.000 claims description 11
- 150000001989 diazonium salts Chemical class 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 9
- 238000006193 diazotization reaction Methods 0.000 claims description 5
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 18
- 239000000835 fiber Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005562 fading Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 230000000712 assembly Effects 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 239000004218 Orcein Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- -1 ammonium salt compound Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- HFIYIRIMGZMCPC-UHFFFAOYSA-J chembl1326377 Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(N=NC=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1N=NC1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-UHFFFAOYSA-J 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 235000019248 orcein Nutrition 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229960003010 sodium sulfate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The present invention relates to a kind of bi-azo active dye, preparation method and composition thereof, described reactive dyestuffs are suc as formula shown in (I), these reactive dyestuffs can be applied to the printing and dyeing of cellulosic fibre separately, and it is bright-coloured to obtain coloured light, water-fastly wash, the good dying product of colour fastness such as rub resistance, perspiration resistance.In addition, also one or more assemblies in the described dyestuff can be mixed and use, obtain having the dye composite of various black coloured light; This dye composite pitch black degree height, lifting force is good, is used for dyeing nitrogenous or the hydroxyl fiber, the non-fading dying product that can obtain being fit for various uses, and every fastness excellent property, effect is splendid.
Description
(1) technical field
The present invention relates to a kind of bi-azo active dye and preparation method thereof, also relate to a kind of composition of described bi-azo active dye.
(2) background technology
Reactive dyestuffs because of its lovely luster, chromatogram is complete, application is easy, the good development dye the most rapidly that becomes of fastness, but traditional reactive dyestuffs shortcoming in dyeing course is obvious, use a large amount of salt to urge to dye as needs, hydrolised dye in the dyeing course can't utilize etc., thereby have influence on its economy and the feature of environmental protection, therefore, how to improve the reactive dyestuffs structure, obtain high colour-fast rate low-salt active dyestuff is the focus of research always.
In the dyeing of reactive dyestuffs, black is the kind of large usage quantity, the most normal use at present be to adopt C.I. reactive black 5 and mixture orange, the red component colorant match, but there is shortcoming in this dyestuff equally when dyeing: dye uptake is not high, generally have only 70～80%, the ionogen consumption is big, and compatibleness neither be fine, thereby causes lifting force deficiency etc.For overcoming above-mentioned defective, need dyestuff direct high to reduce electrolytical usage quantity, fixing part is not water-soluble in the dyeing course simultaneously will get well, and is convenient to eccysis, and in addition, the structure of piecing together the union dyeing material should be similar as far as possible, in order to the improvement of compatibleness.
(3) summary of the invention
Coloured light was bright-coloured when the object of the invention was to provide a kind of dyeing, water-fastly washed, the good bi-azo active dye of colour fastness such as rub resistance, perspiration resistance.
Another purpose of the present invention is to provide a kind of preparation method of described bi-azo active dye.
Another purpose of the present invention also is to provide a kind of composition of described bi-azo active dye.
Bi-azo active dye of the present invention is suc as formula shown in (I),
In its Chinese style (I), phenyl ring or the naphthalene nucleus of A for replacing, the substituting group on described phenyl ring or the naphthalene nucleus be one or more following radicals :-OH ,-SO
3H ,-NHR
5, R wherein
5Be H or C
1-C
4Alkyl; M, n independently are 0,1 or 2 separately; X
1, X
2Have one at least for being selected from the group of formula (II-a)～(II-f):
-SO
2CH
2CH
2U formula (II-a)
-NHSO
2CH
2CH
2U formula (II-b)
-SO
2NHCH
2CH
2U formula (II-c)
-CONHCH
2CH
2U formula (II-d)
-NHCOCH
2CH
2U formula (II-e)
-NHCOCH
2U formula (II-f)
Wherein U is the alkaline quaternary ammonium salt group that can leave away down in (II-a)～(II-f).
Preferably, described X
1, X
2One of be suc as formula-SO
2C
2H
4The substituting group of Z; Wherein, Z is-OSO
3H ,-OSO
3Na ,-SSO
3H ,-SSO
3Na, Z are preferably-OSO
3H or-OSO
3Na.Most preferably, described X
1, X
2One of be-SO
2CH
2CH
2N
+(CH
3)
3, another is-SO
2C
2H
4OSO
3H.
Preferably, described quaternary ammonium salt group is suc as formula (III-a) or (III-b):
R wherein
1, R
2, R
3Independent separately is C
1-C
4Alkyl, R
4For H or-COOH.
