CN101117449A - High-concentration composite reactive dye - Google Patents
High-concentration composite reactive dye Download PDFInfo
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- CN101117449A CN101117449A CNA2007100127464A CN200710012746A CN101117449A CN 101117449 A CN101117449 A CN 101117449A CN A2007100127464 A CNA2007100127464 A CN A2007100127464A CN 200710012746 A CN200710012746 A CN 200710012746A CN 101117449 A CN101117449 A CN 101117449A
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- dye
- hydrogen
- dyestuff
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- composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000000985 reactive dye Substances 0.000 title claims abstract description 12
- 239000000975 dye Substances 0.000 claims abstract description 70
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- -1 methoxyl group Chemical group 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000002431 hydrogen Chemical group 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Chemical group 0.000 claims description 3
- 239000011591 potassium Chemical group 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 241001597008 Nomeidae Species 0.000 claims description 2
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 15
- 238000004043 dyeing Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 229920003043 Cellulose fiber Polymers 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000001049 brown dye Substances 0.000 abstract 1
- 238000010016 exhaust dyeing Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000008878 coupling Effects 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 239000012954 diazonium Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- QQNXPCCFPQRLMK-UHFFFAOYSA-N S(O)(O)(=O)=O.OCCS(=O)(=O)CCO Chemical compound S(O)(O)(=O)=O.OCCS(=O)(=O)CCO QQNXPCCFPQRLMK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009980 pad dyeing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 2
- KZKGEEGADAWJFS-UHFFFAOYSA-N 2-amino-5-methoxybenzenesulfonic acid Chemical compound COC1=CC=C(N)C(S(O)(=O)=O)=C1 KZKGEEGADAWJFS-UHFFFAOYSA-N 0.000 description 1
- LTPSRQRIPCVMKQ-UHFFFAOYSA-N 2-amino-5-methylbenzenesulfonic acid Chemical compound CC1=CC=C(N)C(S(O)(=O)=O)=C1 LTPSRQRIPCVMKQ-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- TUGNLJZTKXCQMO-UHFFFAOYSA-N 2-benzoylbenzenesulfonamide Chemical class NS(=O)(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 TUGNLJZTKXCQMO-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- UCTREIIEJSFTDI-UHFFFAOYSA-N 3-aminonaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(N)=CC2=C1 UCTREIIEJSFTDI-UHFFFAOYSA-N 0.000 description 1
- IMUUNYPYNWXUBO-UHFFFAOYSA-N 4-aminobenzene-1,3-disulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1S(O)(=O)=O IMUUNYPYNWXUBO-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001086902 Normanbya normanbyi Species 0.000 description 1
- 239000004218 Orcein Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SQYUJKVKVFILNB-UHFFFAOYSA-N methyl 2-amino-4-[(2,5-dichlorophenyl)carbamoyl]benzoate Chemical compound C1=C(N)C(C(=O)OC)=CC=C1C(=O)NC1=CC(Cl)=CC=C1Cl SQYUJKVKVFILNB-UHFFFAOYSA-N 0.000 description 1
- CCCDFCRHGYGKGP-UHFFFAOYSA-N methyl 5-bromo-4-chloro-2-fluorobenzoate Chemical compound COC(=O)C1=CC(Br)=C(Cl)C=C1F CCCDFCRHGYGKGP-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 235000019248 orcein Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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- Coloring (AREA)
Abstract
A high-concentration composite reactive dye belongs to the fine chemical field, relating to the preparing method of the high-concentration composite reactive dye. The invention is characterized in that: the invention discloses a high-concentration composite reactive dye, which comprises any type or more types of compound formula (I), any type or more types of compound formula (II), any type or more types of compound formula (III) and any type or more types of compound formula (IV); according to the percentage by weight, I to II to III is equal to (5-55) to (20-85) to (0-25), and (I plus II plus III) to IV is equal to (100-50) to (0-50). The invention has the beneficial effects that: remixed black and brown dyes possess high exhaust dyeing rate and color fixing rate and excellent level dyeing property, build-up property and repeatability, thereby the dye is particularly suitable to be used in short liquor ratio dyeing of cellulose fiber and polyamide fiber.
Description
Technical field
The present invention relates to composite active dye, especially black or brown composite dye, it is applicable to the dip-dye and the pad dyeing of cellulose fiber peacekeeping tynex.
