CN108624084A - A kind of anthraquinone system peak green reactive dye and its preparation method and application - Google Patents
A kind of anthraquinone system peak green reactive dye and its preparation method and application Download PDFInfo
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- CN108624084A CN108624084A CN201810558921.8A CN201810558921A CN108624084A CN 108624084 A CN108624084 A CN 108624084A CN 201810558921 A CN201810558921 A CN 201810558921A CN 108624084 A CN108624084 A CN 108624084A
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- 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
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
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- 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
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- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
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- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/148—Wool using reactive dyes
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- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/248—Polyamides; Polyurethanes using reactive dyes
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- 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
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Abstract
The present invention relates to a kind of anthraquinone system peak green reactive dye and its preparation method and application, and reactive dye structural formula is：Preparation method includes：Prepared by one contracting liquid, prepared by two contracting liquid, prepared by diazol, prepared by anthraquinone system peak green reactive dye；Reactive dye are applied to cotton, synthetic cotton, fiber crops, regenerated fiber and its printing in textiles or silk, wool, polyamide fibre and its textile dyeing.Dye structure of the present invention is single structure, is prepared simply, at low cost；It is the green reactive dye for being suitable for the protein fibres such as multiple fiber such as cellulose fibre, wool, silk and PA66 printing and dyeing, makes up the vacancy of green reactive dye in the market, there is higher molar extinction coefficient, good printing and dyeing improving performance；By introducing the chromogen of two high light-fast series simultaneously in the molecule, make dyestuff that there is excellent color fastness to light.
Description
Technical field
The invention belongs to reactive dye and its preparation method and application fields, more particularly to a kind of anthraquinone system peak green activity
Dyestuff and its preparation method and application.
Background technology
In reactive dye, anthraquinone dye is the second major class dyestuff being only second in azo dyes, has bright in color light, resistance to
The features such as shining function admirable, but most of is blue coloured light, and molar extinction coefficient is low.
The exploitation of green reactive dye is always the hot spot of dyestuff circle concern.Green dye used is especially tender in the market
Green coloured light is formed by two or more dyestuff blending mostly, the coloured light reproducibility caused by compatibility sex differernce easily occurs
Bad, the problems such as fastness is poor.With the fast development of kinds of fibers and printing technology, Dyestuff Market is to active dye printing performance
Requirement it is also higher and higher, this also promotes reactive dye to develop in terms of improving application performance.Therefore it synthesizes a series of single
Structure, application performance is wide, while suitable for the protein fibres such as multiple fiber such as cellulose fibre, wool, silk and
The green reactive dye of PA66 printing and dyeing make up the vacancy of green reactive dye in the market, are still important research direction.
Invention content
Technical problem to be solved by the invention is to provide a kind of anthraquinone system peak green reactive dye and preparation method thereof and
Using the anthraquinone system peak green reactive dye introduce the chromogen of two high light-fast series simultaneously in the molecule, have higher
Molar extinction coefficient, printing and dyeing improving performance, even more show good washable, fast light, colour fastness to rubbing.
A kind of anthraquinone system peak green reactive dye of the present invention, which is characterized in that the reactive dye structural formula is：
In formula, R1For aromatic amino and its derivative, R2For CONH2Or CH2SO3Na。
The R1For
Wherein x, y or z=0,1,2.
The preparation method of a kind of anthraquinone system peak green reactive dye of the present invention, synthetic route are：
The preparation method of a kind of anthraquinone system peak green reactive dye of the present invention, including：
The preparation of (1) one contracting object：Cyanuric Chloride is dispersed in water, is beaten, 1- amino -2- sulfonic acid -4- (3- ammonia is added
Base -2,4,6- trimethyl -5- sulfonic acid phenylamino) anthraquinone sodium salt 49# color base solution reactions, obtain a contracting liquid, wherein Cyanuric Chloride
Dispersion liquid mass fraction is 10%-30%, and the molar ratio of Cyanuric Chloride and 49# color bases is 1:0.98~1:1；
(2) preparation of the preparation of two contracting things and diazol：Aromatic diamine is added in (1) one contracting liquid of step and is reacted, is obtained
To two contracting liquid, concentrated hydrochloric acid is added, stirring instills sodium nitrite solution reaction, obtains diazol, wherein aromatic diamine and step
(1) molar ratio of Cyanuric Chloride is 0.96~0.98 in:1, the molar ratio of aromatic diamine, concentrated hydrochloric acid and sodium nitrite is 1:1
~2:1~2；
(3) coupling reaction：By 3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone or 3- metilsulfates -4-
Methyl -6- hydroxy-ns-ethylpyridine ketone is added in step (2) diazol, and sodium hydroxide reaction is added, obtains anthraquinone system peak green
Reactive dye, wherein 3- formamido groups -4- methyl -6- hydroxy-ns-ethylpyridine ketone or 3- metilsulfate -4- methyl -6- hydroxyls
The molar ratio of base-N- ethylpyridines ketone and diazol is 0.98:0.9-0.98:1.