Again preferably, described quaternary ammonium salt group is suc as formula shown in (III-a), wherein R
1, R
2, R
3Independent separately is methyl.
Described m, n independently are preferably 0 or 1 separately.
As of the present invention preferred, described bi-azo active dye structure is suc as formula shown in (IV):
Wherein m, n, X
1, X
2Define all the same.
As present invention further optimization, described bi-azo active dye structure is as shown in the formula shown in (IV-a):
Another is preferred as of the present invention, and described bi-azo active dye structure is shown in formula V:
Wherein m, n, X
1, X
2, R
5Define all the same.
As present invention further optimization, described bi-azo active dye structure is shown in (V-a):
The present invention also provides a kind of preparation method of above-mentioned bi-azo active dye, and described preparation method comprises the steps:
1. formula (VI) compound is carried out diazotization, obtain its corresponding diazonium salt;
2. aromatic compound A is dissolved in water, splashes in the diazonium salt of formula (VI) compound,, obtain monoazo-dyes suc as formula (VII) in about 10 ℃, carrying out coupled reaction 2～5 hours under the acidic conditions;
3. formula (VIII) compound is carried out diazotization, obtain being added drop-wise to behind its corresponding diazonium salt in the monoazo-dyes solution suc as formula (VII) and carry out coupling, can make bi-azo active dye suc as formula (I);
Wherein m, n, X
1, X
2, A definition is all the same.
Above-mentioned formula (VI) or (VIII) described quarternary ammonium salt compound can select corresponding sulfate derivative and various reactive tertiary amine for use and get (as described in patent DE1064055), obtain containing the product (as described in patent DE1137155, DE1124172) of quaternary ammonium salt behind the perhaps synthetic corresponding chloro thing with various reactive tertiary amines.
Bi-azo active dye of the present invention, in its molecular structure, the quaternary ammonium salt group that exists one or two to leave away, these quaternary ammonium salt groups not only can be used as active group and use, can make that also dyestuff has the characteristic of cationic dyestuff, thereby reduce electrolytical usage quantity in the cellulose dyeing process, reach the purpose of low salt dyeing.In addition, because of cation group in the structural formula is to exist as active group, after dyeing, anchor at like this in the dyestuff on the fiber and do not contain cation group, and have identical fastness ability with common reactive dyestuffs, can not reduce the dyestuff fastness ability because of the introducing of cation group, and the cation group of leaving away after the dyeing is an amine structure, very easy degraded in water, thus reduced the pressure of dyeing back to environment.
Bi-azo active dye composition of the present invention, percentage ratio meter by weight, comprising: one or more of 1～50% are suc as formula the bi-azo active dye of (I) and one or more bi-azo active dyes suc as formula (IX) of 50～99%;
Wherein m, n, X
1, X
2Define all the same.
Preferably, described bi-azo active dye composition by the described reactive dyestuffs of formula (IV-a), the described reactive dyestuffs of formula (V-a) and formula (IX-a) or (IX-b) described reactive dyestuffs form;
Preferably, in the described bi-azo active dye composition, percentage ratio meter by weight, the described reactive dyestuffs content of formula (IV-a) is 1～34%, the described reactive dyestuffs content of formula (V-a) is 1～34%, formula (IX-a) or (IX-b) described reactive dyestuffs content be 65～95%.
The preparation of reactive dye compositions of the present invention can be adopted on the dyestuff colorant match method commonly used, mixes mutually as formula (I) dyestuff, formula (IX) dyestuff with above-mentioned metering ratio, can add reactive dyestuffs commercialization usual auxiliaries in the mixing process, as Sodium sulfate anhydrous.min(99) etc.
Reactive dyestuffs of the present invention can be applied to the printing and dyeing of cellulosic fibre separately, and it is bright-coloured to obtain coloured light, water-fastly wash, the good dying product of colour fastness such as rub resistance, perspiration resistance.In addition, also can with in formula (I) dyestuff one or more, one or more dyestuffs in formula (IX) dyestuff piece together to mix and use, and obtain having the dye composite of various black coloured light; This dye composite pitch black degree height, lifting force is good, is used for dyeing nitrogenous or the hydroxyl fiber, the non-fading dying product that can obtain being fit for various uses, and every fastness excellent property, effect is splendid.
