CN108530940A - Blue K-type reactive dye and preparation method thereof - Google Patents
Blue K-type reactive dye and preparation method thereof Download PDFInfo
- Publication number
- CN108530940A CN108530940A CN201810607217.7A CN201810607217A CN108530940A CN 108530940 A CN108530940 A CN 108530940A CN 201810607217 A CN201810607217 A CN 201810607217A CN 108530940 A CN108530940 A CN 108530940A
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- Prior art keywords
- blue
- indigoidine
- condensation product
- reactive dye
- dyestuffs
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- GFRXAFYFWFQCFS-UHFFFAOYSA-N OS(C(C=CC1)=CC1Nc1nc(Cl)nc(Cl)n1)(=O)=O Chemical compound OS(C(C=CC1)=CC1Nc1nc(Cl)nc(Cl)n1)(=O)=O GFRXAFYFWFQCFS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
Abstract
The invention discloses a kind of blue K-type reactive dye, general structure is：
Description
Technical field
The present invention relates to a kind of blue K-type reactive dye and preparation method thereof.
Background technology
2015, the one group of researcher led by Jixun doctors Zhan of the state university of Utah, U.S.A utilized large intestine bar
Bacterium is manufactured that a kind of referred to as bipseudoindoxyl dye of Indigoidine, and realizes scale volume production.The indigo dyes of Indigoidine
There is material pure blue color can serve as the coloring agent in food, beverage or cosmetics after further purified treatment.
The blue natural dye obtains more and more extensive concern due to the characteristics such as nontoxic, pollution-free in textile industry.However, should
There are two primary amine groups (- NH in dye structure2), oxidation resistent susceptibility and heat resistance are poor, can be taken off quickly under the conditions of boiling is boiled
Blue is gone, brown materials are oxidized to.In addition, the dissolubilities of Indigoidine in a solvent are poor, only have in DMF and DMSO
There is smaller solubility, it is difficult to which dyeing is realized using aqueous medium.Therefore, carried out it is structurally-modified be possible to improve dyestuff it is molten
The dye species with practical value are made in Xie Xing, oxidative resistance and heat resistance.
Cotton fabric is also known as cotton, is using cotton yarn as the woven fabric of raw material.Cotton fabric is become most with excellent wearability
One of common fabric, is widely used in garment material, drapery and TECHNICAL FABRIC.Cotton is most popular clothes and home textile
Fabric.Multi-functional, soft, ventilative, moisture absorption, the comfort of annual dress, function admirable and endurable only cotton enjoy great popularity
The main reason for.Cotton fiber is only second to terylene in the annual consumption of textile industry at present.
Reactive dye are also known as chemically-reactive dyes, are a kind of new type water-solubility dyestuff occurred the 1950s, activity dye
Containing the active group (such as chloro s-triazine structure) that can react with the hydroxyl in cotton fiber in material molecule, when dyeing with it is fine
Dimension generates covalent bond, generates " dye-fibre " compound.Reactive dye have it is bright-colored, equalization is good, colouring method letter
Just, the features such as dyefastness is high, and chromatography is complete and cost is relatively low, be mainly used in the fibers such as cotton, fiber crops, viscose, silk, wool and
The dyeing of its blended fabric and stamp.
Cotton fiber may be used reactive dye and realize dyeing, and obtain preferable moisture resistant fastness, wherein a chlorine equal three
Piperazine type reactive dye to cotton fiber color fixing temperature close to 90 DEG C, it is more demanding to the heat resistance of dyestuff.
Invention content
The technical problem to be solved in the present invention is to provide a kind of blue K-type reactive dye and preparation method thereof, use this kind
Dyestuff can realize the efficient dyeing to cotton fiber in aqueous systems, and improve the oxidative resistance and heat resistance of dyestuff, in turn
Improve its sunlight fastness on cotton fiber.
In order to solve the above technical problem, the present invention provides a kind of blue K-type reactive dye, general structure is as follows：
Note：Contain s-triazine group and water soluble group (- SO in its molecular structure3H)。
The present invention goes back while providing the preparation method of above-mentioned novel blue K-type reactive dye, uses Indigoidine
Dyestuff, Cyanuric Chloride are reacted with the condensation product of aminobenzenesulfonic acid, specifically include following steps：
1), Indigoidine dyestuffs are dispersed in water, obtain dyestuff suspension (that is, dye dispersion liquid)；
It after the condensation product of Cyanuric Chloride and aminobenzenesulfonic acid is dissolved in water, is added into above-mentioned dyestuff suspension, then adds
Enter the potassium carbonate as acid binding agent, 1~6hr is reacted at 40-60 DEG C；
The Indigoidine dyestuffs：The condensation product of Cyanuric Chloride and aminobenzenesulfonic acid：Potassium carbonate=1:2:1 mole
Than；
The structural formula of the Indigoidine dyestuffs is：
The condensation product of the Cyanuric Chloride and aminobenzenesulfonic acid is(Cyanuric Chloride with to amino
The condensation product of benzene sulfonic acid),(condensation product of Cyanuric Chloride and metanilic acid).