Background technology
Reactive dyestuffs are main dyestuffs of a class that cellulose dyeing is used.In the present requirement to reactive dyestuffs, dye level is an extremely important index, requires dyestuff that good lifting force is arranged when especially dying spy's dark color, and the while is the easy again flush away of dyestuff of set not.Black and active dye is the bigger kind of application quantity, relevant patent (CN1858118A, CN1746231A) is though the relevant black composite active dye structure of introducing all has pitch black degree preferably, but insufficient be the orange and purplish blue look dye fixing rate that wherein adopts have only～60%, not only reduced economic benefit, and dyeing residual liquid has caused environmental pollution.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of high-concentration composite reactive dye, solves the not high problem of existing black and active dye degree of fixation, is particularly useful for short liquor dyeing and low-temperature alkali pad dyeing.
General structure in the high-concentration composite reactive dye of the present invention is as (I) with (II):
W is hydrogen or carboxyl in the general formula (I).
When W=hydrogen, then U is SO
2Y or SO
3H corresponds respectively to formula (Ia) and (Ib);
Wherein Y is CH
2CH
2OSO
3H, CH=CH
2Or Cl; M is hydrogen, sodium, potassium or lithium.
When the W=carboxyl, then U is D
5, the structure of general formula (I) can be expressed as:
Dyestuff (I) and (II) in D
1～D
5Be equivalent to following groups formula (1) or naphthalene sulfonic acid derivant;
R wherein
1And R
2It is the derivative (formula 2) of hydrogen, methyl, methoxyl group, sulfonic group, chlorine or benzanilide;
R wherein
3And R
4Be hydrogen, methyl, methoxyl group, sulfonic group and chlorine; Z is hydrogen or SO
2Y, wherein Y is CH
2CH
2OSO
3H, CH=CH
2Or Cl.
The present invention relates to that coupling component is 2 in general structure (Ia) dyestuff, 4-diamino-phenyl-2-hydroxyethyl sulfone sulfate, its structural formula is shown in (3):
2, the preparation of 4-diamino-phenyl-beta-hydroxyethyl sulfone sulfate is with 2, the 4-dinitrochlorobenzene is that raw material obtains 2 with the mercaptoethanol reaction earlier, 4-dinitrophenyl-beta-hydroxyethyl thioether, in the presence of catalyzer (tungstate), make 2 then, 4-dinitrophenyl-beta-hydroxyethyl sulfuryl with hydrogen peroxide oxidation; The reduction of nitro is in alcoholic solution to be that catalyzer is made reductive agent with hydrazine and carried out with iron, obtain 2,4-diamino-phenyl-beta-hydroxyethyl sulfuryl carries out esterification with sulfuric acid again.
The preparation method of dyestuff (Ia) uses corresponding to D
1The arylamine diazonium salt under the condition of pH4～5, carry out coupling obtain in the middle of dyestuff, and then use arylamine diazonium salt under the condition of pH5.5～7, to carry out the secondary coupling corresponding to D2, the reaction back dye liquor that finishes can directly carry out drying.
The preparation method of the Benzoylbenzene sulfonamide derivatives that the present invention relates to (formula 2) sees patent 200710011064.1.
Include at least one dyestuff (III) in the dye composition that the present invention relates to corresponding to the following formula structure:
R in the general formula (III)
5And R
6For hydrogen or contain C
1～C
4Alkyl; D
6And D
7For containing the anils of an active group at least, formula (3):
R wherein
7～R
8Be hydrogen, methyl, methoxyl group, sulfonic group or chlorine; Z is hydrogen or group SO
2Y, Y are CH
2CH
2OSO
3H, CH=CH
2Or Cl.
Dyestuff (I), (II) and (III) in group D
1～D
7Its corresponding arylamine can be 4-(beta-hydroxyethyl the sulfone sulfate)-aniline that contains active group, 3-(beta-hydroxyethyl sulfone sulfate)-aniline, 2-(beta-hydroxyethyl sulfone sulfate)-aniline, 2-chloro-4-(beta-hydroxyethyl sulfone sulfate)-aniline, 2-methoxyl group-5-(beta-hydroxyethyl sulfone sulfate)-aniline, 2-sulfonic group-4-(beta-hydroxyethyl sulfone sulfate)-aniline, 2-methyl-4-(beta-hydroxyethyl sulfone sulfate)-aniline, 2,5-dimethoxy-4 '-(beta-hydroxyethyl sulfone sulfate)-aniline, 2-methoxyl group-5-methyl-4-(beta-hydroxyethyl sulfone sulfate)-aniline, 3-amino-N-[4-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[4-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[3-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 3-amino-N-[3-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[2-methoxyl group-4-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[2-methoxyl group-5-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[2-chloro-4-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[2-sulfonic group-4-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[2,5-dimethoxy-4 '-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide, 4-amino-N-[2-methoxyl group-5-methyl-4-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide.