Mashing, addition 49# color bases solution are carried out under the conditions of 0~5 DEG C in the step (1)；Beating time is
0.5-1h。
49# color base liquid quality fractions are 10%-20% in the step (1)；Reaction temperature is 0~5 DEG C, pH value in reaction
It is 4~4.5, the reaction time is 2~4h.
It is 25~35 DEG C that reaction temperature in a contracting liquid, which is added, in aromatic diamine in the step (2), pH value in reaction for 3.5~
4.5, the reaction time is 4~6h.
It is -5~0 DEG C that sodium nitrite solution reaction temperature is instilled in the step (2), reaction time 1-3h.
3- metilsulfates -4- methyl -6- hydroxy-ns-ethylpyridine ketone is 3- sodium methanesulfonates -4- in the step (3)
The preparation method of methyl -6- hydroxy-ns-ethylpyridine ketone, 3- sodium methanesulfonate -4- methyl -6- hydroxy-ns-ethylpyridine ketone is：
(1) sodium pyrosulfite is added in formaldehyde under stiring, obtains solution, the wherein molar ratio of formaldehyde and sodium pyrosulfite is 2:0.99
~2:1；(2) 3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone is soluble in water, 0.5h is stirred, anhydrous phosphorus is added
Acid dihydride sodium uses 20%NaOH aqueous solution tune pH value to 6.0 after stirring 20min, after stablizing 5min, then adjusts pH value to 6.5, rises
Temperature is added solution in (1), is warming up to 58~60 DEG C to 45 DEG C, after reacting 1.5h, is cooled to 35 DEG C of spare, wherein 3- formyls ammonia
The ratio of base -4- methyl -6- hydroxy-ns-ethylpyridine ketone and water is 1:1.8~1:2,3- formamido group -4- methyl -6- hydroxyls -
The molar ratio of formaldehyde and anhydrous sodium dihydrogen phosphate is 2.2 in N- ethylpyridines ketone, (1):2.5:1~2.2:2.6:1.
Sodium hydroxide is added in the step (3) and adjusts pH value to 8.0；Reaction is：5-10min is maintained at 0~5 DEG C, so
The reaction was continued at normal temperatures afterwards 1-3h.
Anthraquinone system peak green reactive dye can also contain some other dye component in the step (3) and part is miscellaneous
Matter because dyestuff be conventionally synthesized or salting-out process in inevitably carry fraction impurity dyestuff and electrolyte powder (chlorine
Change sodium etc.), the presence of these substances has no effect on the technique effect of the present invention.
The coupling solution that coupling reaction obtains in the step (3) is added dispersant, cosolvent, filler or other performances and changes
Kind auxiliary agent, is made power-product after spray drying treatment.
The preparation method of a kind of anthraquinone system peak green reactive dye of the present invention, primary condensation reaction, consecutive condensation
Intermediate is according to 49# color bases, R1Determined respectively with the size of Cyanuric Chloride respond, the relatively weak elder generation of respond with
Cyanuric Chloride carry out primary condensation reaction, respond it is moderate then with a contracting object progress consecutive condensation.
The preparation method of a kind of anthraquinone system peak green reactive dye of the present invention, according to a contracting, two contracting reaction intermediates
Difference, synthesis technology can also be following sequence：The preparation of (1) one contracting object；(2) preparation of diazol；(3) coupling reaction；(4)
The preparation of two contracting things；(5) saltout (6) purification.
A kind of anthraquinone system peak green reactive dye of the present invention are applied to cotton, synthetic cotton, fiber crops, regenerated fiber and its textile
Stamp or silk, wool, polyamide fibre and its textile dyeing.
