CN106905718A - A kind of H acid is bisazo double-active radical reactive brilliant bule color dyestuff and its preparation method and application - Google Patents
A kind of H acid is bisazo double-active radical reactive brilliant bule color dyestuff and its preparation method and application Download PDFInfo
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- CN106905718A CN106905718A CN201710032421.6A CN201710032421A CN106905718A CN 106905718 A CN106905718 A CN 106905718A CN 201710032421 A CN201710032421 A CN 201710032421A CN 106905718 A CN106905718 A CN 106905718A
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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
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo dyes
-
- 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
- D06P1/384—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 not 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
- D06P3/02—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
-
- 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
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not 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
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8219—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and amide groups
Abstract
It is bisazo double-active radical reactive brilliant bule color dyestuff and its preparation method and application the present invention relates to a kind of H acid, Dyes structural formulae isWherein, R1=SO3During Na or H, R2=H；R2During=COONa, R1=H；Preparation method includes：The anthraquinone derivative that Cyanuric Chloride and the tri-methyl p-toluenesulfonate amino of 3,5 diaminourea 2,4,6 replace is reacted into obtain a contracting liquid；2,4 diamino benzene sulfonic acids (sodium) or 3 are added, 5 diaminobenzoic acids (sodium), reaction obtains two contracting things；Para-ester or meta ester diazotising, obtain diazol；H acid, reaction is added to obtain acid coupling product；By two contracting things diazotising, two contracting things diazol is obtained；Two contracting things diazol is added in acid coupling product, reaction, is obtained final product.Dye shade of the invention is gorgeous, and degree of fixation is high, and fastness is good, and equilibrium time is short, direct high, can be used for dyeing and the stamp of cellulose fiber peacekeeping protein fibre.
Description
Technical field
The invention belongs to dyestuff and its preparation field, more particularly to a kind of H acid is bisazo double-active radical reactive brilliant bule color
Dyestuff and its preparation method and application.
Background technology
Reactive dye have lovely luster, chromatogram is complete, fastness to washing is excellent, price is relatively cheap, technique for applying is easy
The characteristics of, and carcinogenic aromatic amine is free of in structure, so being constantly subjected to the great attention on printing and dyeing circle.Almost 60% cellulose
Fabric all uses reactive dyeing, also, the most of synthetic dyestuffs for using now are azo active dyestuffs.However,
The problems such as reactive dye generally existing degree of fixation is low, lifting force is low, reproducibility is poor, and in dyeing course, produce a large amount of
Colorful wastewater, the damage ratio to environment is more serious, and treatment cost is also higher.
Black dyes is always the color kind of consumption maximum in dyestuff.In the dyeing and stamp of bafta, black chromatogram is accounted for
More than the 50% of whole chromatograms.But active black dye is so far still without can be uniform, complete in 400~700nm wave-length coverages
The dyestuff commodity of absorption.C.I. reactive black 5 accounts for very big proportion in black chromatogram, because its price is low, active easily with other
Dyestuff compatibility, but have that lifting force is poor, salt dosage is more, mainly also have the shortcomings that pitch black degree is not high.Therefore, crow high in recent years
Blackness, the research of the novel active black dyestuff of high colour-fast rate, exploitation are increasingly paid attention to.High colour-fast rate, dark color are good, can
Black to spell, brightly painted cobalt blue reactive dye are always that people most seek target.
Traditional black and active dye main active black 5, the i.e. black KN-B of Commercial active, its structure are as follows：
Dyestuff 1 (C.I. reactive black 5s)
But C.I. reactive black 5s are navy, and not enough, degree of fixation is low and lifting force is poor, and equilibrium time is long for pitch black degree,
Cobalt blue can not be contaminated to obtain, quantity of wastewater effluent is big, dyeing salt is more, and environmental pollution is serious.Therefore the reactive dye of invention new construction
There is important meaning.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of H acid be bisazo double-active radical reactive brilliant bule color dyestuff and
Its preparation method and application, the dye shade are gorgeous, and degree of fixation is high, and fastness is good, and equilibrium time is short, direct high, can use
Dyeing and stamp in cellulose fiber peacekeeping protein fibre.