2) reaction solution obtained by step 1), is adjusted pH value (to adjust for 4~6% HCl solution using mass concentration
Section) to 1~2, filtering, filtration cakes torrefaction obtains blue K-type reactive dye.
The improvement of the preparation method of blue K-type reactive dye as the present invention, in the step 1)：
It is first that Indigoidine dyestuffs is levigate to the sieve that can cross 300 mesh；Then it is contaminated according to 0.01mol Indigoidine
The solid-liquid ratio for expecting adapted 20 ± 5mL water, will be levigate after Indigoidine dyestuffs be scattered in, obtain dyestuff suspension；
According to the solid-liquid ratio of 0.02mol Cyanuric Chlorides and condensation product adapted 20 ± 5mL water of aminobenzenesulfonic acid, by three polychlorostyrene
The condensation product of cyanogen and aminobenzenesulfonic acid is dissolved in water.
The preparation method of blue K-type reactive dye as the present invention is further improved：
In the step 2), filter cake is first subjected to pickling (per 100~200ml of 0.01mol Indigoidine dyestuff adapteds
A concentration of 4~6% aqueous hydrochloric acid solution carries out pickling), re-dry (50 ± 5 DEG C of dryings to constant weight) obtains blue K-type activity dye
Material.
When the condensation product of Cyanuric Chloride and aminobenzenesulfonic acid is selectedWhen, the blue K-type of gained is lived
The structural formula of property dyestuff is：
When the condensation product of Cyanuric Chloride and aminobenzenesulfonic acid is selectedWhen, the blue K-type of gained
The structural formula of reactive dye is：
The condensation product of Cyanuric Chloride and aminobenzenesulfonic acid's
Preparation method is known technology, such as can be prepared in accordance with the following steps：
5g trash ices are added in 250mL three-necked flasks, 3.66g (20mmol) three is added in 25mL acetone under agitation
Polychlorostyrene cyanogen, is sufficiently stirred in ice-water bath.After mixing, 20mmol p-aminobenzene sulfonic acid or metanilic acid are added for solution
Enter reaction in 5% sodium carbonate liquor 20ml to clarify and be slowly dropped in above-mentioned three-necked flask to solution.In reaction process
Keep system pH 4~5 with 5% sodium carbonate liquor, in 0 DEG C or so reaction time 2h.After the completion of reaction under condition of ice bath
5mol/L HCl are slowly added dropwise, pH value of solution is adjusted to 1.Filtered after standing 0.5h, obtained solid, that is, corresponding for Cyanuric Chloride with
The condensation product of aminobenzenesulfonic acid
The present invention introduces one chloro-s-triazine structure of electrophilic active group on Indigoidine dyestuff amino structures, together
When introduce water soluble group (- SO3H), to be water-soluble reactive colour by water-insoluble Indigoidine modifications, make
This kind of dyestuff has higher solubility and reactivity in water, and improves the sunlight fastness of dyestuff itself.
The present invention develops a kind of blue K-type reactive dye, and this kind of dyestuff has good water solubility, and deposits in the structure
It can realized in aqueous systems solid to the upper dye of cotton fiber with a chloro-s-triazine active group of cotton fiber hydroxyl reaction
Color.In addition, the suction of s-triazine structure can electrically reduce the electronics in Indigoidine dye matrix structures on amino N atom
Cloud density promotes the oxidative resistance and heat-resistant stability of dyestuff.This kind of Dyestuff synthesis is simple for process, is contaminated by Indigoidine
Further condensation can be prepared by material with the condensation product of Cyanuric Chloride and aminobenzenesulfonic acid.By the blue K-type activity dye developed
Material has excellent dyefastness, application prospect extensive in cotton fiber.
