CN104311462A - Preparation method of nitrogen aniline active dye intermediate - Google Patents
Preparation method of nitrogen aniline active dye intermediate Download PDFInfo
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- CN104311462A CN104311462A CN201410598573.9A CN201410598573A CN104311462A CN 104311462 A CN104311462 A CN 104311462A CN 201410598573 A CN201410598573 A CN 201410598573A CN 104311462 A CN104311462 A CN 104311462A
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- reactive dyestuffs
- mixture
- amine reactive
- pyridine amine
- aniline
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Abstract
The invention provides a preparation method of a nitrogen aniline active dye intermediate. The method specifically comprises the following steps: adding p-ethyl chloroaniline and acetic anhydride into a reaction kettle in a molar ratio of (1:1.2) to (1:1.5); then adding an organic solvent in a molar ratio with a mixture of p-ethyl chloroaniline and acetic anhydride (1:1) to (3:1); mixing and stirring for 20-30 minutes; adding 1-3% of an acid catalyst based on total mass of the mixture; dropwise adding within 30-40 minutes; heating to 80-90 DEG C and insulating to react for 3-4 hours; cooling to room temperature; washing the reactant to neutral and removing water in a system by using a drier; then, adding vinyl sulfone with the molar ratio with ethyl chloroaniline (1:1.2)-(1:1.3), heating to 60-70 DEG C and stirring for 30-40 minutes; adding 3-5% of sodium ethanol based on total mass of the mixture of ethyl chloroaniline and vinyl sulfone; maintaining 60-70 DEG C for reaction for 2-3 hours; cooling to room temperature to separate out crystals; filtering crystals; and rotatably evaporating residual mixture to remove the solvent to obtain the nitrogen aniline active dye intermediate.
Description
Technical field
The present invention relates to dyestuff intermediate preparation field, particularly relate to a kind of preparation of pyridine amine reactive dyestuffs intermediate.
Background technology
Reactive dyestuffs form with parent dye, concatenating group and active group due to it, make its in use can with processbearing astrocyte firmly covalent bonds, and possess the incomparable feature of other cellulosic fibre dyestuff a series of, establish it as the development of Dyestuffs Used for Cellulose Fibres and the status using emphasis, show following four aspects highlightedly:
(1) reactive dyestuffs replace prohibitive dye with other types of fibers element dyestuff as one of optimal selection of thioxine dyes, glacial dye and vat dyes etc.
(2) reactive dyestuffs can obtain high-caliber every strong performance particularly wet fastness with economic dyeing and simple dying operation.
(3) chromatogram of reactive dyestuffs is wide, lovely luster, excellent performance, suitability are strong, and its form and aspect and performance adapt with the requirement of market to fiber and dress material substantially.
(4) reactive dyestuffs are applicable to the needs that new cellulosic product is printed and dyed as Lyocell fiber etc.
But, also there are some problems in reactive dyestuffs, as utilization ratio is not high enough, be generally 60% ~ 70%, produce a large amount of coloured sewage, in order to suppress the electric charge of fiber surface, reactive dyestuffs need consume the ionogen of a great deal of when using, both add labour intensity, and caused again chlorine ion concentration in waste water up to more than 10 ten thousand ppm, substantially increase the difficulty of administering reactive dyed wastewater.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of pyridine amine reactive dyestuffs intermediate is provided, pyridine amine reactive dyestuffs intermediate prepared by the method, utilization ratio is high and of many uses, the pollutent that preparation process produces is few, may be used for synthesis various active dyestuff, S (a sorption rate/substantivity) > 85% of the reactive dyestuffs synthesized after testing, LDF (level-dyeing property factor) >80%, effectively raises the dye uptake of reactive dyestuffs.
