CN100503736C - Bisdiazo metal complex dye and its preparation method - Google Patents
Bisdiazo metal complex dye and its preparation method Download PDFInfo
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- CN100503736C CN100503736C CNB2006100590165A CN200610059016A CN100503736C CN 100503736 C CN100503736 C CN 100503736C CN B2006100590165 A CNB2006100590165 A CN B2006100590165A CN 200610059016 A CN200610059016 A CN 200610059016A CN 100503736 C CN100503736 C CN 100503736C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000434 metal complex dye Substances 0.000 title description 2
- 239000000975 dye Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 8
- 210000002268 wool Anatomy 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- -1 disazo metal complex Chemical class 0.000 abstract description 3
- 239000004677 Nylon Substances 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920001778 nylon Polymers 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical class [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 5
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical class NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YGNDWDUEMICDLW-UHFFFAOYSA-N 7-anilino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C=1C=C2C(O)=CC(S(O)(=O)=O)=CC2=CC=1NC1=CC=CC=C1 YGNDWDUEMICDLW-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- ZRRGOUHITGRLBA-UHFFFAOYSA-N stattic Chemical compound [O-][N+](=O)C1=CC=C2C=CS(=O)(=O)C2=C1 ZRRGOUHITGRLBA-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
This invention relates to a disazo metal complex dyestuff and its preparation method, the dyestuff said is displayed by formula (I), the method includes following procedures. Compound (II) is mixed with compound (III), pH value is adjusted to 6.0-10.0, then temperature is warmed to 60-90 degrees centigrade for agitation reaction, then the product is got after treatment. The acidic black metal complex dyestuff is propitious to color of wool and its blending, silk and nylon. Its color technique is simple and reliable, it is especially propitious to wool bulk fiber, tops low temperature coloration, the color gain ratio is high, sun-proof and moisture-proof fastness is good, it also propitious to coloration of auto interior decoration dry goods.
Description
(1) technical field
The present invention relates to a kind of tetrazo metallized dye and preparation method thereof.
(2) background technology
Black dyeing, the stamp that is mainly used in wool, silk and polyamide fibre of acid complexing can use separately and colorant match is used.Stipulate according to European Union: when acid metal complex dye was used for relevant dyeing keratin-fiber, dye liquor is discharged into the amount of handling in the waste water should be less than 7%, and promptly the dye uptake of metallized dye will surpass 93%.Present conventional acid black dye can't satisfy above requirement well, and mainly show: degree of fixation is relatively poor, causes poor performance such as water-fast, washable, perspiration resistance fastness, to cellulosic fibre, natural wool fiber and synthetic polyester fibers can not with aterrimus.Chinese patent ZL01802267.7 discloses a kind of asymmetric tetrazo metallized dye, and this dyestuff has good high color depth and fastness.
(3) summary of the invention
The object of the invention is to provide a kind of dyefastness height, tetrazo metallized dye that depth is good and preparation method thereof.
Described tetrazo metallized dye is suc as formula shown in (I),
R wherein
1, R
2, R
3, R
4Independent separately is hydrogen, nitro, sulfonic group, chlorine atom or sulfoamido.
Described R
1, R
3Be preferably sulfonic group separately, R
2, R
4Be preferably nitro separately.
The preparation method of tetrazo metallized dye of the present invention comprises the steps: formula (II) compound and formula (III) compound, transfers pH to 6.0～10.0, is warming up to 60～90 ℃ of stirring reactions, and aftertreatment promptly gets product;
R wherein
1, R
2, R
3, R
4Definition the same.
Preparation method of the present invention preferably includes following steps:
With formula (II) compound and formula (III) compound, transfer pH to 8.0, be warming up to 80 ℃ of stirring reactions 4 hours, saltout with the sodium-chlor of 15～20% slurry weight, cold filtration, concentrate drying promptly gets described tetrazo metallized dye.
The present invention also provides the preparation method of a kind of above-mentioned formula (III) compound, described formula (III) compound makes by following step: make its diazonium liquid by formula (IV) compound earlier, add the formula V compound again, transfer pH=9～12, carry out coupled reaction under stirring, promptly get described formula (III) compound; The weight ratio of its Chinese style (IV) compound and formula V compound is 0.4～0.6:1.
R wherein
1, R
2Definition the same.
