CN104387796A - Reactive dye and preparation method thereof - Google Patents
Reactive dye and preparation method thereof Download PDFInfo
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- CN104387796A CN104387796A CN201410505099.0A CN201410505099A CN104387796A CN 104387796 A CN104387796 A CN 104387796A CN 201410505099 A CN201410505099 A CN 201410505099A CN 104387796 A CN104387796 A CN 104387796A
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- active dye
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000985 reactive dye Substances 0.000 title abstract description 7
- 239000000047 product Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000006277 sulfonation reaction Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 abstract description 3
- 229920000742 Cotton Polymers 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 abstract description 2
- 241000208202 Linaceae Species 0.000 abstract 1
- 235000004431 Linum usitatissimum Nutrition 0.000 abstract 1
- 210000002268 wool Anatomy 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010009 beating Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a reactive dye and a preparation method thereof. The structural formula of the reactive dye is shown in the specification. The prepared blue reactive dye is improved in color fixing rate, alkali resistance and solarization fastness and also improved in solubility, and has the obvious advantage that the alkali resistance of the blue reactive dye is capable of satisfying the strong-basicity requirement of cold pad batch. The blue reactive dye is applicable to dyeing of cotton, flax and wool fiber.
Description
Technical field
The invention belongs to dye chemical industry technical field, relate to dyestuff chemistry structure and preparation method thereof, particularly relate to bright blue reactive dyestuffs structure and preparation method thereof.
Background technology
Reactive dyestuffs bright in color light, wet fastness are good, have its performance advantage, but also have weak point, and degree of fixation, alkali resistance and light fastness are general lower, and particularly blue Series Reactive Dyes, this deficiency is comparatively obvious.Therefore blue active dye containing heterocycle color bodies is in succession developed for performances such as degree of fixation, alkali resistance and light fastnesss abroad, but alkali resistance still cannot meet cold pad--batch requirement, and solubleness is affected, blue active dye prepared by the present invention not only increases degree of fixation, alkali resistance and light fastness (light fastness reaches 6-7 level), also improve solubleness, with the obvious advantage is alkali resistance, can meet the requirement of cold pad--batch strong basicity.
US 4629788 discloses a kind of naphthalene nucleus β bit amino derivative dye, a kind of naphthalene nucleus α of exploitation bit amino derivative of novelty of the present invention, performance advantage is more obvious, alkali resistance and light fastness have again new raising, go for the high density strong basicity requirement of cold-rolling heap staining completely, light fastness comparatively β bit derivant is high half grade, and color development degree and degree of fixation exceed more than 8%, and the present invention is the ideal blue dyestuff of alternative Reactive Blue 19 100 in addition.
Another innovative point of the present invention is sulfonic introducing, is not to introduce in advance on naphthalene derivative, but introduces in dyestuff color bodies building-up process, i.e. esterification, closed loop, sulfonation, with having bathed, reduce the complexity of technique process greatly.
Summary of the invention
The object of this invention is to provide a kind of blue active dye and preparation method thereof.Blue active dye prepared by the present invention not only increases degree of fixation, alkali resistance and light fastness, also improves solubleness, and with the obvious advantage is alkali resistance, can meet the requirement of cold pad--batch strong basicity.
The technical solution used in the present invention is:
A kind of blue active dye, the structural formula of this blue active dye is as shown in formula I or formula II:
Present invention also offers the preparation method of above-mentioned blue active dye, comprise the steps:
(1) condensation
In 1000ml beaker, add end water, then add
in wherein a kind of, be warmed up to 60 DEG C, add tetrachlorobenzoquinone gradually, use NaHCO
3regulate pH=6-8, joining day general control is in 0.5-2 hour, and temperature control 55-65 DEG C, after reaction terminates, is cooled to less than 30 DEG C, and filter, filter cake washes with water 2-3 time, in 60-80 DEG C of drying, obtains condenses dry product;
(2) closed loop, esterification, sulfonation
In 500ml four-hole bottle, add the oleum of 20% concentration, slowly add above-mentioned condenses dry product, with cooling water temperature, charge temperature≤30 DEG C; Finish maintenance and slowly add Potassium Persulphate (K again in 2 hours
2s
2o
8) control temperature 30-60 DEG C, feed time 3-8 hour, finishes, and keeps 2 hours, then adds liquid SO
3, and keep 2-4 hour in 60-100 DEG C, and obtain sulfonation reaction liquid, by below this sulfonation reaction liquid cooling water temperature to 30 DEG C, to be diluted.
(3) dilute, neutralize
Be diluted in mixture of ice and water by above-mentioned sulfonation reaction liquid, temperature≤0 DEG C, dilution is finished and is added KCl and saltout, and saltout time 2-3 hour, filters, and filter cake use water is pulled an oar, and uses NaHCO
3adjust pH=5-7, continue with KCl saltout, filter, filtration cakes torrefaction obtains finished product.