Reactive dye blue parent anthraquinone ring is introduced into light yellow intermediate 3- first by the present invention by condensation, coupling reaction
In acylamino- -4- methyl -6- hydroxy-ns-ethylpyridine ketone or 3- metilsulfate -4- methyl -6- hydroxy-ns-ethylpyridine ketone,
By colorant match in dye molecule, a series of anthraquinone system peak green reactive dye have been synthesized.
Advantageous effect
(1) anthraquinone system peak green reactive dye structure of the invention is single structure, is prepared simply, at low cost；
(2) present invention is to be suitable for the green activity of the protein fibres such as cellulose fibre, wool, silk and PA66 printing and dyeing
Dyestuff compensates for the vacancy of green reactive dye in the market, has higher molar extinction coefficient, good printing and dyeing enhancing
Energy；
(3) anthraquinone system green reactive dye of the invention by introducing the color development of two high light-fast series simultaneously in the molecule
Body makes dyestuff have excellent color fastness to light.
Description of the drawings
Fig. 1 is the infrared spectrogram of anthraquinone system peak green reactive dye in embodiment 1；
Fig. 2 is the infrared spectrogram of anthraquinone system peak green reactive dye in embodiment 2；
Fig. 3 is the infrared spectrogram of anthraquinone system peak green reactive dye in embodiment 3；
Fig. 4 is the infrared spectrogram of anthraquinone system peak green reactive dye in embodiment 4；
Fig. 5 is that anthraquinone system peak green reactive dye promote force curve to the stamp of cotton fabric in embodiment 5；
Fig. 6 is anthraquinone system peak green reactive dye in embodiment 6 to the dyeing figure of silk fabric；
Fig. 7 is that anthraquinone system peak green reactive dye promote force curve to the dyeing of silk fabric in embodiment 6；
Fig. 8 is anthraquinone system peak green reactive dye in embodiment 7 to the dyeing figure of wool fabric；
Fig. 9 is that anthraquinone system peak green reactive dye promote force curve to the dyeing of wool fabric in embodiment 7；
Figure 10 is that anthraquinone system peak green reactive dye promote force curve to the dyeing of PA66 fabrics in embodiment 8.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The synthesis technology of the following anthraquinone system peak green reactive dye of structure：
The preparation of (1) one contracting object：By 18.6g (0.1mol) Cyanuric Chlorides under the conditions of 0-2 DEG C in 80g mixture of ice and water
Mashing 1 hour.Accurately weigh 54.7g (0.099mol) 1- amino -2- sulfonic acid -4- (3- amino -2,4,6- trimethyl -5- sulfonic acid
Phenylamino) anthraquinone sodium salt be made into 15% solution, adjust pH value be 5.8~6.5, blue clear solution is dissolved as, at 0~5 DEG C
Under the conditions of be added drop-wise in 1 hour in the uniform Cyanuric Chloride of mashing, 5 DEG C of temperature, the reaction of pH value 4~4.5 3 are kept after being added dropwise
Hour, thin-layered chromatography detects a contracting reaction end.
(2) preparation of the preparation of two contracting things and diazol：By 18.23g (0.097mol) 2,4- diamino benzene sulfonic acid dry powder
It is added in above-mentioned contracting liquid, adjustment pH value is to slowly warm up to 30 DEG C to 4.0~4.5, this pH value and temperature condition is kept to react
4h, thin-layered chromatography detect two contracting reaction ends, obtain two contracting liquid, be cooled to -5~0 DEG C, 17.00g is once added
(0.17mol) concentrated hydrochloric acid is slowly dropped into 6.97g (0.101mol) sodium nitrite in 1 hour and is made under the conditions of -5~0 DEG C
30% aqueous solution, reacted 1.5 hours under the conditions of -5~0 DEG C after dripping off.It is excessive with sulfamic acid elimination after having reacted
Nitrous acid.