(4) embodiment
Further specify the present invention below in conjunction with specific embodiment, but protection scope of the present invention is not limited to this.Unless specialize, " part " among the following embodiment all refers to weight part.
Embodiment 1
24.3 the substituted aniline of part formula (VI-a), add after 100 parts of water stir, be cooled to 0-5 ℃, add 18 parts of concentrated hydrochloric acids, keeping 0-5 ℃, to drip 6.9 parts of content be 30% sodium nitrite in aqueous solution, added in 10 minutes, continues to stir after 20 minutes, add thionamic acid and eliminate excessive nitrous acid, obtain diazonium salt.
The mphenylenediamine ortho-sulfonic acid joined in the 100ml water for 18.8 parts stir, regulating pH is 7, after the dissolving, be added drop-wise in the diazonium salt of formula (VI-a), 10 ℃ of coupling temperature, regulator solution pH 2.5-3 dropwises in 30min simultaneously, drip the back and reacted 3 hours at 2.5-3, obtain the monoazo-dyes of formula (VII-a) with 10% sodium carbonate solution regulator solution pH.
With 38.3 parts of the sulfonation para-ester of formula (VIII-a), be added in the 100ml water and stir, add the 18ml concentrated hydrochloric acid, keep 0-5 ℃ of 30% aqueous solution that drips 6.9 parts of Sodium Nitrites, in 10min, drip, continue stirring reaction then after 20 minutes, add thionamic acid and eliminate excessive nitrous acid.
In the monoazo-dyes solution of the formula (VII-a) above the para-ester diazonium salt of formula (VIII-a) is added drop-wise in 20min, 10 ℃ of coupling temperature, regulate pH5.5, continued stirring reaction three hours, coupling finishes, spraying drying makes the Powdered dyestuff of formula (IV-a), can offer cellulosic fibre material with orange color and luster.
Embodiment 2～8
According to the preparation method of embodiment 1, different is replaces formula (VI-a), formula (VIII-a) in the example 1 respectively with the compound of listing in the table 1, can obtain serial orange dye as shown in the table.
Embodiment 9
24.3 the substituted aniline of part formula (VI-a), add after 100 parts of water stir, be cooled to 0-5 ℃, add 18 parts of concentrated hydrochloric acids, keep 0-5 ℃ of 30% aqueous solution that drips 6.9 parts of Sodium Nitrites, in 10 minutes, add, continue to stir after 20 minutes, add thionamic acid and eliminate excessive nitrous acid, obtain diazonium salt.
2-amino-5-naphthols-7-sulfonic acid is joined in the 100ml water for 21.58 parts and stirs, after regulating pH to 7 dissolving, be added drop-wise in the diazonium salt solution of the formula (VI-a) that obtains above, 10 ℃ of coupling temperature, while regulator solution pH 2-2.5, in 30min, dropwise, drip the back and reacted 3 hours at 2-2.5, obtain the monoazo-dyes of formula (VII-b) with 10% sodium carbonate solution regulator solution pH.
With the sulfonation para-ester of 38.3 parts of formulas (VIII-a), be added in the 100ml water and stir, add the 18ml concentrated hydrochloric acid, keep 0-5 ℃ of 30% aqueous solution that drips 6.9 parts of Sodium Nitrites, in 10min, drip, continue stirring reaction then after 20 minutes, add thionamic acid and eliminate excessive nitrous acid.
In the monoazo-dyes solution of the formula (VII-b) above the para-ester diazonium salt of formula (VIII-a) is added drop-wise in 20min, 10 ℃ of coupling temperature are regulated pH4.5 with 10% sodium carbonate solution, continue stirring reaction 1 hour, the pH to 6 that raises again continues reaction 2 hours, and coupling finishes.The dye solution that obtains makes the Powdered dyestuff of formula (V-a) by spraying drying, can offer cellulosic fibre material with red color and luster.
Formula (V-a)
Embodiment 10～15
According to implementing the method described in 9, different is replaces formula (VI-a), formula A, formula (VIII-a) among the embodiment 9 respectively with the compound of listing in the table 2, can obtain serial orchil as shown in the table.
Table 2
Embodiment 16
According to embodiment 1 described method, different is, with etc. after the compound diazotization of following formula A of mol ratio, carry out coupling with the compound shown in formula (VI--n), the formula (VIII-m) respectively, make the black compound of following formula (IX-a):
Embodiment 17
Piece together the dyestuff of 70 parts of following formulas (IX-a), the dyestuff of 15 parts of following formulas (IV-a), the dyestuff of 15 parts of following formulas (V-a) mixed, the aqueous solution separately that maybe will contain corresponding umber amount mixes mutually, spraying drying, the dye mixture that obtains (containing the electrolytic salt that comes from synthetic) can make cellulosic fibre material with aterrimus.