Group D in the dyestuff (I)
1, D
2And D
5, its corresponding amine also can be the arylamine of not being with active group.As 2-aniline sulfonic acid, 3-aniline sulfonic acid, 4-aniline sulfonic acid, aniline-2,5-disulfonic acid, aniline-2,4-disulfonic acid, 4-anisidine-2-sulfonic acid, 4-monomethylaniline-2-sulfonic acid, 4-anisidine-2,5-disulfonic acid, 2-amino-naphthene sulfonic acid, 2-amino-3,6-naphthalene disulfonic acid, 2-amino-1, the 5-naphthalene disulfonic acid.
In each dye composition that the present invention relates to, can include at least one auxiliary agent (IV) corresponding to the following formula structure:
(IVa) (IVb)
R wherein
9Be hydrogen, methyl, ethyl or benzyl, R
10Be methyl, propyl group, alkane hydroxyl, m is 1～2, and n is 2～10.
((I) be (III) and proportioning (IV) (II), according to weight percent I: II: III=(5～55): (20～85): (0～25) for dyestuff in the above-mentioned reactive dyestuffs mixture; (I+II+III): IV=(100～50): (0～50) can obtain the black of different tones and brown.
Effect of the present invention and benefit are that composite active dye has good dyeing behavior, and degree of fixation height, level-dyeing property and lifting force are good.Add auxiliary agent in the dye composition, be particularly useful for short liquor dyeing and low-temperature alkali pad dyeing.
Embodiment
In the following example, except that specified otherwise, be the parts by weight of folding hundred.
Embodiment 1
36.2 parts of 4-(beta-hydroxyethyl sulfone sulfate)-aniline is mixed making beating～60min with 350 parts of water, drip 46 parts of 30% sodium nitrite solutions under the liquid level, under this temperature, stir and reach home until diazotization at 0～5 ℃.
The aqueous solution that will contain 29.6 parts of compounds (3) joins in the above-mentioned diazonium salt, carries out a coupling at～5 ℃, and pH remains on 4～5 ℃; With sodium bicarbonate pH is transferred to 6～6.5 after reaction is finished, temperature maintenance is at 8～10 ℃.Reaction is reached home, and temperature is raised to 40 ℃, adds 5 parts of gacs, stirs 12～20min, filters, and dye solution directly carries out spraying drying, obtains the dyestuff (101) of following structural:
Dyestuff dyes cotton fibre for yellow, and every fastness is good.
Embodiment 2～15
Method with reference to embodiment 1 can obtain the listed yellowish-orange dyestuff of table 1.
Table 1
Embodiment 16
With 32 parts of 3-amino-N-[4-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide mixes making beating～60min with 350 parts of water, slowly drips 46 parts of 30% sodium nitrite solutions at 0～5 ℃, and under this temperature, stir and reach home until diazotization.
To contain 18.8 part 2, the aqueous solution of 4-diamino benzene sulfonic acid joins in the above-mentioned diazonium salt, carries out a coupling at～5 ℃, and pH remains on 3～4; After reaction is finished, add and carry out the secondary coupling by 28.1 parts of 4-diazonium salt that (beta-hydroxyethyl sulfone sulfate)-aniline is made, with sodium bicarbonate pH is transferred to 6～6.5, temperature maintenance is at 8～10 ℃.Reaction is reached home, and temperature is raised to 40 ℃, adds 5 parts of gacs, stirs 12～20min, filters, and dye solution directly carries out spraying drying, obtains the dyestuff (201) of following structural:
It is pale brown look that dyestuff dyes cellulosic fibre, has good degree of fixation.
Embodiment 17～23
Method with reference to embodiment 16 can obtain the listed yellowish-orange dyestuff of table 2.
Table 2
Embodiment 24
17.3 parts of Sulphanilic Acid are mixed making beating～60min with 150 parts of water, add 18.2 part 30% hydrochloric acid, drip 23 parts of 30% sodium nitrite solutions, under this temperature, stir and reach home until diazotization at 0～5 ℃.
To contain 15.2 part 3, the aqueous solution of 4-diaminobenzoic acid joins in the above-mentioned diazonium salt, carries out a coupling at～5 ℃, and pH remains on 3～4; After reaction is finished, add and carry out secondary and three couplings by 56.2 parts of 4-diazonium salt that (beta-hydroxyethyl sulfone sulfate)-aniline is made, with sodium bicarbonate pH is transferred to 6～6.5 gradually, temperature maintenance is at 8～10 ℃.Reaction is reached home, and temperature is raised to 40 ℃, adds 5 parts of gacs, stirs 12～20min, filters, and dye solution directly carries out spraying drying, obtains the dyestuff of following structural:
Embodiment 25～29
Method with reference to embodiment 24 can obtain the listed orange dye of table 3.
