CN109971209A - A kind of amino naphthol sulfonic acid class azo reactive dye and preparation method thereof - Google Patents
A kind of amino naphthol sulfonic acid class azo reactive dye and preparation method thereof Download PDFInfo
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- CN109971209A CN109971209A CN201910326395.7A CN201910326395A CN109971209A CN 109971209 A CN109971209 A CN 109971209A CN 201910326395 A CN201910326395 A CN 201910326395A CN 109971209 A CN109971209 A CN 109971209A
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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
- C09B62/78—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 with other reactive groups
- C09B62/82—Azo dyes
- C09B62/825—Monoazo dyes
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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
- C09B62/78—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 with other reactive groups
- C09B62/82—Azo dyes
- C09B62/83—Disazo or polyazo 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
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Abstract
The present invention relates to technical field of organic synthesis, more particularly, to a kind of amino naphthol sulfonic acid class azo reactive dye and preparation method thereof.The amino naphthol sulfonic acid class azo reactive dye has the structure of general formula (I), (II) or (III): Wherein, X is indicatedR1、R2、R3、R4And R5In at least one sulfonic group；Y1And Y2In one be selected from hydroxyl, another be selected from amino.The present invention cooperates amino naphthol sulfonic acid and its derivative and active group, the compound containing azo structure is prepared, by the introducing of-COF active group, can reduce the cloud density of dye matrix, be conducive to improve photostability of the dyestuff on fiber, improve light fastness.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly, to a kind of amino naphthol sulfonic acid class azo reactive dye
And preparation method thereof.
Background technique
Reactive dye are also known as chemically-reactive dyes, and contain in reactive dyestuff molecule such as cotton, hair, silk, can gather with by dye fiber
The active group of covalent bond is formed between phthalein amine fiber etc., thus, using reactive dyeing, there is excellent washable and antifriction
Wipe color fastness.In addition, reactive dye also have many advantages, such as that bright-colored, equalization is good, colouring method is convenient, chromatography is complete, because
This it be the maximum veriety of yield in cotton fiber dyestuff.
Occupy biggish ratio in reactive dye by the dyestuff of colour base of azo structure.Various amino naphthol sulfonic acids
It can be used as coupling component and be used to prepare azo reactive dye, since it is with good color, water solubility, occupy certain
The market share.But the dyestuff being prepared in the prior art using the coupling of the amino naphthol sulfonic acids such as H acid, γ acid, J acid is more prominent
The problem of be that light fastness is not high, to limit its application under the conditions of more demanding to light fastness.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of amino naphthol sulfonic acid class azo reactive dye, the dye composition
Structure is simple, and light fastness is good.
The second object of the present invention is to provide the preparation method of above-mentioned dyestuff, and the preparation method is easy to operate, reacts item
Part is mild, and yield is high.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of amino naphthol sulfonic acid class azo reactive dye, the structure with general formula (I), (II) or (III):
Wherein, X is indicatedR6、R7、R8And R9Be each independently selected from H, halogen, hetero atom replace or not
Substituted C1-20Alkyl；
R1、R2、R3And R4It is each independently selected from the substituted or unsubstituted C of H, halogen, sulfonic group, amino, hetero atom1-20Hydrocarbon
Base；
R5Selected from H, halogen, sulfonic group, amino, the substituted or unsubstituted C of hetero atom1-20Alkyl ,-N=N-X；
And R1、R2、R3、R4And R5In at least one sulfonic group；
Y1And Y2In one be selected from hydroxyl, another be selected from amino.
Preferably, work as R5When for-N=N-X, R5With Y2Positioned at ortho position or contraposition.
It is to be prepared by amino naphthol sulfonic acid and its derivative as coupling component in dyestuff of the invention, in amino
Introducing-COF active group, obtains the compound containing azo structure in the molecular structure of naphtholsulfonic acid and its derivative.Pass through
The introducing of acyl fluorides-COF active group, can reduce the cloud density of dye matrix, be conducive to improve dyestuff on fiber
Photostability, and then improve the light fastness of dye composition.