The preparation method of above-mentioned formula (II) compound is well known to those skilled in the art, as can be make the diazonium compound of formula (VI) representative and beta naphthal carry out coupled reaction earlier (weight ratio is preferably 2.2～1.6:1), the control pH value is 8～9, obtain the azo-compound of formula (VII), be complexing under the condition of 4.0～3.4:1 again with azo-compound and chromium sesquioxide, make chromium complex suc as formula (II) in weight ratio;
Erie black metallized dye of the present invention is applicable to the dyeing of wool and blending thereof, silk, polyamide fibre, dyeing is easy to be reliable, is particularly suitable for the low temperature dyeing of loose wool fiber, wool top, the degree of fixation height, sun-proof and moisture-proof fastness are good, also are applicable to the dyeing of internal decoration textile of automobile.
(4) embodiment
Further specify the present invention with specific embodiment below, but protection scope of the present invention is not limited to this.
Embodiment 1
The first step, with 6-nitro-1,2,4-acid oxysome and beta naphthal carry out coupling:
With 20 gram 6-nitros-1,2,4-acid oxysome shown in (VI-a), adds the making beating of 60ml water, on the rocksly is cooled to 8 ℃, and the liquid caustic soda 10ml with 30% regulates material liquid PH value to the Congo red indigo plant that do not show.The beta naphthal that in the water of 7ml, adds 10.5 grams, adding 8.5ml content is 30% liquid caustic soda, is warming up to 80 ℃, make the beta naphthal dissolving, this solution is cooled to 30 ℃, flow into above-mentioned 6-nitro-1 then, 2, in the 4-acid oxysome solution, under vigorous stirring, in 1 hour, be warming up to 40 ℃, with the salt acid for adjusting pH value is 8.5 to carry out coupled reaction, after reaction finishes, filter, wash, dry, make conjugates dry product 26 grams shown in the following formula (VII-a).
In second step, conjugates and chromic oxide that the first step is made carry out the 1:1 complexing:
Get the there-necked flask of 250ml, add water 150ml, chromium sesquioxide 7 grams were warmed up to 102 ℃ in 1 hour, slowly add the above-mentioned conjugates dry product that makes, and added formic acid 40ml, reacted 3 hours, formed the chromium complex as shown in the formula the 1:1 shown in (II-a).
In the 3rd step, 2-amino-4-nitrophenols and phenyl J acid are carried out coupling:
With content be 99% as shown in the formula 2-amino-4 nitrophenols shown in (IV-a) 10.8 gram, in 60ml water and 20ml technical hydrochloric acid, pull an oar, on the rocksly be cooled to 6 ℃, in 15 minutes, drip the 14ml aqueous solution that contains 5.2 gram Sodium Nitrites and carry out diazotization reaction, keep 10 ℃ of diazotization temperature, after dripping Sodium Nitrite, stirred 40 minutes, destroy excessive Sodium Nitrite with thionamic acid.
With content be 91.15% as shown in the formula the phenyl J shown in (V-a) acid 24.4 grams, in the water of 110ml, pull an oar, the liquid caustic soda that adds 20 grams 30%, stirring and dissolving, flow in the diazonium liquid of above-mentioned 2-amino-4 nitrophenols, regulating pH value with 30% liquid caustic soda is 9.0 to react, and reacts completely until diazonium liquid, promptly gets the conjugates of following formula (III-a).
The 4th step, complexing for the second time
Second complex compound and the 3rd conjugates that goes on foot the formula (III-a) that makes that goes on foot the formula (II-a) that obtains mixed, regulate PH to 8.0, be warming up to 80 ℃, stirred 4 hours, reaction is saltoutd cold filtration after finishing with the sodium-chlor of 15% slurry weight, concentrate drying makes the black dyes of following formula (I-a).
Embodiment 2
Be prepared according to embodiment 1 identical method, different is to replace above-mentioned (VI-a) with following formula (VI-b), makes the Monoazo compound of formula (VII-b), the chromium complex of formula (II-b), the black dyestuff of azo metal complexed acidic of formula (I-b) in succession.
Embodiment 3～6
According to the preparation method of embodiment 1, use monoazo complex compound and the azo-compound listed in the following table 1, make the black dyestuff of azo metal complexed acidic of corresponding construction.
Table 1
Embodiment 7
Take by weighing the dyestuff that 1 gram the foregoing description 1～6 makes, place the beaker of 150ml, add 85 ℃ distilled water 100ml, stirring is fully dissolved it, it is mixed with dye level again and is 2%, bath raio is the dye liquor of 1:50, puts into nylon cloth, dye vat normal temperature is placed in the proof press, be heated to 40 ℃, be incubated 15 minutes, the speed with 1 ℃/min is warming up to 100 ℃ then, be incubated 30 minutes, dye to finish dye vat is taken out, cooling 10-15min takes out and dyes thing through the washing oven dry.Adopt the method for determining among GB/T3920-1997, GB/T 3921-1997, GB/T 5713-1997, the GB/T 8427-1998 to test its colour fastness to rubbing, colour fastness to perspiration, color fastness to water.Test result sees Table 2.