3,5- diaminourea -2, the anthraquinone derivative of 4,6- tri-methyl p-toluenesulfonate amino substitution is a cobalt blue intermediate,
But its affinity very little to fiber, it is reacted with three chlorotriazines, then reacted with m-phenylenediamine derivatives, form an anthracene
Then quinone system can be introduced into H acid systems with diazotizing intermediate by alkaline coupling, forms a very gorgeous gorgeous indigo plant
Color.
A kind of H acid of the invention is bisazo double-active radical reactive brilliant bule color dyestuff, and structural formula is：
Wherein, R1=-SO3Na
Or during H, R2=-H；R2During=- COONa, R1=-H；
Described H acid is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, including：
The preparation of (1) one contracting thing：Cyanuric Chloride is dispersed in mixture of ice and water, 0~15 DEG C of 3,5- bis- is then added dropwise
Amino -2, the anthraquinone derivative aqueous solution of 4,6- tri-methyl p-toluenesulfonate amino substitution, in pH=3~4.5, temperature is 0~15 DEG C
Under conditions of react 2~4h, the solution of a contracting thing is obtained for a contracting liquid, with thin-layer chromatography detection reaction end (solvent：Positive third
Alcohol：Isobutanol：Ethyl acetate：Water=2:4:1:3, above-mentioned is volume ratio)；
(2) preparation of two contracting things：2,4- diamino benzene sulfonic acids sodium or 3,5- diaminobenzoic acid sodium are added to step (1)
In a contracting liquid in, regulation pH be 3.5~5.5,3-5h is reacted under conditions of 30-45 DEG C, obtain two contracting things；
Or：2,4- diamino benzene sulfonic acids or 3,5- diaminobenzoic acid are added in the contracting liquid in step (1), used
Na2CO3Regulation pH is 3.5~5.5, and 3-5h is reacted under conditions of 30-45 DEG C, obtains two contracting things；
(3) preparation of diazol：Para-ester or meta ester is soluble in water, 0~15 DEG C is cooled to, concentrated hydrochloric acid is added,
Sodium nitrite solution is added dropwise, 0~15 DEG C of reaction 1-2h, reaction eliminates unnecessary nitrous acid, obtains weight after terminating with sulfamic acid
Nitrogen salt；
(4) acid coupling reaction：H acid is added in the diazol that step (3) is obtained, 10~25 DEG C of reaction 3-5h are obtained
To acid coupling product；
(5) diazo-reaction of two contracting things：The two contracting things that step (2) is obtained is soluble in water, is cooled to 0~15 DEG C, plus
Enter concentrated hydrochloric acid, sodium nitrite solution is added dropwise, 0~15 DEG C of reaction 1-2h, reaction eliminates unnecessary nitrous after terminating with sulfamic acid
Acid, obtains the diazol of two contracting things；
(6) alkaline coupling reaction：The diazol of the two contracting things obtained in step (5) is added to the acid that step (4) is obtained
Property coupling product in, 15-25 DEG C, 5-8h is reacted under conditions of pH=5-6.0, saltout, purify, dry, it is bisazo to obtain H acid
Double-active radical reactive brilliant bule color dyestuff.
The anthraquinone that Cyanuric Chloride replaces with 3,5- diaminourea -2,4,6- tri-methyl p-toluenesulfonates amino in the step (1) spreads out
Biological mass ratio is 18.4-20.24：52.62.
Reaction condition is preferred in the step (1)：0~5 DEG C, pH is 3~3.5.
2,4- diamino benzene sulfonic acids sodium or 3,5- diaminobenzoic acids sodium and 3,5- diaminourea -2,4 in the step (2),
The mass ratio of the anthraquinone derivative of 6- tri-methyl p-toluenesulfonates amino substitution is 21-23：53.15；The 2,4- diamino benzene sulfonic acids
Or the mass ratio of 3,5- diaminobenzoic acids and the anthraquinone derivative of 3,5- diaminourea -2,4,6- tri-methyl p-toluenesulfonates amino substitution
It is 21-23：53.15.
The structural formula of the anthraquinone derivative of 3,5- diaminourea -2,4,6- tri-methyl p-toluenesulfonates amino substitution is：
The manufacturer of the anthraquinone derivative of 3,5- diaminourea -2,4,6- tri-methyl p-toluenesulfonates amino substitution is：Platform
Advance Chemical Co., Ltd. of state city (25 kilograms of packagings).
Reaction condition is preferred in the step (2)：30~35 DEG C, pH is 4~4.5.