Also, in dye composition of the invention, when dyeing in alkaline medium, hydroxyl becomes negative oxygen ion (O-), it can
The electron-donating enhancing for making auxochrome, promotes the electronics in conjugated system more active, and intensifying can be smaller, so that absorption spectrum is to length
Wave direction is mobile, realizes hyperchromic effect.Simultaneously because in molecular structure the groups such as hydroxyl, amino and sulfonic group presence, make
Obtaining the compound has certain water solubility, and hydrophily is preferable.
In said structure, work as Y1When for hydroxyl, Y2For amino；Work as Y1When for amino, Y2For hydroxyl.
Active group-COF in the compound of the present invention has excellent binding performance with cellulose, is with chemical compounds I
Example is illustrated, and concrete principle is as follows:
Cell-OH indicates cellulose；
Fluorine has stronger nonmetal character, and the hydrogen fluoride stability that fluorine obtains in conjunction with hydrogen after leaving away is strong, promotes reaction
Forward direction carries out, so that compound be made sufficiently to be combined with cellulose.Also, the acyl fluorides group Molecule amount in the compounds of this invention is small,
Molecular weight is much smaller compared with the regular activated group such as s-triazine, ethyl sulfonyl sulfate, so that the dyestuff being prepared
Adduct molecule amount is small, and compared with existing regular activated dyestuff, under the premise of identical dye dosage, dyeing brightness is high, has
High dye utilization rate.
C1-20Alkyl such as methyl, ethyl, methylmethylene, propyl, isopropyl, butyl or its isomers, amyl or its is different
Structure body, hexyl or its isomers, nonyl or its isomers, decyl or its isomers, eicosyl or its isomers, vinyl or
Its isomers, acrylic or its isomers, cyclobutenyl or its isomers, pentenyl or its isomers, hexenyl or its isomers,
Icosa alkene alkyl or its isomers, benzyl or its isomers, phenylpropyl or its isomers, benzene butyl or its isomers, naphthalene first
Base or its isomers, or the hetero atom of the above alkyl replace, and hetero atom includes N, S, O, P etc., the C that hetero atom replaces1-20Hydrocarbon
Base such as methoxy alkyl, ethoxy alkyl etc..
In above compound structure, work as R5When for-N=N-X, R5With Y2Positioned at ortho position or contraposition, structural formula can be following
Several is any:
The present invention is further preferably as follows to each substituent group in above-mentioned general formula:
Preferably, in certain embodiments of the present invention, R1、R2、R3And R4It is each independently selected from H, halogen, sulfonic acid
Base, amino, C1-10The C that alkyl or hetero atom replace1-10Alkyl.
Preferably, in certain embodiments of the present invention, R1、R2、R3、R4And R5In there are two sulfonic group.It is furthermore preferred that
R5When for-N=N-X, R1、R2、R3、R4In there are two sulfonic group and two hydrogen.
In the present invention, in structure X, R6、R7、R8And R9Selected halogen can be fluorine, chlorine, bromine or iodine.
Preferably, in certain embodiments of the present invention, R6、R7、R8And R9It is each independently selected from H, halogen, C1-10Hydrocarbon
The C that base or hetero atom replace1-10Alkyl.
Preferably, in certain embodiments of the present invention, the structural formula that X is indicated can be with are as follows: Etc..
The present invention also provides above-mentioned amino naphthol sulfonic acid class azo reactive dyes (I), (II) or (III) mainly to pass through
Following synthetic routes are prepared:
After diazo-reaction, withOrCoupling reaction is carried out, corresponding compound (I), (II) or (III) is obtained.
Amino-compound is changed into diazenium compound by diazo-reaction, coupling reaction be diazenium compound and phenol or
Amine is coupled to form corresponding compound.
Preferably, the condition of diazo-reaction are as follows: under the action of acid and diazo reagent,It carries out
Diazo-reaction.
The acid that diazo-reaction uses preferably includes any one of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, diazo reagent
For nitrite.