Table 3
Embodiment 30
With 32 parts of 4-amino-N-[3-(beta-hydroxyethyl sulfone sulfate)-phenyl] benzamide mixes making beating～60min with 350 parts of water, add 18 parts of 30% hydrochloric acid, slowly drip 23 parts of 30% sodium nitrite solutions at 0～5 ℃ then, under this temperature, stir and reach home until diazotization.
To contain 34.3 parts of H aqueous acids and join in the above-mentioned diazonium salt, and carry out a coupling at～5 ℃, pH remains on 2～3; After reaction is finished, add and carry out the secondary coupling by 28.1 parts of 4-diazonium salt that (beta-hydroxyethyl sulfone sulfate)-aniline is made, with sodium bicarbonate pH is transferred to 6～6.5, temperature maintenance is at 8～10 ℃.Reaction is reached home, and temperature is raised to 40 ℃, adds 5 parts of gacs, stirs 12～20min, filters, and dye solution directly carries out spraying drying, obtains the dyestuff (401) of following structural:
Embodiment 31～39
Method with reference to embodiment 30 can obtain the listed purplish blue look dyestuff of table 4.
Table 4
Embodiment 40～62
At 30 ℃ 5 parts of cotton fabrics are joined in 100 parts of water that contain 0.24 part of dyestuff (403), 0.06 part of dyestuff (102) and 6 parts of Sodium sulfate anhydrous.min(99), in 30min, be warmed up to 60 ℃, add 1.5 parts of yellow soda ash, and under this temperature, keep 45min; Take out DYED FABRICS, wash, soap, drying.The degree of fixation height of this composite dye, the dyeing residual liquid look shallow, and DYED FABRICS is a black, has good fastness.Dye composition shown in the table 5 has good performance equally, and its proportioning can be regulated in the proportional range according to the present invention's regulation as required.
Table 5
| Embodiment | Dyestuff (I) | Dyestuff (II) | Tone |
| 41 42 43 44 45 46 47 48 49 50 51 52 53 54 | 103 104 105 107 109 110 114 115 201 201 203 203 205 206 | 404 405 405 405 406 409 408 408 404 408 407 409 408 405 | Black black black black black black black black black black black black black black |
| 55 56 57 58 59 60 61 62 | 208 208 301 302 303 304 305 306 | 404 409 409 408 405 410 408 404 | Black black black black black black black black |
Embodiment 63～68
Method with reference to embodiment 30 can obtain the listed orchil of table 6.
Table 6
Embodiment 69～101
At 30 ℃ 5 parts of cotton fabrics are joined in 100 parts of water that contain 0.24 part of dyestuff (403), 0.06 part of dyestuff (102) and 6 parts of Sodium sulfate anhydrous.min(99), in 30min, be warmed up to 60 ℃, add 1.5 parts of yellow soda ash, and under this temperature, keep 45min; Take out DYED FABRICS, wash, soap, drying.The degree of fixation height of this composite dye, the dyeing residual liquid look shallow, and DYED FABRICS is a black, has good fastness.Dye composition shown in the table 7 has good performance equally.