The mass ratio of para-ester or meta ester, concentrated hydrochloric acid and natrium nitrosum is 28.02-30.8 in the step (3)：
10：23.
The mass fraction of concentrated hydrochloric acid is 36.5% in the step (3), and the mass fraction of sodium nitrite solution is 30%.
H acid dry powder and the mass ratio of para-ester or meta ester are 34.1-37.5 in the step (4)：28.02.
The purchase producer of H acid is：Zhejiang Ji Hua Chemical Co., Ltd.s.
The mass ratio of two contracting things, concentrated hydrochloric acid and natrium nitrosum is 20.79 in the step (5)：20：23.
Reaction condition is preferred in the step (6)：15~20 DEG C, pH is 6.0.
Saltoutd in the step (6) for：The 10% of total liquid measure weighs KCl and is saltoutd at the end of by reaction, suction filtration, drying
Obtain crude product；The purification and drying process are：Above-mentioned gained crude product is dissolved in appropriate DMF (DMF), suction filtration,
Insoluble matter is filtered, filtrate is placed in ice bath, quickly to proper amount of acetone is poured into filtrate, there is Precipitation, suction filtration, vacuum is done
It is dry, obtain dyestuff sterling.
Described H acid is the application of bisazo double-active radical reactive brilliant bule color dyestuff, and the application is in cellulose fiber
The dyeing of the blend fabric of the dyeing of peacekeeping protein fibre and stamp or cellulose fiber peacekeeping protein fibre and stamp.
The reaction equation being related in the present invention：
(wherein, R1=-SO3Na and R2=H)
In the present invention, a contracting reaction is with two contracting reaction intermediates according to RNH2Determined with the size of Cyanuric Chloride respond
Fixed, the relatively weak elder generation of respond and Cyanuric Chloride carry out a contracting reaction, and respond is relatively strong then to be entered with a contracting thing
The contracting reaction of row two.
It is bisazo double-active radical reactive brilliant blue K-GR preparation method as the H acid replaced containing amino anthraquinones in the present invention
And application, according to a contracting, the difference of two contracting reaction intermediates, synthesis technique can also be order below：(1) para-ester diazol
Preparation；(2) H acid acid coupling reaction；The preparation of (3) one contracting things；(4) preparation of two contracting things；(5) diazotising of two contracting things；
(6) alkaline coupling reaction, (7) saltout；(8) purify.
Beneficial effect
(1) the cobalt blue reactive dye of the class new construction in the present invention, with double color development systems and double-active radical, color
It is very gorgeous；
(2) of the invention is bisazo double-active radical reactive brilliant bule color dyestuff as the H acid replaced containing amino anthraquinones, is prepared
Process is simple, synthesis is convenient, and yield is high；
(3) of the invention is bisazo double-active radical reactive brilliant bule color dyestuff, fixation as the H acid replaced containing amino anthraquinones
Rate is high, and fastness is good, and equilibrium time is short, direct high；
(4) of the invention is bisazo double-active radical reactive brilliant bule color dyestuff as the H acid replaced containing amino anthraquinones, can be used
Dyeing and stamp in cellulose fiber peacekeeping protein fibre；
(5) double-active radical reactive brilliant bule color dyestuff of the invention, it can also be used to cellulose fiber peacekeeping protein fibre it is mixed
The dyeing of yarn fabric and stamp.
Brief description of the drawings
Fig. 1 is the ultraviolet spectrogram of dyestuff prepared in embodiment 1；
Fig. 2 is the infrared spectrogram of dyestuff prepared in embodiment 1；
Fig. 3 is the nuclear magnetic resonance figures of dyestuff prepared in embodiment 1.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
It is related to pH regulations in embodiment and is Na2CO3Regulation.
Embodiment 1
The present embodiment prepares the dye structure (D-1) of para-ester acid coupling, and structural formula is as follows：
The preparation of (1) one contracting thing：18.4 parts of Cyanuric Chlorides are dispersed in 50 parts of mixture of ice and water in beaker.