Above-mentioned diazo-reaction carries out at low temperature.Preferably, the temperature of diazo-reaction is 0-20 DEG C.It is furthermore preferred that
The temperature of diazo-reaction is 0-5 DEG C.
The condition of coupling reaction is preferred are as follows: under alkaline condition, the diazo-reaction product obtained after diazo-reaction
WithCarry out coupling reaction.
Coupling reaction preferably carries out under cryogenic.Preferably, the temperature of coupling reaction is 0-20 DEG C.It is furthermore preferred that
The temperature of coupling reaction is 0-5 DEG C.
Preferably, when carrying out twice or when coupling reaction more than twice, first time coupling reaction is in the item that pH is 4.0-6.9
It is carried out under part, second of coupling reaction carries out under conditions of pH is 7.1-9.0.
The reaction raw materials ratio of coupling reaction can be adjusted according to coupling reaction number, when being only coupled one time, coupling
Component and the ratio of diazo component are 1:1；When being coupled twice, the ratio of coupling component and diazo component is 1:2；As coupling n
When secondary, the ratio of coupling component and diazo component is 1:n.
Specifically, if pH is 4.0-6.9, coupling reaction occurs in-NH when the pH of coupling reaction is faintly acid2Place
- NH on phenyl ring2Ortho position；When your pH of coupling reaction is alkalescent, if pH is 7.1-9.0, coupling reaction occurs in-OH institute
The ortho position-OH on phenyl ring.For secondary coupling, coupling carries out in weak acidic medium for the first time, first in-NH2Ortho attack
Coupling reaction occurs, is then coupled in alkaline medium again, the ortho position second made azo group attack-OH.
It, can be using different media as molten for the dyestuff of water-soluble and non-aqueous type when carrying out coupling reaction
Agent, for water-soluble type dye, using aqueous medium, preferably distilled water；It is excellent using organic media for non-aqueous type dye
It is selected as acetone, tetrahydrofuran etc..
Compound for coupling reactionOrThe compound that can be used can be for Etc..
Raw material involved in above-mentioned preparation methodCommercially available product can be used, or be prepared by the following method
It obtains:
A) acyl chloride reaction occurs for compounds Ⅳ, obtains compound V；
B) compound V is reacted with fluorization agent, obtains compound VI；
C) compound VI sloughs protecting group, obtains compound
Wherein, each structural formula of compound is as follows:
R be amide groups or alkoxycarbonyl amido,
Preferably, the chloride reagent of the acyl chloride reaction in step a) be phosphorus trichloride, phosphorus pentachloride, thionyl chloride,
One of sulfuryl chloride, chlorine, hydrogen chloride and phosgene are a variety of.
Preferably, the fluorization agent used in step b) includes NH4F、LiF、NaF、KF、CsF、AgF、SbF3、BrF3、MnF3、
CuF、(CH3)4NF and its hydrochlorate or (C4H9)4One of NF and its ackd salt or a variety of.
Preferably, in step c), when R is amide groups, the reactive mode for sloughing protecting group is that compound VI is placed in acid
It is hydrolyzed under the conditions of property, the temperature of hydrolysis is preferably 20-200 DEG C, the preferred 0.1-48h of hydrolysis time；When R is alkoxycarbonyl amido
When, the reactive mode for sloughing protecting group is that compound VI is carried out catalytic hydrogenolysis or reduction reaction etc..In catalytic hydrogenolysis process
In, use H2Or other hydrogen donors, it may be selected to hydrogenate at normal temperatures and pressures.When in molecule exist it is sensitive to catalytic hydrogenolysis or passivation
When the group of catalyst, acid cleavage or restoring method are more applicable.Meanwhile to avoid generating by-product, for acidolysis cracking
Acid is preferably HBr etc..