(3) coupling reaction：On 0.1mol 3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone is once added
In the diazol for stating preparation, pH value is quickly adjusted with 20%NaOH to 8.0,10min is kept under the conditions of this pH value, 0~5 DEG C,
The reaction was continued at normal temperatures afterwards 2h, thin-layered chromatography detection coupling terminal, obtains anthraquinone system peak green reactive dye, yield
83%.Dyestuff ethyl alcohol recrystallization, infrared spectrum are shown in Fig. 1.Dyestuff 2990cm-1、1456cm-1Place is CH3Bending vibration；
1600cm-1、1500cm-1、1450cm-1Nearby there is the skeletal vibration peak of phenyl ring；1633cm-1Place is two on a ring on anthraquinone
The stretching vibration absworption peak of carbonyl C=O；1668cm-1For the stretching vibration absworption peak of carbonyl C=O；1300cm-1For secondary amine C-N
Stretching vibration absworption peak；1571cm-1For the absorption peak of N=N；1620cm-1The absorption peak at place is mainly by the NH in amide groups2It is curved
Qu Zhendong causes.
Above-mentioned anthraquinone system peak green reactive dye are configured to a concentration of 2.0 × 10-5The aqueous solution of mol/L measures dyestuff
Ultraviolet-visible absorption spectroscopy, absorption peak reaches 2.59 × 10 in 426nm, molar extinction coefficient4(L·mol-1·cm-1) and
At 584nm, molar extinction coefficient reaches 0.83 × 104(L·mol-1·cm-1), obtain the light green of bright-coloured, high molar extinction coefficient
Color reactive dye.
Embodiment 2
The synthesis technology of the following anthraquinone system peak green reactive dye of structure：
The preparation of (1) one contracting object：By 18.6g (0.1mol) Cyanuric Chlorides under the conditions of 0-2 DEG C in 80g mixture of ice and water
Mashing 1 hour.Accurately weigh 54.7g (0.099mol) 1- amino -2- sulfonic acid -4- (3- amino -2,4,6- trimethyl -5- sulfonic acid
Phenylamino) anthraquinone sodium salt be made into 15% solution, adjust pH value be 5.8~6.5, blue clear solution is dissolved as, at 0~5 DEG C
Under the conditions of be added drop-wise in 1 hour in the uniform Cyanuric Chloride of mashing, keep 5 DEG C of temperature, pH value 4 to react after being added dropwise 3 hours,
Thin-layered chromatography detects a contracting reaction end.
(2) preparation of the preparation of two contracting things and diazol：By 18.23g (0.097mol) 2,4- diamino benzene sulfonic acid dry powder
It is added in above-mentioned contracting liquid, adjustment pH value is to slowly warm up to 30 DEG C to 4.0~4.5, this pH value and temperature condition is kept to react
4h, thin-layered chromatography detect two contracting reaction ends, obtain two contracting liquid, be cooled to -5~0 DEG C, 17.00g is once added
(0.17mol) concentrated hydrochloric acid is slowly dropped into 6.97g (0.101mol) sodium nitrite in 1 hour and is made under the conditions of -5~0 DEG C
30% aqueous solution, reacted 1.5 hours under the conditions of -5~0 DEG C after dripping off.It is excessive with sulfamic acid elimination after having reacted
Nitrous acid.
(3) preparation method of 3- sodium methanesulfonates -4- methyl -6- hydroxy-ns-ethylpyridine ketone is：(1) formaldehyde is being stirred
Lower addition sodium pyrosulfite is mixed, solution is obtained, the wherein molar ratio of formaldehyde and sodium pyrosulfite is 2:1；(2) by 3- formyl ammonia
Base -4- methyl -6- hydroxy-ns-ethylpyridine ketone is soluble in water, stirs 0.5h, and anhydrous sodium dihydrogen phosphate is added, after stirring 20min
With 20%NaOH aqueous solution tune pH value to 6.0, after stablizing 5min, then pH value is adjusted to 6.5, be warming up to 45 DEG C, be added molten in (1)
Liquid, is warming up to 58~60 DEG C, after reacting 1.5h, is cooled to 35 DEG C of spare, wherein 3- formamido groups -4- methyl -6- hydroxy-ns-second
The ratio of yl pyridines ketone and water is 1:Formaldehyde and nothing in 1.8,3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone, (1)
The molar ratio of water sodium dihydrogen phosphate is 2.2:2.5:1.