Weigh 53.15 × 0.99 part 100% 3 .5- diaminourea -2,4,6- tri-methyl p-toluenesulfonates amino substitution anthraquinone derivative in
Mesosome, the water for being added thereto to 100 parts stirs, and is placed in and 0-5 DEG C is cooled in ice bath.By this 3 .5- diaminourea -2,4,6-
The anthraquinone derivative midbody solution of tri-methyl p-toluenesulfonate amino substitution is dropped in the Cyanuric Chloride in ice-water bath, in pH=
2h is reacted under the conditions of 3.5, T=5 DEG C, reaction end is detected with thin-layer chromatography, reaction equation is as follows.(solvent：Positive third
Alcohol：Isobutanol：Ethyl acetate：Water=2:4:1:3；Above-mentioned is volume ratio).
(2) preparation of two contracting things：The 2,4- diamino benzene sulfonic acids dry powder for weighing 21 × 0.99 part 100% adds a contracting liquid
In, the pH value of reaction solution is adjusted after adding 3.5, reaction temperature is controlled at 30 DEG C, and 5h is reacted at this temperature and pH value, with thin
Layer chromatography detects reaction end (solvent：Normal propyl alcohol：Isobutanol：Ethyl acetate：Water=2:4:1:3；Above-mentioned is volume ratio), it is standby
With.Reaction equation is as follows.
(3) preparation of para-ester diazol：By 100% 28.3 × 0.99 parts of para-ester (4- ethene sulfone sulfate ester aniline)
Plus a certain amount of water (50 parts) stirring to pulp is to uniform, it is placed in ice bath and is cooled to 0 DEG C, adds 10 parts of mass fractions to be
36.5% concentrated hydrochloric acid, the mass fraction that 23 parts of natrium nitrosum preparation is slowly added dropwise is 30% solution, carries out diazotising, temperature
It is 5 DEG C to spend, and reacts 1h.Reaction eliminates unnecessary nitrous acid after terminating with sulfamic acid.Reaction equation is as follows.
(4) acid coupling reaction：H 34.1 parts of the dry powder of acid for weighing 100% is directly added into above-mentioned diazol, temperature control
At 10 DEG C, 5h is reacted.Reaction end is detected with thin-layer chromatography.Reaction equation is as follows.
(5) diazo-reaction of two contracting things：The diazo-reaction of two contracting things and the preparation method of para-ester diazol, desalination
Sour consumption is the concentrated hydrochloric acid that 20 parts of mass fractions are 36.5%, and other are identical.
(6) alkaline coupling reaction：During the diazo-reaction of two contracting things is once added to for the first time with para-ester diazol
In sour idol liquid, temperature control is in 15 DEG C, pH=5 reactions 6h.
(7) saltout：The 10% of total liquid measure weighs KCl and is saltoutd at the end of by reaction, suction filtration, drying, obtains crude product.Carry
It is pure：Above-mentioned gained crude product is dissolved in appropriate DMF (DMF), suction filtration filters insoluble matter, filtrate is placed in into ice
Bath, quickly to proper amount of acetone is poured into filtrate, there is Precipitation, and suction filtration, vacuum drying obtains dyestuff sterling, yield 85.3%.Dye
The UV, visible light electronic of material, infrared spectrum and nuclear magnetic spectrum are as shown in FIG. 1 to 3.Wherein, the infrared number in Fig. 2
According to being IR (KBr, cm-1):3433,2346,1751,1630,1579,1483,1409,1341,1202,1044,896,638.Fig. 3
Middle nuclear magnetic data is：1H NMR (600MHz, DMSO) δ 10.69 (s, 2H), 8.27 (d, J=33.6Hz, 1H), 8.04-7.80
(m, 2H), 7.64 (s, 1H), 7.42 (d, J=50.4Hz, 1H), 7.24-6.92 (m, 1H), 6.66 (s, 1H), 5.32 (s, 1H),
3.76 (t, J=130.9Hz, 2H), 3.36 (s, 10H), 2.81 (d, J=96.0Hz, 4H), 2.66-2.53 (m, 1H), 2.39
(s, 1H), 2.06 (dd, J=81.8,34.2Hz, 2H), 1.59-1.04 (m, 2H), 0.85 (d, J=7.1Hz, 1H).
Gained dyestuff contaminates pure cotton fabric under the conditions of 60 DEG C, obtains bright-coloured beautiful cobalt blue, and every color fastness is excellent, such as
Shown in table 1.
The dyed fabric of table 1 items fastness properties
Embodiment 2
Acid coupling is carried out using 3- ethene sulfone sulfate ester aniline (meta ester), the dye structure (D-2) for obtaining, yield
83.7%, it is as follows：
Synthetic method changes the para-ester in raw material into meta ester with embodiment 1, and remaining reaction condition is with embodiment 1.