Compared with prior art, the invention has the benefit that
(1) the compound of the present invention cooperation amino naphthol sulfonic acid and its derivative and active group, be prepared containing
The compound of azo structure can reduce the cloud density of dye matrix by the introducing of-COF active group, be conducive to mention
Photostability of the high dyestuff on fiber；
(2) the compound of the present invention has excellent binding performance with cellulose as dyestuff, with excellent light jail
Degree；
(3) preparation method of the compound of the present invention is easy to operate, and reaction condition is mild, high income.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the compound that the embodiment of the present invention 1 synthesizesNuclear-magnetism F spectrogram；
Fig. 2 is the compound that the embodiment of the present invention 1 synthesizesIR Characterization map；
Fig. 3 is the compound that the embodiment of the present invention 7 synthesizesIR Characterization map.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment and attached drawing, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1-6
Embodiment 1-6 provides 6 kinds of different structuresPreparation method, include the following steps:
1) by compounds Ⅳ, 1 ﹕ 1 is added in reaction kettle in molar ratio with thionyl chloride, is warming up to 120-130 DEG C, in stirring
Reaction 12-14h is carried out under the conditions of mixing, and obtains compound V；Hydrogen chloride and sulfur dioxide gas for generating in reaction process etc. are logical
It crosses vacuum pump and is evacuated in slot containing alkali and handle；
2) it by after the drying of compound V obtained in step 1), is added in reaction kettle, dissolution in advance is added into reaction kettle
The sodium fluoride of Yu Shuizhong, after being warming up to 70-80 DEG C, reaction 1-6h (reaction time can monitor by TLC) is changed
Close object VI；Wherein, the molar ratio of sodium fluoride and compound V is 1 ﹕ (1.5-3), can be according to the extent of reaction and production in practical operation
Rate is adjusted；
3) it by after the drying of compound VI obtained in step 2), is added in reaction kettle, hydrochloric acid solution is added thereto, heat
To 40-80 DEG C, be hydrolyzed reaction under stirring condition, mixing speed 1000-1500rpm, when in reaction system without precipitating
When object, the centrifuged supernatant in reaction system is taken, with alkalimetric titration, is largely settled out current, stopping reaction when having.It is done after filtering
It is dry, obtain target product.
Wherein, it the compounds Ⅳ that is used in above-mentioned steps, compound V, compound VI and obtains
Structural formula it is as shown in table 1 below:
1 part of compounds structural formula of table
Wherein, compoundNuclear-magnetism F spectrum and infared spectrum difference it is as illustrated in fig. 1 and 2.Other realities
It applies each structure of example and has carried out structural characterization also by nuclear-magnetism F spectrum and infared spectrum, this will not be repeated here.
Embodiment 7-12
Embodiment 7-12 provides the method for synthetic dyestuffs, and synthetic route is as follows:
The synthetic route of chemical compounds I are as follows:
The synthetic route of compound ii are as follows:
The synthetic route of compound III are as follows:
Wherein, first step reaction is diazo-reaction, and second step reaction is coupling reaction；It is only carried out in second step reaction
The component raw material (compound J, compound K, compound L) of coupling is different.
Each raw material compound and intermediate compound structure employed in embodiment 7-12 are as shown in table 2 below:
The structural formula of 2 embodiment 7-12 part of compounds of table
The reaction process of the various embodiments described above is as follows:
Embodiment 7
The first step, diazotising:
The 4- aminobenzoic acyl fluorides for taking 139g dry is raw material, is added into 1L alcohol, after the dilution of 1L water is then added, is added
Enter 40mL concentrated hydrochloric acid (36%), slightly excessive 23%NaNO is added under conditions of 0 DEG C2Solution carries out weight under the conditions of 0-5 DEG C
Nitridation reaction measures reaction end with starch KI test paper.
Second step, coupling:
It takes and 4- aminobenzoic acyl fluorides equimolar ratio in diazotation stepUse NH4Cl adjustment
The diazotising liquid that the first step obtains slowly is added thereto, in 0-5 DEG C of item by medium pH to faintly acid 5.5-6.5 under the conditions of 0 DEG C
40min is reacted under part.After reaction, it saltouts filtering, solid is dried at 40 DEG C or less, obtains dyestuffYield is 88%.
To compoundStructure characterized by infared spectrum, as shown in Figure 3.Remaining each reality
The structure for applying example has also carried out infared spectrum characterization, does not repeat below.