The beneficial effect that the present invention has:
Blue active dye prepared by the present invention not only increases degree of fixation, alkali resistance and light fastness, also improves solubleness, and with the obvious advantage is alkali resistance, can meet the requirement of cold pad--batch strong basicity.Blue active dye of the present invention is applicable to the dyeing of cotton, fiber crops, hair fibre.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1
A kind of blue active dye, the structural formula of this blue active dye is for shown in formula I:
The preparation method of this formula I blue active dye, comprises the steps:
Water 65g at the bottom of 500ml is added in 1000ml beaker
be warmed up to 60 DEG C, add tetrachlorobenzoquinone 29.9g gradually, use NaHCO
3regulate pH=6-8, joining day general control at 1 hour, temperature control 55-65 DEG C.After reaction terminates, be cooled to less than 30 DEG C, filter, filter cake washes 3 times with water, in 60-80 DEG C of drying, obtains condenses dry product.
In 500ml four-hole bottle, add the oleum 300g of 20% concentration, slowly add above-mentioned condenses dry product 70.7g, with cooling water temperature, charge temperature≤30 DEG C.Finish maintenance 2 hours, start slowly to add 54gK
2s
2o
8control temperature 30-60 DEG C, feed time 4 hours, finishes, and keeps 2 hours.16gSO is dripped in this four-hole bottle
3liquid, and keep 2 hours in 60-100 DEG C, with below cooling water temperature to 30 DEG C, obtain sulfonation reaction liquid, to be diluted.
Above-mentioned sulfonation reaction liquid is diluted in mixture of ice and water, temperature≤0 DEG C.Dilution is finished the KCl adding cumulative volume 20% and is saltoutd (diluent cumulative volume V*10%=KCl add-on), stirs and saltouts 3 hours.Filter, filter cake 400ml water making beating, uses NaHCO
3adjust pH=5-7, the KCl adding liquor capacity 7% saltouts 3 hours, and filter, filter cake, in 60-80 DEG C of drying, obtains formula III blue active dye.
The performance of the dyestuff of embodiment 1 is as follows:
Embodiment 2
By in embodiment 1
replace with
Other steps, with embodiment 1, namely obtain the blue active dye shown in following formula II:
The performance of the dyestuff of embodiment 2 is as follows:
Embodiment 3
A kind of dyestuff intermediate, the structural formula of this dyestuff intermediate is:
The preparation method of this dyestuff intermediate, comprises the steps:
Raw material used is 4-sulfonic acid-naphthalidine-8-hydroxyl (CAS:83-64-7), is commonly called as S acid (structure b-1).
1). acetylize: be added to the water 1 part of 4-sulfonic acid-naphthalidine-8-hydroxyl making beating, is warmed up to 30-40 DEG C, drips 15% (quality) sodium carbonate, regulates pH=6-6.5, makes it to dissolve gradually; The diacetyl oxide of 1.2 parts is added drop-wise in above system in 15 minutes, keeps temperature 30-40 DEG C, drip off maintenance 1 hour; After chromatographic determination complete reaction, cool to room temperature; Product is separated out in a large number, stirs 1 hour; Filtration obtains filter cake, filter cake is placed in 60 DEG C of baking boxs and dries and obtain dry product;
2). chlorosulphonation: add chlorsulfonic acid 5 parts in the four-hole bottle of drying, water bath heat preservation less than 20 DEG C, slowly adds step 1) product dry product 1 part; Be warming up to 25-30 DEG C, keep 4 hours; After liquid chromatogram measuring complete reaction, reaction solution is slowly added drop-wise to ice in the beaker that mixture of ice and water is housed and analyses, temperature remains at less than 0 DEG C; Filtration obtains filter cake;
3). reduction: 1.3 parts of sodium bisulfites are added to the water dissolving, pH=7.5-8 is regulated with NaOH (30% quality), at ice-water bath keeps temperature 15-20 DEG C, by 1 part of step 2) product slowly joins in system, keeps system pH=7-8 with NaOH (30% quality); Add, Keep agitation 1 hour, keep pH=7.5-8, temperature 20-25 DEG C; Add NaCl to saltout, product is separated out in a large number; Filtration obtains filter cake;
4). hydroxyethylation: by step 3) product 1 part of use water making beating, be warmed up to 55-60 DEG C, make it to dissolve completely, at 60 DEG C, in system, pass into ethylene oxide gas, use H simultaneously
2sO
4(30% quality) regulates pH=6.8-7.2. to continue to pass into 18-20 hour, and system solution has solid particulate to separate out gradually, is generation product; After reacting completely with liquid chromatogram measuring, cool to 40 DEG C, filter, it is hydroxyethyl thing that washing obtains product;
5) being hydrolyzed: by 1 part of step 4) product hydroxyethyl thing is added to the water making beating, regulates pH=9-10 with NaOH (30% quality); Be heated to 70-75 DEG C, keep 1.5h; With HCl (30% quality) by pH regulator to 6.5-7, cryosel water-bath is cooled to 0-5 DEG C, and product is separated out in a large number; Filter filter cake is dyestuff intermediate structure b-2.