Concrete steps comprise: by mol ratio be 1:1.2-1:1.5 join in reactor to ethyl chloride aniline, diacetyl oxide, then add and the organic solvent to ethyl chloride aniline and diacetyl oxide mixture mol ratio 1:1-3:1, mix and blend 20-30 minute, add the acid catalyst of said mixture total mass 1-3%, dropwise in 30-40 minute, temperature rises to 80-90 degree insulation reaction 3-4 hour, and temperature is down to room temperature, reactants water is washed till neutrality, the water in siccative removing system; Adding with ethyl chloride aniline mol ratio is again the vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) of 1:1.2-1:1.3, be warming up to 60-70 degree and stir 30-40 minute, add ethyl chloride aniline and vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) mixture total mass 3-5% sodium ethylate, keep 60-70 degree reaction 2-3 hour, being cooled to room temperature has crystal to separate out, cross and filter crystal, remaining mixture rotary evaporation removes desolventizing and obtains pyridine amine reactive dyestuffs intermediate.
Reaction equation is as follows:
Further, in reaction process, described acid catalyst is hydrochloric acid and sulfuric acid.
Further, in reaction process, described organic solvent is octane-iso or sherwood oil, or is the mixture of the two, and blending ratio is 1:1.
Further, in reaction process, described siccative is silica-gel drier and molecular sieve desiccant.
Beneficial effect of the present invention: pyridine amine reactive dyestuffs intermediate prepared by the present invention contains acetyl group; from intermediate; again through a series of organic synthesis unit process; various baroque dye composition can be obtained; introduce ethene sulfuryl active group to intermediate, obtained intermediate can be used for synthesizing various active dyestuff.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
156 grams are joined in reactor to ethyl chloride aniline, 122 grams of diacetyl oxides, then octane-iso 251 grams, mix and blend 20 minutes, add hydrochloric acid catalyst 5.3 grams, dropwise in 30 minutes, temperature rises to 80 degree of insulation reaction 3 hours, and temperature is down to room temperature, reactants water is washed till neutrality, the water in silica-gel drier removing system; Add the vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) of 82 grams again, be warming up to 60 degree and stir 30 minutes, add 7.2 grams of sodium ethylates, keep 60 degree of reactions 2 hours, being cooled to room temperature has crystal to separate out, and crosses and filters crystal, and remaining mixture rotary evaporation removes desolventizing and obtains 125 grams, pyridine amine reactive dyestuffs intermediate.
Embodiment 2
156 grams are joined in reactor to ethyl chloride aniline, 143 grams of diacetyl oxides, then sherwood oil 195 grams is added, mix and blend 30 minutes, add sulfuric acid catalyst 15 grams, dropwise in 40 minutes, temperature rises to 90 degree of insulation reaction 4 hours, and temperature is down to room temperature, reactants water is washed till neutrality, the water in molecular sieve desiccant removing system; Add vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) 153 grams again, be warming up to 70 degree and stir 40 minutes, add sodium ethylate 16 grams, keep 70 degree of reactions 3 hours, being cooled to room temperature has crystal to separate out, and crosses and filters crystal, and remaining mixture rotary evaporation removes desolventizing and obtains 136 grams, pyridine amine reactive dyestuffs intermediate.
Embodiment 3
156 grams are joined in reactor to ethyl chloride aniline, 153 grams of diacetyl oxides, then octane-iso 251 grams is added, mix and blend 30 minutes, add hydrochloric acid catalyst 6 grams, dropwise in 30 minutes, temperature rises to 85 degree of insulation reaction 4 hours, and temperature is down to room temperature, reactants water is washed till neutrality, the water in molecular sieve desiccant removing system; Add vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) 148 grams again, be warming up to 70 degree and stir 40 minutes, add sodium ethylate 12 grams, keep 65 degree of reactions 2 hours, being cooled to room temperature has crystal to separate out, and crosses and filters crystal, and remaining mixture rotary evaporation removes desolventizing and obtains 140 grams, pyridine amine reactive dyestuffs intermediate.