Embodiment 8
The first step, diazotising:
The 3- aminobenzoic acyl fluorides for taking 139g dry is raw material, is added into 1L alcohol, after the dilution of 1L water is then added, is added
Enter 40mL concentrated hydrochloric acid (36%), slightly excessive 23%NaNO is added under conditions of 0 DEG C2Solution carries out weight under the conditions of 0-5 DEG C
Nitridation reaction measures reaction end with starch KI test paper.
Second step, primary coupling:
It takes and 3- aminobenzoic acyl fluorides equimolar ratio in diazotation stepUse NH4Cl adjustment
The diazotising liquid that the first step obtains slowly is added thereto, in 0-5 DEG C of item by medium pH to faintly acid 5.5-6.5 under the conditions of 0 DEG C
40min is reacted under part.
Third step, secondary coupling:
In the same manner, the reaction solution of previous step is added to and uses Na2CO3Adjust medium pH to alkalescent 7.5-8.5
Medium in, add the 3- aminobenzoic acyl fluorides with second step (primary coupling) same amount, reacted under the conditions of 0-5 DEG C
40min.After reaction, it saltouts filtering, solid is dried at 40 DEG C or less, obtains dyestuffYield is 81%.
Embodiment 9
The preparation method of the dye composition of the preparation method reference implementation example 7 of the dye composition of embodiment 9, difference is only
It is:
4- aminobenzoic acyl fluorides replaces with 3- amino-4-methoxyl benzoyl fluoride, willReplacement
ForNH will be used4Cl adjustment medium pH to faintly acid 5.5-6.5 is changed to use Na2CO3Adjust medium pH
To alkalescent 7.5-8.5, dyestuff is obtainedYield is 83%.
Embodiment 10
The preparation method of the dye composition of the preparation method reference implementation example 7 of the dye composition of embodiment 10, difference
It is only that:
4- aminobenzoic acyl fluorides replaces with 2- amino -4- fluorobenzoyl fluorine, willIt replaces withNH will be used4Cl adjustment medium pH to faintly acid 5.5-6.5 is changed to use Na2CO3Medium pH is adjusted to alkalescent
7.5-8.5 obtaining dyestuffYield is 81%.
Embodiment 11
The preparation method of the dye composition of the preparation method reference implementation example 7 of the dye composition of embodiment 11, difference
It is only that:
4- aminobenzoic acyl fluorides replaces with 3- amino -5- eicosyl benzoyl fluoride, will use NH4Cl adjusts medium pH to weak
Acid 5.5-6.5 is changed to use Na2CO3Medium pH is adjusted to alkalescent 7.5-8.5, obtains dyestuffYield is 82%.
Embodiment 12
The preparation method of the dye composition of the preparation method reference implementation example 7 of the dye composition of embodiment 12, difference
It is only that:
4- aminobenzoic acyl fluorides replaces with 3- amino-4-methoxyl benzoyl fluoride, willReplacement
ForNH will be used4Cl adjustment medium pH to faintly acid 5.5-6.5 is changed to use Na2CO3Adjust medium pH
To alkalescent 7.5-8.5, dyestuff is obtainedYield is 85%.
Comparative example
Comparative example 1-6 is reactive dye in the prior art, fabric after listing its dye structure in table 3 respectively and dyeing
Fastness ability.
Table 3 is containing the fastness ability after the fluorine-based amino naphthol sulfonic acid class azo reactive dye dyed fabric of sulphonyl
Experimental example
For the dyeing property of the dyestuff of the comparative illustration embodiment of the present invention, the dyestuff that embodiment is prepared is to fabric
The fastness ability of dyeing carries out test test result the following table 4:
Fastness ability after the Fabrics Dyed with Reactive Dyes of the different embodiments of table 4
Wherein, fastness ability test is referring to existing data in existing literature, in fact to the dyestuff of comparative example 1-6 on the fabric
Apply the dyestuff of a 7-12 on the fabric fastness ability test referring to national standard: where the measurement of fastness to light is referring to GB/
T8426--1998: " textile color stability tests color fastness to light: daylight ".