Description of the drawings
Fig. 1 is dyeing curve graph.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1, a kind of preparation method of blue K-type reactive dye, follow the steps below successively：
1), by after Indigoidine dyestuff the mortars levigate sieve of 300 mesh (can cross), equipped with blender, thermometer
In there-necked flask, 0.01mol levigate Indigoidine dyestuffs and 20mL water is added, stirring forms dispersion liquid (dyestuff suspension),
For use；
2) it, will be added after the condensation product and 20ml water mixed dissolutions of 0.02mol Cyanuric Chlorides and p-aminobenzene sulfonic acid again
It states in dye dispersion liquid, 0.01mol potassium carbonate is then added as acid binding agent, reacts 6hr at 40 DEG C；
The condensation product of the Cyanuric Chloride and p-aminobenzene sulfonic acid is
3) the HCl solution adjusting pH that 5% (quality %), after completion of the reaction, is added in reaction solution is 1, makes blue product
It is precipitated；After filtering, filter cake is carried out pickling, and (a concentration of 5% aqueous hydrochloric acid solution carries out pickling, and each dosage is 50ml, altogether
Pickling 3 times) and it is dry (50 DEG C of dryings to constant weight), obtain blue K-type reactive dye.
The structural formula of the blue K-type reactive dye is as follows：
That is, for above structure general formula, in formula：Sulfonic group is located at imino group contraposition.
1H NMR(400MHz,DMSO-d6)：δ10.05(s,2H),7.68(d,4H),6.74(d,4H),6.42(s,2H),
4.0 (m,4H)；ESI MS (m/z, %):815.01([M-H]-,100)。
Embodiment 2, a kind of blue K-type reactive dye and preparation method thereof, follow the steps below successively：
1), by Indigoidine dyestuff mortars it is levigate after, in the there-necked flask equipped with blender, thermometer, be added
The Indigoidine dyestuffs and 20mL water that 0.01mol is levigate, stirring form dispersion liquid, for use；
2) it, will be added after the condensation product and 20ml water mixed dissolutions of 0.02mol Cyanuric Chlorides and metanilic acid again
It states in dye dispersion liquid, 0.01mol potassium carbonate is then added as acid binding agent, reacts 1hr at 60 DEG C；
The condensation product of Cyanuric Chloride and metanilic acid is
3) the HCl solution adjusting pH that 5%, after completion of the reaction, is added in reaction solution is 1, and blue product is made to be precipitated；Filtering
Afterwards, filter cake is subjected to pickling (a concentration of 5% aqueous hydrochloric acid solution carries out pickling, and each dosage is 50ml, pickling 3 times altogether)
With drying (50 DEG C of dryings to constant weight), blue K-type reactive dye are obtained.
The structural formula of the blue K-type reactive dye is as follows：
That is, for above structure general formula, in formula：Sulfonic group is located at imino group meta position.
1H NMR(400MHz,DMSO-d6)：δ10.03(s,2H),7.29(m,4H),7.13(s,2H),6.50(d,2H),
6.42 (s,2H),4.0(m,4H)；ESI MS (m/z, %):815.01([M-H]-,100)。
Illustrate application of the blue K-type reactive dye of the present invention in cotton fiber dyeing below by experiment.
Experiment 1 takes the blue K-type reactive dye that above-described embodiment synthesizes by following technique to cotton fiber dyeing：
Blue K-type reactive dye 2%owf, peregal 2g/L, NaCl 25g/L, 60 DEG C of dyeing temperature, time 30min；
Alkaline agent Na3PO412g/L, 90 DEG C of color fixing temperature, fixation time 30min；Bath raio 1：50.
It is as shown in Figure 1 to dye curve.
After dyeing, dyeing cloth specimen is taken out, washing, merges dyeing residual liquid and cleaning solution, constant volume survey its absorbance, utilizes
Lambert-Beer's law solves the dye-uptake and degree of fixation of dyestuff.
Above-mentioned dyeing cloth specimen is used into national standard《The assay method of reactive dyeing coloured light and intensity》(GB/T
2387-1980) dyeing post-processing after, obtain its color fastness to water, resistance to dry fastness, wet rubbing fastness, resistance to distillation color,
Light fastness.Specific acquired results are as described in Table 1.
Table 1
Comparative example 1 makes the condensation product of Cyanuric Chloride and p-aminobenzene sulfonic acid in embodiment 1 intoMole is constant, remaining is equal to embodiment.
Products therefrom is
Compared with Example 1, the alkyl introduced on Indigoidine dyestuffs amino can not effectively reduce the electronics of N atoms
Cloud density, light fastness are substantially less than embodiment 1.
Comparative example 2 makes the condensation product of Cyanuric Chloride and p-aminobenzene sulfonic acid in embodiment 1 into
Mole is constant, and solvent for use is changed to DMF, remaining is equal to embodiment.
Products therefrom is
Performance is as described in Table 1 obtained by above-mentioned 2 products.