Embodiment 4
156 grams are joined in reactor to ethyl chloride aniline, 133 grams of diacetyl oxides, then octane-iso 57 grams, sherwood oil 98 grams is added, mix and blend 30 minutes, add sulfuric acid catalyst 6 grams, dropwise in 30 minutes, temperature rises to 80 degree of insulation reaction 3 hours, and temperature is down to room temperature, reactants water is washed till neutrality, the water in molecular sieve desiccant removing system; Add vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) 142 grams again, be warming up to 70 degree and stir 30 minutes, add 10 grams of sodium ethylates, keep 70 degree of reactions 3 hours, being cooled to room temperature has crystal to separate out, and crosses and filters crystal, and remaining mixture rotary evaporation removes desolventizing and obtains 130 grams, pyridine amine reactive dyestuffs intermediate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a pyridine amine reactive dyestuffs intermediate, its structural formula is as follows:
2. a kind of pyridine amine reactive dyestuffs intermediate according to claim 1, preparation process comprises: by mol ratio be 1:1.2-1:1.5 join in reactor to ethyl chloride aniline, diacetyl oxide, then add and the organic solvent to ethyl chloride aniline and diacetyl oxide mixture mol ratio 1:1-3:1, mix and blend 20-30 minute, add the acid catalyst of said mixture total mass 1-3%, dropwise in 30-40 minute, temperature rises to 80-90 degree insulation reaction 3-4 hour, temperature is down to room temperature, reactants water is washed till neutrality, the water in siccative removing system; Adding with ethyl chloride aniline mol ratio is again the vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) of 1:1.2-1:1.3, be warming up to 60-70 degree and stir 30-40 minute, add ethyl chloride aniline and vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) mixture total mass 3-5% sodium ethylate, keep 60-70 degree reaction 2-3 hour, being cooled to room temperature has crystal to separate out, cross and filter crystal, remaining mixture rotary evaporation removes desolventizing and obtains pyridine amine reactive dyestuffs intermediate.
3. a kind of pyridine amine reactive dyestuffs intermediate according to claim 1, reaction equation is as follows:
4. the preparation process of a kind of pyridine amine reactive dyestuffs intermediate according to claim 2, it is characterized in that, described acid catalyst is hydrochloric acid and sulfuric acid.
5. the preparation process of a kind of pyridine amine reactive dyestuffs intermediate according to claim 2, it is characterized in that, described organic solvent is octane-iso or sherwood oil, or is the mixture of the two, and blending ratio is 1:1.
6. the preparation process of a kind of pyridine amine reactive dyestuffs intermediate according to claim 2, it is characterized in that, described siccative is silica-gel drier and molecular sieve desiccant.
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| CN201410598573.9A CN104311462A (en) | 2014-10-30 | 2014-10-30 | Preparation method of nitrogen aniline active dye intermediate |
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| CN201410598573.9A CN104311462A (en) | 2014-10-30 | 2014-10-30 | Preparation method of nitrogen aniline active dye intermediate |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275028A (en) * | 2013-05-29 | 2013-09-04 | 苏州大学 | Vinyl sulfone-substituted cysteine-N-carboxyanhydride, polymer thereof and application of polymer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275028A (en) * | 2013-05-29 | 2013-09-04 | 苏州大学 | Vinyl sulfone-substituted cysteine-N-carboxyanhydride, polymer thereof and application of polymer |
Non-Patent Citations (3)
| Title |
|---|
| 乐一鸣 等: "乙烯砜染料水解动力学及其反应机理的研究", 《华东化工学院学报》, vol. 14, no. 1, 1 March 1988 (1988-03-01), pages 37 - 45 * |
| 孙卫东 主编: "《精细有机化学品化学》", 28 February 2006, article "2.6.2 乙烯砜型活性染料" * |
| 宋心远 等编: "《活性染料染色的理论和实践》", 30 September 1991, article "亲核加成反应", pages: 200 * |
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Application publication date: 20150128 |