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of amino naphthol sulfonic acid class azo reactive dye, which is characterized in that the knot with general formula (I), (II) or (III)
Structure:
Wherein, X is indicatedR6、R7、R8And R9It is substituted or unsubstituted to be each independently selected from H, halogen, hetero atom
C1-20Alkyl；
R1、R2、R3And R4It is each independently selected from the substituted or unsubstituted C of H, halogen, sulfonic group, amino, hetero atom1-20Alkyl；
R5Selected from H, halogen, sulfonic group, amino, the substituted or unsubstituted C of hetero atom1-20Alkyl ,-N=N-X；
And R1、R2、R3、R4And R5In at least one sulfonic group；
Y1And Y2In one be selected from hydroxyl, another be selected from amino.
2. amino naphthol sulfonic acid class azo reactive dye according to claim 1, which is characterized in that work as R5For-N=N-X
When, R5With Y2Positioned at ortho position or contraposition.
3. amino naphthol sulfonic acid class azo reactive dye according to claim 2, which is characterized in that the knot of the dyestuff
Structure formula includes the following:
4. amino naphthol sulfonic acid class azo reactive dye according to claim 1, which is characterized in that R1、R2、R3、R4With
R5In there are two sulfonic group.
5. amino naphthol sulfonic acid class azo reactive dye according to claim 4, which is characterized in that work as R5For-N=N-X
When, R1、R2、R3、R4In there are two sulfonic group and two hydrogen.
6. amino naphthol sulfonic acid class azo reactive dye according to claim 1-5, which is characterized in that X table
The structural formula shown is any one of following:
7. the preparation method of amino naphthol sulfonic acid class azo reactive dye described in any one of claims 1-6, feature exist
In including the following steps:
After diazo-reaction, with Carry out coupling reaction, obtain the amino naphthol sulfonic acid class azo reactive dye (I), (II) or
(Ⅲ)。
8. the preparation method of amino naphthol sulfonic acid class azo reactive dye according to claim 7, which is characterized in that institute
State the condition of diazo-reaction are as follows: under the action of acid and diazo reagent,Carry out diazo-reaction；
Preferably, the temperature of the diazo-reaction is 0-20 DEG C.
9. the preparation method of amino naphthol sulfonic acid class azo reactive dye according to claim 7, which is characterized in that institute
State the condition of coupling reaction are as follows: the diazo-reaction product that is obtained after diazo-reaction withCarry out coupling reaction；
Preferably, the temperature of the coupling reaction is 0-20 DEG C.
10. the preparation method of amino naphthol sulfonic acid class azo reactive dye according to claim 9, which is characterized in that
When carrying out twice or when coupling reaction more than twice, first time coupling reaction carries out under conditions of pH is 4.0-6.9, and second
Coupling reaction carries out under conditions of pH is 7.1-9.0.
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|---|---|---|---|---|
| GB790797A (en) * | 1955-07-23 | 1958-02-19 | Ciba Ltd | New fat-soluble azo-dyestuffs and process for their manufacture |
| US4142901A (en) * | 1976-11-12 | 1979-03-06 | Eastman Kodak Company | Photographic materials comprising azo sensitizing dyes |
| CN1730565A (en) * | 2005-08-30 | 2006-02-08 | 大连理工大学 | Black and active dye |
| CN103408961A (en) * | 2013-05-31 | 2013-11-27 | 中国科学院福建物质结构研究所 | Dye for supercritical carbon dioxide dying and preparation and application of dye |
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2019
- 2019-04-23 CN CN201910326395.7A patent/CN109971209B/en active Active
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| US4142901A (en) * | 1976-11-12 | 1979-03-06 | Eastman Kodak Company | Photographic materials comprising azo sensitizing dyes |
| CN1730565A (en) * | 2005-08-30 | 2006-02-08 | 大连理工大学 | Black and active dye |
| CN103408961A (en) * | 2013-05-31 | 2013-11-27 | 中国科学院福建物质结构研究所 | Dye for supercritical carbon dioxide dying and preparation and application of dye |
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