Number described in embodiment 3 is molfraction.
Embodiment 4
4-sulfonic acid in embodiment 3-naphthalidine-8-hydroxyl is replaced with 7-sulfonic acid-naphthalidine-5-hydroxyl, and other are with embodiment 3, namely corresponding obtained:
Claims (2)
1. a blue active dye, is characterized in that: the structural formula of this blue active dye is as shown in formula I or formula II:
2. the preparation method of blue active dye described in claim 1, is characterized in that: comprise the steps:
(1) condensation
In 1000ml beaker, add end water, then add
in wherein a kind of, be warmed up to 60 DEG C, add tetrachlorobenzoquinone gradually, use NaHCO
3regulate pH=6-8, joining day general control is in 0.5-2 hour, and temperature control 55-65 DEG C, after reaction terminates, is cooled to less than 30 DEG C, and filter, filter cake washes with water 2-3 time, in 60-80 DEG C of drying, obtains condenses dry product;
(2) closed loop, esterification, sulfonation
In 500ml four-hole bottle, add the oleum of 20% concentration, slowly add above-mentioned condenses dry product, with cooling water temperature, charge temperature≤30 DEG C; Finish maintenance and slowly add Potassium Persulphate (K again in 2 hours
2s
2o
8) control temperature 30-60 DEG C, feed time 3-8 hour, finishes, and keeps 2 hours, then adds liquid SO
3, and keep 2-4 hour in 60-100 DEG C, and obtain sulfonation reaction liquid, by below this sulfonation reaction liquid cooling water temperature to 30 DEG C, to be diluted.
(3) dilute, neutralize
Be diluted in mixture of ice and water by above-mentioned sulfonation reaction liquid, temperature≤0 DEG C, dilution is finished and is added KCl and saltout, and saltout time 2-3 hour, filters, and filter cake use water is pulled an oar, and uses NaHCO
3adjust pH=5-7, continue with KCl saltout, filter, filtration cakes torrefaction obtains finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410505099.0A CN104387796B (en) | 2014-09-26 | 2014-09-26 | A kind of reactive dye and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410505099.0A CN104387796B (en) | 2014-09-26 | 2014-09-26 | A kind of reactive dye and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN104387796A true CN104387796A (en) | 2015-03-04 |
| CN104387796B CN104387796B (en) | 2019-01-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB815840A (en) * | 1955-11-23 | 1959-07-01 | Cassella Farbwerke Mainkur Ag | New sulphur dyestuffs of the dioxazine series |
| EP0234778A2 (en) * | 1986-02-17 | 1987-09-02 | Sumitomo Chemical Company, Limited | Dioxazine compound having vinylsulfone type fiber reactive group |
| JPH0617047A (en) * | 1992-06-30 | 1994-01-25 | Sanyo Electric Co Ltd | Organic electroluminescent element |
| US5518825A (en) * | 1993-09-20 | 1996-05-21 | Pioneer Electronic Corporation | Organic electroluminescent device |
| CN102504585A (en) * | 2011-09-28 | 2012-06-20 | 天津德凯化工股份有限公司 | Blue active dye, preparation method and application thereof |
-
2014
- 2014-09-26 CN CN201410505099.0A patent/CN104387796B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB815840A (en) * | 1955-11-23 | 1959-07-01 | Cassella Farbwerke Mainkur Ag | New sulphur dyestuffs of the dioxazine series |
| EP0234778A2 (en) * | 1986-02-17 | 1987-09-02 | Sumitomo Chemical Company, Limited | Dioxazine compound having vinylsulfone type fiber reactive group |
| JPH0617047A (en) * | 1992-06-30 | 1994-01-25 | Sanyo Electric Co Ltd | Organic electroluminescent element |
| US5518825A (en) * | 1993-09-20 | 1996-05-21 | Pioneer Electronic Corporation | Organic electroluminescent device |
| CN102504585A (en) * | 2011-09-28 | 2012-06-20 | 天津德凯化工股份有限公司 | Blue active dye, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN104387796B (en) | 2019-01-22 |
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Effective date of registration: 20230131 Granted publication date: 20190122 |