Table 7
| Embodiment | Dyestuff (I) | Dyestuff (II) | Dyestuff (III) | Proportioning | Tone |
| 70 71 72 73 74 75 76 77 78 79 80 81 82 83 | 103 109 105 112 104 114 201 203 205 205 206 208 301 302 | 401 403 404 407 408 409 404 407 408 404 408 404 408 404 | 501 502 503 506 503 505 503 502 503 505 503 506 503 501 | 20∶68∶12 25∶65∶10 20∶70∶10 20∶68∶12 25∶65∶10 20∶68∶12 18∶12∶70 21∶11∶68 13∶17∶70 18∶12∶70 21∶11∶68 17∶11∶72 13∶17∶70 15∶75∶10 | Black black black |
| Embodiment | Dyestuff (I) | Dyestuff (II) | Dyestuff (III) | Proportioning | Tone |
| 84 85 86 87 88 | 302 302 303 304 305 | 407 408 407 409 410 | 503 503 501 504 502 | 16∶72∶12 18∶76∶6 18∶76∶6 20∶68∶12 16∶72∶12 | Black black |
| 89 90 91 92 93 94 95 96 97 98 99 100 101 | 307 102 107 113 205 208 203 207 302 301 304 305 306 | 410 404 407 410 408 408 407 404 408 407 408 409 408 | 505 501 504 502 503 503 501 503 503 504 502 505 504 | 20∶65∶15 51∶29∶19 48∶28∶24 45∶33∶22 52∶29∶19 49∶28∶23 48∶30∶22 49∶28∶23 52∶30∶18 51∶28∶19 48∶28∶24 45∶33∶22 52∶29∶19 | Black palm fibre palm fibre palm fibre palm fibre palm fibre palm fibre palm fibre palm fibre palm fibre palm fibre palm fibre palm fibre |
Embodiment 102
At 30 ℃ 5 parts of cotton fabrics are joined in 100 parts of water that contain 0.21 part of dyestuff (404), 0.035 part of dyestuff (205), 0.055 part of dyestuff (506) and 0.3 part of auxiliary agent (IVa), in 30min, be warmed up to 60 ℃, add 1.5 parts of yellow soda ash, and under this temperature, keep 45min; Take out DYED FABRICS, wash, soap, drying.The degree of fixation height of this composite dye, the dyeing residual liquid look shallow, and DYED FABRICS is a black, has good fastness.
Embodiment 103
51 parts of dyestuffs (205), 19 parts of dyestuffs (501), 28 parts of dyestuffs (404) and 50 parts of auxiliary agents (IVb) are mixed, and the dye composition dyeing cotton fabric that obtains obtains brown, has good dyeing ability and fastness.
Claims (5)
1. a high-concentration composite reactive dye is characterized in that: the dyestuff that contains one or more general formulas (I) in this composite dye;
W is hydrogen or carboxyl in the general formula (I);
When W=hydrogen, then U is SO
2Y or SO
3H, the structure of general formula (I) is corresponding to formula (Ia) or (Ib), wherein Y is CH
2CH
2OSO
3H, CH=CH
2Or Cl;
When the W=carboxyl, then U is D
5, the structure of general formula (I) can be expressed as (Ic)
The dyestuff that contains one or more general formulas (II) in this composite dye;
(II)
M is hydrogen, sodium, potassium or lithium;
The dyestuff that contains one or more general formulas (III) in this composite dye;
Wherein M is hydrogen, sodium, potassium or lithium;
The dyestuff that contains one or more general formulas (IV) in this composite dye, general formula (IV) are (IVa) or (IVb);
R wherein
9Be hydrogen, methyl, ethyl or benzyl; R
10Be methyl, propyl group or alkane hydroxyl; M is 1～2; N is 2～10.
2. according to a kind of high-concentration composite reactive dye of claim 1, it is characterized in that D in the composite dye
1～D
5Be equivalent to following groups (formula 1) or naphthalene sulfonic acid derivant,
R wherein
1And R
2Be the derivative of hydrogen, methyl, methoxyl group, sulfonic group, chlorine or benzanilide, formula (2);
R wherein
3And R
4Be hydrogen, methyl, methoxyl group, sulfonic group and chlorine; Z is hydrogen or SO
2Y, wherein Y is CH
2CH
2OSO
3H, CH=CH
2Or Cl.
3. according to a kind of high-concentration composite reactive dye of claim 1, it is characterized in that D in the composite dye
1～D
4At least contain a fibrous active radical.
4. according to a kind of high-concentration composite reactive dye of claim 1, R in the general formula (III)
5And R
6For hydrogen or contain C
1～C
4Alkyl; D
6And D
7For containing the anils of an active group at least, formula (3);
R wherein
7, R
8Be hydrogen, methyl, methoxyl group, sulfonic group or chlorine, Z is hydrogen or group SO
2Y, Y are CH
2CH
2OSO
3H, CH=CH
2Or Cl.
5. according to claim 1,2 or 3 described a kind of high-concentration composite reactive dyes, it is characterized in that: according to weight percent I: II: III=(5～55): (20～85): (0～25); (I+II+III): IV=(100～50): (0～50).
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100127464A CN101117449B (en) | 2007-09-04 | 2007-09-04 | High-concentration composite reactive dye |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100127464A CN101117449B (en) | 2007-09-04 | 2007-09-04 | High-concentration composite reactive dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101117449A true CN101117449A (en) | 2008-02-06 |
| CN101117449B CN101117449B (en) | 2012-05-16 |
Family
ID=39053715
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|---|---|---|---|
| CN2007100127464A Expired - Fee Related CN101117449B (en) | 2007-09-04 | 2007-09-04 | High-concentration composite reactive dye |
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