Since water soluble group being not present in the dye structure, dyestuff dissolubility in aqueous systems is poor, causes that dye can not be gone up
Cotton fiber, dye-uptake and degree of fixation are extremely low, of light color, can not be to color fastness grading.
Finally, it should also be noted that it is listed above be only the present invention several specific embodiments.Obviously, this hair
Bright to be not limited to above example, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (4)
1. blue K-type reactive dye, it is characterized in that general structure is：
2. the preparation method of blue K-type reactive dye as described in claim 1, it is characterized in that：It is contaminated using Indigoidine
Material, Cyanuric Chloride are reacted with the condensation product of aminobenzenesulfonic acid, are included the following steps：
1), Indigoidine dyestuffs are dispersed in water, obtain dyestuff suspension；
After the condensation product of Cyanuric Chloride and aminobenzenesulfonic acid is dissolved in water, it is added in dyestuff suspension, adding as tiing up
The potassium carbonate of sour agent reacts 1~6hr at 40~60 DEG C；
The Indigoidine dyestuffs：The condensation product of Cyanuric Chloride and aminobenzenesulfonic acid：Potassium carbonate=1:2:1 molar ratio；
The structural formula of the Indigoidine dyestuffs is：
The condensation product of the Cyanuric Chloride and aminobenzenesulfonic acid is
2) reaction solution obtained by step 1), is adjusted into pH value to 1~2, filtering, filtration cakes torrefaction obtains blue K-type activity dye
Material.
3. the preparation method of blue K-type reactive dye according to claim 2, it is characterized in that in the step 1)：
It is first that Indigoidine dyestuffs is levigate to the sieve that can cross 300 mesh；Then match according to 0.01mol Indigoidine dyestuffs
With the solid-liquid ratio of 20 ± 5mL water, will be levigate after Indigoidine dyestuffs be scattered in, obtain dyestuff suspension；
According to the solid-liquid ratio of 0.02mol Cyanuric Chlorides and condensation product adapted 20 ± 5mL water of aminobenzenesulfonic acid, by Cyanuric Chloride with
The condensation product of aminobenzenesulfonic acid is dissolved in water.
4. the preparation method of blue K-type reactive dye according to claim 2 or 3, it is characterized in that：
In the step 2), filter cake is first subjected to pickling, re-dry obtains blue K-type reactive dye.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233322A (en) * | 2018-10-19 | 2019-01-18 | 绍兴金美珂化工有限公司 | A kind of Vickery blue and preparation method thereof |
| CN111040468A (en) * | 2019-12-26 | 2020-04-21 | 杭州天马思宏数码科技有限公司 | Blue temporary water-soluble reactive dye and preparation method thereof |
| CN111286211A (en) * | 2020-03-30 | 2020-06-16 | 金华双宏化工有限公司 | Sun-proof blue acid dye and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329521A (en) * | 2011-09-29 | 2012-01-25 | 天津德凯化工股份有限公司 | Red reactive dye and preparation method thereof |
| WO2012036568A1 (en) * | 2010-09-14 | 2012-03-22 | Victoria Link Limited | Methods of identifying and characterizing natural product gene clusters |
| CN102952813A (en) * | 2012-10-26 | 2013-03-06 | 东北电力大学 | Synthetic method and extraction process of blue natural dye |
-
2018
- 2018-06-13 CN CN201810607217.7A patent/CN108530940B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012036568A1 (en) * | 2010-09-14 | 2012-03-22 | Victoria Link Limited | Methods of identifying and characterizing natural product gene clusters |
| CN102329521A (en) * | 2011-09-29 | 2012-01-25 | 天津德凯化工股份有限公司 | Red reactive dye and preparation method thereof |
| CN102952813A (en) * | 2012-10-26 | 2013-03-06 | 东北电力大学 | Synthetic method and extraction process of blue natural dye |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233322A (en) * | 2018-10-19 | 2019-01-18 | 绍兴金美珂化工有限公司 | A kind of Vickery blue and preparation method thereof |
| CN109233322B (en) * | 2018-10-19 | 2020-04-07 | 绍兴金美珂化工有限公司 | Blue acid dye and preparation method thereof |
| CN111040468A (en) * | 2019-12-26 | 2020-04-21 | 杭州天马思宏数码科技有限公司 | Blue temporary water-soluble reactive dye and preparation method thereof |
| CN111286211A (en) * | 2020-03-30 | 2020-06-16 | 金华双宏化工有限公司 | Sun-proof blue acid dye and preparation method thereof |
| CN111286211B (en) * | 2020-03-30 | 2021-02-23 | 金华双宏化工有限公司 | Sun-proof blue acid dye and preparation method thereof |
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