Table 2
| Test event | Color | Rub resistance | Anti-soaping | Water-fast soaking | Sun-resistant |
| Embodiment 1 | Pitch black | 5 grades | 5 grades | 5 grades | 6 |
| Embodiment 2 | Pitch black | 5 grades | 4～5 grades | 4～5 grades | 6 |
| Embodiment 3 | Pitch black | 5 grades | 4～5 grades | 4～5 grades | 6 |
| Embodiment 4 | Pitch black | 5 grades | 4～5 grades | 4～5 grades | 6 |
| Embodiment 5 | Pitch black | 5 grades | 4～5 grades | 4～5 grades | 6 |
| Embodiment 6 | Pitch black | 5 grades | 4～5 grades | 4～5 grades | 6 |
Can find out that from the said determination result the every fastness of erie black metallized dye provided by the invention is good.
Claims (5)
1, a kind of tetrazo metallized dye suc as formula (I),
R wherein
1, R
2, R
3, R
4Independent separately is hydrogen, nitro, sulfonic group or chlorine atom.
2, tetrazo metallized dye as claimed in claim 1 is characterized in that described R
1, R
3The sulfonic group of respectively doing for oneself, R
2, R
4The nitro of respectively doing for oneself.
3, the preparation method of the described tetrazo metallized dye of a kind of claim 1 comprises the steps: formula (II) compound and formula (III) compound, transfers pH to 6.0～10.0, is warming up to 60～90 ℃ of stirring reactions, and aftertreatment promptly gets product;
R wherein
1, R
2, R
3, R
4Definition with claim 1.
4, the preparation method of tetrazo metallized dye as claimed in claim 3 is characterized in that comprising the steps:
With formula (II) compound and formula (III) compound, transfer pH to 8.0, be warming up to 80 ℃ of stirring reactions 4 hours, saltout with the sodium-chlor of 15～20% slurry weight, cold filtration, concentrate drying promptly gets described tetrazo metallized dye.
5, as the preparation method of claim 3 or 4 described tetrazo metallized dyes, it is characterized in that described formula (III) compound makes by following step: make its diazonium liquid by formula (IV) compound earlier, add the formula V compound again, coupled reaction is carried out in stirring, transfers pH=9～12 promptly to get institute's formula (III) compound; The weight ratio of its Chinese style (IV) compound and formula V compound is 0.4～0.6:1;
R wherein
1, R
2Definition with claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100590165A CN100503736C (en) | 2006-01-26 | 2006-02-24 | Bisdiazo metal complex dye and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610049370 | 2006-01-26 | ||
| CN200610049370.X | 2006-01-26 | ||
| CNB2006100590165A CN100503736C (en) | 2006-01-26 | 2006-02-24 | Bisdiazo metal complex dye and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1831045A CN1831045A (en) | 2006-09-13 |
| CN100503736C true CN100503736C (en) | 2009-06-24 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712815B (en) * | 2009-11-23 | 2012-08-22 | 浙江大井化工有限公司 | Environment-friendly acid black dye composition |
| CN102796400B (en) * | 2011-05-25 | 2013-12-04 | 上海雅运纺织化工股份有限公司 | Yellow azo metallized dye composition, method and application thereof |
| CN102516795B (en) * | 2011-12-09 | 2014-04-02 | 青岛双桃精细化工（集团）有限公司 | Preparation method of blue dye |
| CN104559314B (en) * | 2014-12-12 | 2017-01-25 | 青岛双桃精细化工（集团）有限公司 | Black dye composition and application thereof in polyamide microfiber leather dyeing |
| CN105385186B (en) * | 2015-10-19 | 2017-03-29 | 广州市纬庆化工科技有限公司 | A kind of resistance to migration orchil, preparation method and application |
| CN105566176B (en) * | 2015-11-26 | 2018-06-22 | 浙江奇彩环境科技股份有限公司 | A kind of production technology of the sour oxysome of improved 6- nitros -1,2,4 |
| CN105623300B (en) * | 2016-01-05 | 2017-08-01 | 湖北省纬庆高分子科技有限公司 | A kind of preparation method of complex dyestuff |
| CN105733292A (en) * | 2016-01-28 | 2016-07-06 | 江苏盛吉化工有限公司 | Preparation method of acid black ACE |
| CN108912724B (en) * | 2018-05-31 | 2020-11-10 | 上海青石化学有限公司 | Asymmetric metal complex black dye and preparation method thereof |
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