(4) coupling reaction：The 0.1mol 3- sodium methanesulfonate -4- methyl -6- hydroxy-ns-ethylpyridine that will be prepared in (3)
Ketone is once added in the diazol prepared in (2), and pH value is quickly adjusted with 20%NaOH to 8.0, in this pH value, 0~5 DEG C of condition
The reaction was continued at normal temperatures after lower maintenance 10min 2h, thin-layered chromatography detection coupling terminal, obtains anthraquinone system peak green activity dye
Material.Measure the ultraviolet-visible absorption spectroscopy of dyestuff, absorption peak at 428nm and 586nm, molar extinction coefficient is respectively 2.41 ×
104, 0.79 × 104(L·mol-1·cm-1), obtain bright-coloured peak green reactive dye, yield 79%.Dyestuff is tied again with ethyl alcohol
Crystalline substance, infrared spectrum are shown in Fig. 2.Dyestuff 2988cm-1、1454cm-1Place is CH3Bending vibration；1053cm-1、1110cm-1, 900~
600cm-1Place is mainly the C-H out-of-plane bending vibrations of aromatic ring；1633cm-1Place is the stretching vibration absworption peak of anthraquinone C=O；
1668cm-1For the stretching vibration absworption peak of carbonyl C=O；1300cm-1For the stretching vibration absworption peak of secondary amine C-N；1571cm-1For
The absorption peak of N=N；3363cm-1For NH2Stretching vibration absworption peak；1618cm-1The absorption peak at place is mainly by NH2Bending vibration
Cause；730cm-1For the stretching vibration peak of C-Cl；1176cm-1、1100cm-1、1055cm-1It is sulfonate that, which there is strong absworption peak at place,
Absorption peak；1528cm-1、1419cm-1For triazine C=N ring stretching vibration vibration peaks.
Embodiment 3
The synthesis technology of the following anthraquinone system peak green reactive dye of structure：
The preparation of (1) one contracting object：By 18.6g (0.1mol) Cyanuric Chlorides under the conditions of 0-2 DEG C in 80g mixture of ice and water
Mashing 1 hour.Accurately weigh 54.7g (0.099mol) 1- amino -2- sulfonic acid -4- (3- amino -2,4,6- trimethyl -5- sulfonic acid
Phenylamino) anthraquinone sodium salt be made into 15% solution, adjust pH value be 5.8~6.5, blue clear solution is dissolved as, at 0~5 DEG C
Under the conditions of be added drop-wise in 1 hour in the uniform Cyanuric Chloride of mashing, 5 DEG C of temperature, the reaction of pH value 4~4.5 4 are kept after being added dropwise
Hour, thin-layered chromatography detects a contracting reaction end.
(2) preparation of the preparation of two contracting things and diazol：By 18.23g (0.097mol) 2,5- diamino benzene sulfonic acid dry powder
It is added in above-mentioned contracting liquid, adjustment pH value is to slowly warm up to 30 DEG C to 4.0~4.5, this pH value and temperature condition is kept to react
4h, thin-layered chromatography detect two contracting reaction ends, obtain two contracting liquid, be cooled to -5~0 DEG C, 17.00g is once added
(0.17mol) concentrated hydrochloric acid is slowly dropped into 6.97g (0.101mol) sodium nitrite in 1 hour and is made under the conditions of -5~0 DEG C
30% aqueous solution, reacted 1.5 hours under the conditions of -5~0 DEG C after dripping off.It is excessive with sulfamic acid elimination after having reacted
Nitrous acid.
(3) coupling reaction：On 0.1mol 3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone is once added
In the diazol for stating preparation, pH value is quickly adjusted with 20%NaOH to 8.0,10min is maintained under the conditions of this pH value, 0~5 DEG C,
The reaction was continued at normal temperatures afterwards 2h, thin-layered chromatography detection coupling terminal, obtains anthraquinone system peak green reactive dye, yield
84.1%.Dyestuff ethyl alcohol recrystallization, infrared spectrum are shown in Fig. 3.Dyestuff 3363cm-1For NH2Stretching vibration absworption peak；
2993cm-1、1456cm-1Place is CH3Bending vibration；In 1605cm-1、1503cm-1、1455cm-1Nearby there is the skeleton of phenyl ring to shake
Dynamic peak；1635cm-1The stretching vibration absworption peak that place is two carbonyl C=O on a ring on anthraquinone；1670cm-1For carbonyl C=O
Stretching vibration absworption peak；1300cm-1For the stretching vibration absworption peak of secondary amine C-N；1571cm-1For the absorption peak of N=N；
1618cm-1The absorption peak at place is mainly by the NH in amide groups2Bending vibration causes.