Dyestuff contaminates pure cotton fabric under the conditions of 60 DEG C, also obtains bright-coloured beautiful cobalt blue, and every color fastness is excellent, such as table
Shown in 2.
The dyed fabric of table 2 items fastness properties
Embodiment 3
Acid coupling is carried out using 4- ethene sulfone sulfate ester aniline (para-ester), two are carried out using 2,4- diaminobenzoic acids
Contracting, remaining reaction condition is with embodiment 1, and yield 87.9%, the dye structure for obtaining (D-3) is as follows：
Gained dyestuff contaminates pure cotton fabric under the conditions of 60 DEG C and also obtains bright-coloured beautiful cobalt blue, and every color fastness is excellent,
As shown in table 3.
The dyed fabric of table 3 items fastness properties
Embodiment 4
Acid coupling is carried out using 3- ethene sulfone sulfate ester aniline (meta ester), two are carried out using 2,4- diaminobenzoic acids
Contracting, remaining reaction condition is with embodiment 1, and yield 82.6%, the dye structure for obtaining (D-4) is as follows：
Gained dyestuff contaminates pure cotton fabric under the conditions of 60 DEG C, also obtains bright-coloured beautiful cobalt blue, and every color fastness is excellent,
As shown in table 4.
The dyed fabric of table 4 items fastness properties
Embodiment 5
Wool fabric is dyeed using product in embodiment 1, dyestuff dyeing wool fabric under the conditions of 60 DEG C is also obtained
Bright-coloured beautiful cobalt blue, every color fastness is excellent, as shown in table 5.
The dyed fabric of table 5 items fastness properties
Embodiment 6
Silk fabric is dyeed using product in embodiment 2, dyestuff contaminates silk fabric under the conditions of 60 DEG C, also obtains
Bright-coloured beautiful cobalt blue, every color fastness is excellent, as shown in table 6.
The dyed fabric of table 6 items fastness properties
Embodiment 7
Cotton/silk blend fabric (80/20) is dyeed using product in dye embodiments 1, dyestuff is in 60 DEG C of conditions
Lower dye cotton/silk blend fabric also obtains bright-coloured beautiful cobalt blue, and assorted item fastness is excellent, as shown in table 7.
The dyed fabric of table 7 items fastness properties
Embodiment 8
Using product in embodiment 2 and black 300 (the two kinds of mass ratios of dyestuff 1 of dispersion:1) to cotton/polyester blended fabric
(50/50) two bath dyeing are carried out, cotton/polyester blended fabric is first contaminated under the conditions of 60 degree, it is then mixed in 130 degree of resisdye cotton/terylene
Yarn fabric, also obtains bright-coloured beautiful cobalt blue, and every color fastness is excellent, as shown in table 8.
The dyed fabric of table 8 items fastness properties
The number being related in above-described embodiment is weight portion.
Be related in above-described embodiment fastness test standard be：《Textile color stability tests colour fastness to rubbing》
GB/T 3920—2008；《Textile color stability tests color fastness to washing》GB/T 3921.3—2008；《Textile color stability is tried
Test color fastness to hot pressing》GB/T 6152—1997；《Textile colour fastness to perspiration test method》GB/T 3922—2013.