Embodiment 18～24
According to the foregoing description 17 described methods, the dyestuff shown in the following table 3 is compared with by weight mixed, get final product to such an extent that cellulosic fibre material with black composite dyestuff.
Table 3
| Embodiment | Formula (IX) dyestuff | Formula (IV) dyestuff | The formula V dyestuff | Weight ratio |
| 18 | (IX-a) | (IV-b) | (V-b) | 55：30：15 |
| 19 | (IX-a) | (IV-c) | (V-c) | 60：10：30 |
| 20 | (IX-a) | (IV-d) | (V-d) | 70：20：10 |
| 21 | (IX-b) | (IV-e) | (V-e) | 80：15：5 |
| 22 | (IX-b) | (IV-f) | (V-f) | 85：5：10 |
| 23 | (IX-b) | (IV-g) | (V-g) | 90：6：4 |
| 24 | (IX-b) | (IV-h) | (V-a) | 95：3：2 |
Embodiment 25 dyeing embodiment
Respectively with 4 parts of the dyestuffs that make in the foregoing description 1～24, join in 1000 parts of water, add 30 parts of sodium sulfate, after the dissolving back adds 50 parts of cottons immersion 10min, dye bath is warmed up to 60 ℃ in 20min, add 15 parts of yellow soda ash after keeping 30min, behind the continuation insulation dyeing 30min, take out cloth specimen, behind the cold water washing loose colour, join 60 ℃ of rinsing 10min in the soap lye of 30 grams per liters, take out cloth specimen, dry.Test its colour fastness to rubbing, colour fastness to perspiration, color fastness to water by the method for determining among GB/T 3920-1997, GB/T 3922-1997 and the GB/T 5713-1997 respectively, test result sees the following form 4.
Table 4
| Embodiment | Rub resistance | Perspiration resistance | Water-fast soaking | Color |
| Embodiment 1 | 4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 2 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 3 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 4 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 5 | 4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 6 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 7 | 4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 8 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 9 | 4 grades | 4～5 grades | 4～5 grades | Red |
| Embodiment 10 | 3～4 grades | 4～5 grades | 4～5 grades | Red |
| Embodiment 11 | 4 grades | 4～5 grades | 4～5 grades | Red |
| Embodiment 12 | 3～4 grades | 4～5 grades | 4～5 grades | Red |
| Embodiment 13 | 3～4 grades | 4～5 grades | 4～5 grades | Red |
| Embodiment 14 | 4 grades | 4～5 grades | 4～5 grades | Red |
| Embodiment 15 | 3～4 grades | 4～5 grades | 4～5 grades | Red |
| Embodiment 16 | 3～4 grades | 4～5 grades | 4～5 grades | Black |
| Embodiment 17 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
| Embodiment 18 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
| Embodiment 19 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
| Embodiment 20 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
| Embodiment 21 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
| Embodiment 22 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
| Embodiment 23 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
| Embodiment 24 | 4 grades | 4～5 grades | 4～5 grades | Pitch black |
Can find out that from the said determination result the every fastness of bi-azo active dye provided by the invention and composition thereof is good.
Claims (15)
1, a kind of bi-azo active dye suc as formula (I),
In its Chinese style (I), A is the substituting group shown in one of following formula:
M, n independently are 0,1 or 2 separately; X
1, X
2Have one at least for being selected from the group of formula (II-a)～(II-f):
-SO
2CH
2CH
2U formula (II-a)
-NHSO
2CH
2CH
2U formula (II-b)
-SO
2NHCH
2CH
2U formula (II-c)
-CONHCH
2CH
2U formula (II-d)
-NHCOCH
2CH
2U formula (II-e)
-NHCOCH
2U formula (II-f)
Wherein U is the alkaline quaternary ammonium salt group that can leave away down in (II-a)～(II-f).
2, bi-azo active dye as claimed in claim 1 is characterized in that described X
1, X
2One of be suc as formula-SO
2C
2H
4The substituting group of Z; Wherein, Z is-OSO
3H ,-OSO
3Na ,-SSO
3H or-SSO
3Na.