Embodiment 4
The synthesis technology of the following anthraquinone system peak green reactive dye of structure：
The preparation of (1) one contracting object：By 18.6g (0.1mol) Cyanuric Chlorides under the conditions of 0-2 DEG C in 80g mixture of ice and water
Mashing 1 hour.Accurately weigh 54.7g (0.099mol) 1- amino -2- sulfonic acid -4- (3- amino -2,4,6- trimethyl -5- sulfonic acid
Phenylamino) anthraquinone sodium salt be made into 15% solution, adjust pH be 5.8~6.5, blue clear solution is dissolved as, in 0~5 DEG C of item
Part is added drop-wise in lower 1 hour in the uniform Cyanuric Chloride of mashing, and 5 DEG C of temperature, pH value 4~4.5, reaction 4 are kept after being added dropwise
Hour, thin-layered chromatography detects a contracting reaction end.
(2) preparation of the preparation of two contracting things and diazol：An above-mentioned contracting is added in 10.49g (0.097mol) p-phenylenediamine
In liquid, adjustment pH value is to slowly warm up to 28 DEG C to 4.0~4.5, this pH value and temperature condition is kept to react 4h, thin-layered chromatography
Two contracting reaction ends are detected, two contracting liquid is obtained, is cooled to -5~0 DEG C, 17.00g (0.17mol) concentrated hydrochloric acid are once added, in -5
Under the conditions of~0 DEG C, 30% aqueous solution that 6.97g (0.101mol) sodium nitrite is made into is slowly dropped into 1 hour, after dripping off
It is reacted 1.5 hours under the conditions of -5~0 DEG C.After having reacted excessive nitrous acid is eliminated with sulfamic acid.
(3) coupling reaction：On 0.1mol 3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone is once added
In the diazol for stating preparation, pH value is quickly adjusted with 20%NaOH to 8.0,10min is maintained under the conditions of this pH value, 0~5 DEG C,
The reaction was continued at normal temperatures afterwards 2h, thin-layered chromatography detection coupling terminal, obtains anthraquinone system peak green reactive dye, yield
85.6%.Dyestuff ethyl alcohol recrystallization, infrared spectrum are shown in Fig. 4.Dyestuff is in 3363cm-1For NH2Stretching vibration absworption peak；
2989cm-1、1454cm-1Place is CH3Bending vibration；1053cm-1、1110cm-1, 900~600cm-1There are the faces C-H of aromatic ring at place
Outside sweep is vibrated；1600cm-1、1500cm-1、1450cm-1Nearby there is the skeletal vibration peak of phenyl ring；1633cm-1Place is C on anthraquinone
The stretching vibration absworption peak of=O；1300cm-1For the stretching vibration absworption peak of secondary amine C-N；1571cm-1For the absorption peak of N=N；
1528cm-1、1419cm-1For triazine C=N ring stretching vibration vibration peaks.
Embodiment 5
Anthraquinone system peak green reactive dye in embodiment 1 are subjected to stamp to cotton fabric, bright-coloured green of fabric can be supplied to
Color tone.
5 parts of urea is taken, 1 part of reserve salt, 2.5 parts of sodium bicarbonate, 86.5 parts of 5 parts of sodium alginate and warm water are tuned into paste in container
Shape, and being sufficiently stirred makes it uniformly be configured to printing gum.By 1 obtained dyestuff of embodiment respectively take 0.5 part (1%), 1 part
(2%), 2 parts (4%), 3 parts (6%), 4 parts (8%), 5 parts (10%), respectively with 49.5 parts of above-mentioned printing gum, 49 parts, 48
Part, 47 parts, 46 parts, 45 parts be uniformly mixed, be modulated into print paste, stamp carried out to cotton with the printing screen of 200 meshes,
4min is baked at 105 DEG C, gas steams 8min.It washes, soaps by a large amount of cold water, hot water wash, cold water is dried after washing.It is apparent to test its
Color depth Integ values are obtained, as shown in Fig. 5, anthraquinone system peak green reactive dye on cotton fabric there is excellent stamp to be promoted
Power performance.