Claims (10)
1. a kind of H acid is bisazo double-active radical reactive brilliant bule color dyestuff, and structural formula is：
Wherein, R1=-SO3Na
Or during H, R2=-H；R2During=- COONa, R1=-H；
2. a kind of H acid as claimed in claim 1 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, including：
The preparation of (1) one contracting thing：Cyanuric Chloride is dispersed in mixture of ice and water, then be added dropwise 0~15 DEG C 3,5- diaminourea-
The anthraquinone derivative aqueous solution of 2,4,6- tri-methyl p-toluenesulfonate amino substitution, in pH=3~4.5, temperature is 0~15 DEG C of condition
2~4h of lower reaction, the solution for obtaining a contracting thing is a contracting liquid；
(2) preparation of two contracting things：2,4- diamino benzene sulfonic acids sodium or 3,5- diaminobenzoic acid sodium are added in step (1)
In one contracting liquid, regulation pH is 3.5~5.5, and 3-5h is reacted under conditions of 30-45 DEG C, obtains two contracting things；
Or：2,4- diamino benzene sulfonic acids or 3,5- diaminobenzoic acid are added in the contracting liquid in step (1), use Na2CO3
Regulation pH is 3.5~5.5, and 3-5h is reacted under conditions of 30-45 DEG C, obtains two contracting things；
(3) preparation of diazol：Para-ester or meta ester is soluble in water, 0~15 DEG C is cooled to, concentrated hydrochloric acid is added, it is added dropwise
Sodium nitrite solution, 0~15 DEG C of reaction 1-2h, reaction eliminates unnecessary nitrous acid after terminating with sulfamic acid, obtains diazol；
(4) acid coupling reaction：H acid is added in the diazol that step (3) is obtained, 10~25 DEG C of reaction 3-5h obtain acid
Property coupling product；
(5) diazo-reaction of two contracting things：The two contracting things that step (2) is obtained is soluble in water, is cooled to 0~15 DEG C, adds dense
Hydrochloric acid, is added dropwise sodium nitrite solution, and 0~15 DEG C of reaction 1-2h, reaction eliminates unnecessary nitrous acid, obtains after terminating with sulfamic acid
To the diazol of two contracting things；
(6) alkaline coupling reaction：The diazol of the two contracting things obtained in step (5) is added to the acidity idol that step (4) is obtained
Close in product, 15-25 DEG C, 5-8h is reacted under conditions of pH=5-6.0, saltout, purify, dry, it is bisazo dual-active to obtain H acid
Property base reactive brilliant bule color dyestuff.
3. a kind of H acid according to claim 2 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, and it is special
Levy and be, Cyanuric Chloride and 3,5- diaminourea -2 in the step (1), the anthraquinone-derivative of 4,6- tri-methyl p-toluenesulfonate amino substitution
The mass ratio of thing is 18.4-20.24：52.62.
4. a kind of H acid according to claim 2 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, and it is special
Levy and be, 2,4- diamino benzene sulfonic acids or 3,5- diaminobenzoic acid and 3,5- diaminourea -2,4,6- front threes in the step (2)
The mass ratio of the anthraquinone derivative of base benzene sulfonic acid amino substitution is 21-23：53.15；The 2,4- diamino benzene sulfonic acids sodium or 3,
The mass ratio of the anthraquinone derivative that 5- diaminobenzoic acids sodium replaces with 3,5- diaminourea -2,4,6- tri-methyl p-toluenesulfonates amino is
21-23：53.15.
5. a kind of H acid according to claim 3 or 4 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, its
It is characterised by, 3,5- diaminourea -2, the structural formula of the anthraquinone derivative of 4,6- tri-methyl p-toluenesulfonate amino substitution is：
6. a kind of H acid according to claim 2 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, and it is special
Levy and be, the mass ratio of para-ester or meta ester, concentrated hydrochloric acid and natrium nitrosum is 28.02-30.8 in the step (3)：10：
23。
7. a kind of H acid according to claim 2 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, and it is special
Levy and be, the mass fraction of concentrated hydrochloric acid is 36.5% in the step (3), the mass fraction of sodium nitrite solution is 30%.
8. a kind of H acid according to claim 2 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, and it is special
Levy and be, H acid dry powder and the mass ratio of para-ester or meta ester are 34.1-37.5 in the step (4)：28.02.
9. a kind of H acid according to claim 2 is the preparation method of bisazo double-active radical reactive brilliant bule color dyestuff, and it is special
Levy and be, the mass ratio of two contracting things, concentrated hydrochloric acid and natrium nitrosum is 20.79 in the step (5)：20：23.
10. a kind of H acid as claimed in claim 1 is the application of bisazo double-active radical reactive brilliant bule color dyestuff, and its feature exists
In dyeing and stamp of the application in cellulose fiber peacekeeping protein fibre or its blend fabric.
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| CN111100478A (en) * | 2019-12-30 | 2020-05-05 | 浙江劲光实业股份有限公司 | Preparation method and application of blue dye with three active groups |
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| CN112625460A (en) * | 2020-12-18 | 2021-04-09 | 江南大学 | Preparation method of pH sensitive dye |
| CN112679980A (en) * | 2020-12-21 | 2021-04-20 | 江苏德美科化工有限公司 | High-performance double-color-body brilliant blue reactive dye and preparation method thereof |
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