3, bi-azo active dye as claimed in claim 2 is characterized in that described Z is-OSO
3H or-OSO
3Na.
4,, it is characterized in that described quaternary ammonium salt group is suc as formula (III-a) or (III-b) as the described bi-azo active dye of one of claim 1～3:
R wherein
1, R
2, R
3Independent separately is C
1-C
4Alkyl, R
4For H or-COOH.
5, bi-azo active dye as claimed in claim 4 is characterized in that described quaternary ammonium salt group suc as formula shown in (III-a), wherein R
1, R
2, R
3Independent separately is methyl.
6,, it is characterized in that described m, n independently are 0 or 1 separately as the described bi-azo active dye of one of claim 1～3.
7, bi-azo active dye as claimed in claim 5 is characterized in that described X
1, X
2One of be-SO
2CH
2CH
2N
+(CH
3)
3, another is-SO
2C
2H
4OSO
3H.
8, bi-azo active dye as claimed in claim 1 is characterized in that structure is suc as formula shown in (IV):
Wherein m, n, X
1, X
2Definition is all with claim 1.
9, bi-azo active dye as claimed in claim 8 is characterized in that structure is as shown in the formula shown in (IV-a):
10, bi-azo active dye as claimed in claim 1 is characterized in that structure is shown in formula V:
Wherein m, n, X
1, X
2, R
5Definition is all with claim 1.
11, bi-azo active dye as claimed in claim 10 is characterized in that structure is shown in (V-a):
12, the preparation method of the described bi-azo active dye of a kind of claim 1 comprises the steps:
1. formula (VI) compound is carried out diazotization, obtain its corresponding diazonium salt;
2. aromatic compound A is dissolved in water, splashes in the diazonium salt of formula (VI) compound, under acidic conditions, carried out coupled reaction 2～5 hours, obtain monoazo-dyes suc as formula (VII) at 10 ℃;
3. formula (VIII) compound is carried out diazotization, obtain being added drop-wise to behind its corresponding diazonium salt in the monoazo-dyes solution suc as formula (VII) and carry out coupling, can make bi-azo active dye suc as formula (I);
Wherein m, n, X
1, X
2, A defines all with claim 1.
13, a kind of bi-azo active dye composition, percentage ratio meter by weight comprises: the described bi-azo active dye of one or more claims 1 of 1～50% and one or more bi-azo active dyes suc as formula (IX) of 50～99%;
Wherein m, n, X
1, X
2Definition is all with claim 1.
14, as the described bi-azo active dye composition of claim 13, it is characterized in that by the described reactive dyestuffs of formula (IV-a), the described reactive dyestuffs of formula (V-a) and formula (IX-a) or (IX-b) described reactive dyestuffs form;
15, bi-azo active dye composition as claimed in claim 14, it is characterized in that percentage ratio meter by weight, the described reactive dyestuffs content of formula (IV-a) is 1～34%, the described reactive dyestuffs content of formula (V-a) is 1～34%, formula (IX-a) or (IX-b) described reactive dyestuffs content be 65～95%.
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| CN100543086C true CN100543086C (en) | 2009-09-23 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2251325A1 (en) * | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Bisazo compounds |
| CN102775335B (en) * | 2012-08-08 | 2013-12-25 | 王钟民 | Black bisazo thioether sulfoacid compound or black bisazo thioether sulfoacid compound salts, and preparation method and application thereof |
| CN102807767B (en) * | 2012-08-08 | 2014-06-04 | 大连福思达专用化学有限公司 | Black bisazo sulfonic acid compound, and salt, preparation method and application thereof |
| CN102876084B (en) * | 2012-10-29 | 2014-07-30 | 上海雅运纺织化工股份有限公司 | Reactive dye composition and application thereof to fabric dyeing |
| CN103073917B (en) * | 2012-12-31 | 2014-09-03 | 浙江瑞华化工有限公司 | Black reactive dye composition |
| CN105602286B (en) * | 2016-03-17 | 2017-12-12 | 浙江瑞华化工有限公司 | A kind of Black reactive dye composition and its production and use |
| CN107501997A (en) | 2017-07-28 | 2017-12-22 | 浙江科永化工有限公司 | A kind of reactive navy blue is to black dye composition and dye preparations |
| CN109456234A (en) * | 2018-12-05 | 2019-03-12 | 营口理工学院 | The parent and preparation method of a kind of X-type reactive dye of indigo bisazo base and application |
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