Embodiment 6
Anthraquinone system peak green reactive dye in embodiment 2 are pressed into silk fabric：4g, dyestuff：X% (o.w.f), bath raio：
1:20, sodium bicarbonate：The dyeing recipe of 4g/L is dyed using heating decoration method, and dyeing is as shown in Fig. 6, respectively
It is that 1%, 2%, 4%, 6%, 8%, 10% measurement dyes lifting force to take X%, as shown in Fig. 7, the results showed that：Anthraquinone system is light green
Color reactive dye have excellent dyeing lifting force performance on silk.
Embodiment 7
Anthraquinone system peak green reactive dye in embodiment 3 are pressed into wool fabric：4g, dyestuff：X% (o.w.f), bath raio：
1:20, glacial acetic acid：The dyeing recipe of 3g/L is dyed using heating decoration method, and dyeing is as shown in Fig. 8, takes respectively
X% is that 1%, 2%, 4%, 6%, 8%, 10% measurement dyes lifting force, as shown in Fig. 9, the results showed that：Anthraquinone system peak green
Reactive dye have excellent dyeing lifting force performance on wool fabric.
Embodiment 8
Anthraquinone system peak green reactive dye in embodiment 4 are pressed into PA66 fabrics：4g, dyestuff：X% (o.w.f), bath raio：
1:20, glacial acetic acid：The dyeing recipe of 3g/L is dyed using heating decoration method, and dyeing is same as Example 7, respectively
It is that 1%, 2%, 4%, 6%, 8%, 10% measurement dyes lifting force to take X%, as shown in Fig. 10, the results showed that：Anthraquinone system is tender
Green reactive dye have excellent dyeing lifting force performance on PA66 fabrics.
Embodiment 9
According to national standard, colorfastness to rubbing ISO 105-X12 (2001), Washing ISO 105-C03 (2010) are resistance to
Photochromic fastness ISO 105-B02 (2013), it is 2% (stamp to measure dye strength in embodiment 5~8：Mass fraction, dyeing
(o.w.f)) every color fastness of textile dyeing and stamp when, the results are shown in Table 1, the results showed that：Anthraquinone system peak green activity
Dyestuff has excellent water-fastness, antifriction scrape along is fast light color jail on cotton fabric, silk fabric, wool fabric and PA66 fabrics
Degree.
Table 1
Claims (10)
1. a kind of anthraquinone system peak green reactive dye, which is characterized in that the reactive dye structural formula is：
In formula, R1For aromatic amino and its derivative, R2For CONH2Or CH2SO3M, M are metal ion.
2. one kind anthraquinone system described in accordance with the claim 1 peak green reactive dye, which is characterized in that the R1ForWherein x, y or z=0,1 or 2.
3. the preparation method of a kind of anthraquinone system peak green reactive dye, including：
(1) Cyanuric Chloride is dispersed in water, is beaten, 1- amino -2- sulfonic acid -4- (3- amino -2,4,6- trimethyls -5- is added
Sulfonic acid phenylamino) anthraquinone sodium salt 49# color base solution reactions, a contracting liquid is obtained, wherein Cyanuric Chloride dispersion liquid mass fraction is
The molar ratio of 10%-30%, Cyanuric Chloride and 49# color bases is 1:0.98~1:1；
(2) aromatic diamine is added in a contracting liquid of step (1) and is reacted, obtain two contracting liquid, concentrated hydrochloric acid is added, stirred, instilled
Sodium nitrite solution reacts, and obtains diazol, and the molar ratio of wherein aromatic diamine and Cyanuric Chloride in step (1) is 0.96~
0.98:1, the molar ratio of aromatic diamine, concentrated hydrochloric acid and sodium nitrite is 1:1~2:1~2；
(3) by 3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone or 3- metilsulfate -4- methyl -6- hydroxy-ns -
Ethylpyridine ketone is added in the diazol of step (2), and sodium hydroxide reaction is added, obtains anthraquinone system peak green reactive dye,
Middle 3- formamido groups -4- methyl -6- hydroxy-ns-ethylpyridine ketone or 3- metilsulfate -4- methyl -6- hydroxy-ns-ethyl pyrrole
The molar ratio of pyridine ketone and diazol is 0.98:0.9~0.98:1.
4. the preparation method of one kind anthraquinone system described in accordance with the claim 3 peak green reactive dye, which is characterized in that the step
Suddenly mashing, addition 49# color bases solution are carried out under the conditions of 0~5 DEG C in (1)；Beating time is 0.5-1h；49# color bases are molten
Liquid mass fraction is 10%-20%.
5. the preparation method of one kind anthraquinone system described in accordance with the claim 3 peak green reactive dye, which is characterized in that the step
Suddenly reaction temperature is 0~5 DEG C in (1), and pH value in reaction is 4~4.5, and the reaction time is 2~4h.
6. the preparation method of one kind anthraquinone system described in accordance with the claim 3 peak green reactive dye, which is characterized in that the step
Suddenly it is 25~35 DEG C that reaction temperature in a contracting liquid, which is added, in aromatic diamines in (2), and pH value in reaction is 3.5~4.5, the reaction time 4
~6h.
7. the preparation method of one kind anthraquinone system described in accordance with the claim 3 peak green reactive dye, which is characterized in that the step
Suddenly it is -5~0 DEG C that sodium nitrite solution reaction temperature is instilled in (2), reaction time 1-3h.
8. the preparation method of one kind anthraquinone system described in accordance with the claim 3 peak green reactive dye, which is characterized in that the step
Suddenly 3- metilsulfates -4- methyl -6- hydroxy-ns-ethylpyridine ketone is 3- sodium methanesulfonate -4- methyl -6- hydroxy-ns-in (3)
The preparation method of ethylpyridine ketone, 3- sodium methanesulfonate -4- methyl -6- hydroxy-ns-ethylpyridine ketone is：(1) formaldehyde is being stirred
Lower addition sodium pyrosulfite is mixed, solution is obtained, the wherein molar ratio of formaldehyde and sodium pyrosulfite is 2:0.99~2:1；(2) by 3-
Formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone is soluble in water, stirs 0.5h, and anhydrous sodium dihydrogen phosphate, stirring is added
With 20%NaOH aqueous solution tune pH value to 6.0 after 20min, after stablizing 5min, then pH value is adjusted to 6.5, be warming up to 45 DEG C, be added
(1) solution in, is warming up to 58~60 DEG C, after reacting 1.5h, is cooled to 35 DEG C of spare, wherein 3- formamido groups -4- methyl -6- hydroxyls
The ratio of base-N- ethylpyridines ketone and water is 1:1.8~1:2,3- formamido group -4- methyl -6- hydroxy-ns-ethylpyridine ketone,
(1) molar ratio of formaldehyde and anhydrous sodium dihydrogen phosphate is 2.2 in:2.5:1~2.2:2.6:1.
9. the preparation method of one kind anthraquinone system described in accordance with the claim 3 peak green reactive dye, which is characterized in that the step
Suddenly sodium hydroxide is added in (3) and adjusts pH value to 8.0；Reaction is：5-10min is maintained at 0~5 DEG C, is then continued at normal temperatures
React 1-3h.
10. the application of a kind of anthraquinone system as described in claim 1 peak green reactive dye, which is characterized in that be applied to cotton, people
Make cotton, fiber crops, regenerated fiber and its printing in textiles or silk, wool, polyamide fibre and its textile dyeing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB993594A (en) * | 1963-01-23 | 1965-05-26 | Magdalena Ernste | Improvements in or relating to dyestuffs comprising anthraquinonyl and azo dye moieties |
| US4242259A (en) * | 1978-03-22 | 1980-12-30 | Bayer Aktiengesellschaft | Anthraquinone-azo reactive dyestuffs |
| US5403360A (en) * | 1993-02-05 | 1995-04-04 | Ciba-Geigy Corporation | Process for dyeing or printing cellulosic fiber materials |
| CN103509370A (en) * | 2012-06-25 | 2014-01-15 | 浙江舜龙化工有限公司 | Active green dye |
-
2018
- 2018-06-01 CN CN201810558921.8A patent/CN108624084A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB993594A (en) * | 1963-01-23 | 1965-05-26 | Magdalena Ernste | Improvements in or relating to dyestuffs comprising anthraquinonyl and azo dye moieties |
| US4242259A (en) * | 1978-03-22 | 1980-12-30 | Bayer Aktiengesellschaft | Anthraquinone-azo reactive dyestuffs |
| US5403360A (en) * | 1993-02-05 | 1995-04-04 | Ciba-Geigy Corporation | Process for dyeing or printing cellulosic fiber materials |
| CN103509370A (en) * | 2012-06-25 | 2014-01-15 | 浙江舜龙化工有限公司 | Active green dye |
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Application publication date: 20181009 |