CN106349745A - Activated azo dye and preparation method and application thereof - Google Patents
Activated azo dye and preparation method and application thereof Download PDFInfo
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- CN106349745A CN106349745A CN201610734390.4A CN201610734390A CN106349745A CN 106349745 A CN106349745 A CN 106349745A CN 201610734390 A CN201610734390 A CN 201610734390A CN 106349745 A CN106349745 A CN 106349745A
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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
- D06P3/58—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
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
The invention relates to an activated azo dye; a structural unit of the activated azo dye contains a plurality of fiber activated groups, particularly fiber activated groups on dye intermediates, the dye has better color-fixing capacity, the color-fixing rate is higher than that of common activated dyes, and good color fastness can be achieved after the dye fixes the color on the surface of fabric; the invention also relates to a preparation method and application of the activated azo dye.
Description
Technical field
The present invention relates to the synthesis field of dyestuff is and in particular to a kind of reactive azo dyes and its preparation method and application.
Background technology
In recent years, reactive dye are bright in colour because of it, and chromatograph is complete, and application is convenient, fastness is excellent and be subject to more and more wider
General concern.Traditional activated azo dye poor color fastness, dye fixing rate is low, and dye-uptake is low, poor solubility, mixes with other dyestuffs
During spelling, compatibility is poor, is extremely restricted in application process, and dyestuff dye-uptake is low will necessarily to produce the organic of high cod high chroma
Waste water, all can cause severe contamination to water body and air.
The reactive dye having 60-70% in the market are all with para-ester as raw material, have and cellulose fiber in para-ester
The reactive group of dimension, is referred to as fixation group, but can produce parachloroanilinum by-product in para-position Lipase absobed, parachloroanilinum is
One of 24 kinds of disabling aromatic amine compounds, disabling specified in oeko-tex standard 100 " Oeko-Tex Standard l00 "
It is more serious that aromatic amine remains more health hazards to harm people in dyestuff, and environment be will also result in very big shadow simultaneously
Ring.
Chinese patent cn200610051936.9, cn200710070412.2 and cn201410032097.4 have been disclosed for
Several reactive dye, by para-ester and sulfonation para-ester diazotising, are then obtained with dyestuff intermediate coupling reaction, but knot
In structure, the active group quantity of dyestuff and relatively other radical position joint effect, lead to the dyeing on cellulose fibre or print
Flower poor-performing.
Content of the invention
Present invention aims to the deficiencies in the prior art, provide a kind of reactive azo dyes and preparation method thereof and
Application, contains multiple fibrous active radicals in the construction unit of reactive azo dyes, especially has fiber on dyestuff intermediate
So that dyestuff has more preferable fixation ability, degree of fixation is higher than general reactive dye to active group, and dyestuff is in fabric face
Good color fastness is can get after fixation.
Technical scheme provided by the present invention is:
A kind of reactive azo dyes, the construction unit containing formula (1) or (2),
Wherein, y1、y2And y3It is expressed as-ch independently of each other2ch2oso3M ,-ch=ch2、-ch2ch2Oh or-
ch2ch2opo3m；M is h, na, li or k；
d1、d2、d4And d5It is expressed as one of group of benzene or naphthalene system diazo component independently of each other；
d3It is expressed as the group of aromatics bisazo component.
In technique scheme, the dyestuff intermediate in construction unit (1) or (2) introduces-ch2ch2oso3m、-ch
=ch2、-ch2ch2Oh or-ch2ch2opo3M group is so that reactive azo dyes have more preferable fixation ability, this dyestuff and fibre
Cellulose fiber has the characteristics that the dye-uptake better than like product and degree of fixation during being combined into chemical bond, improves further
Dye utilization rate, reduces and produces integrated cost.
Preferably, described d1、d2、d4And d5It is expressed as the group of formula (3) or (4) independently of each other,
Wherein, r1-r6Be expressed as independently of each other hydrogen, hydroxyl, amino, carboxyl, methyl, ethyl, methoxyl group, acetylamino,
Nitro, beta-hydroxyethyl sulfuryl sulfate group, β-hydroxyalkyl vinyl sulfuryl, propionamido-, urea groups, sulfonic group, sulphur methyl, halogen atom, c1-
c4Alkyl, c1-c4Alkoxyl or c2-c4Alkanoylamino；
In formula (3), phenyl ring contains one or more r1-r3Substituent group, and at least contain an active group, described activity
Group is-so2ch2ch2oso3m、-so2Ch=ch2、-so2ch2ch2Oh or-so2ch2ch2opo3m；M is h, na, li or k；
In formula (4), naphthalene nucleus contains one or more r4-r6Substituent group, and at least contain a sulfonic group.
Described d1、d2、d4And d5It is expressed as one of group independently of each other:
Preferably, described d1、d2、d4And d5It is expressed as the group of formula (5)～(10) independently of each other,
Wherein, formula (8) is expressed as one of o-, m-, p-aminobenzene sulfonic acid.
Preferably, described d3It is expressed as such as the group of formula (11),
Wherein, r7And r8It is expressed as c independently of each other1-c4Alkyl, c1-c4Alkoxyl, c2-c4Alkanoyl sulfonic group, halogen
Or carboxyl；
r9It is expressed as-ch=ch- ,-nh- ,-co- ,-nh-co- ,-nh-so2- ,-nh-co-nh- ,-o- ,-s- or-so2-.
Preferably, described d3It is expressed as the group of formula (12), (13) or (14),
The present invention provides a kind of preparation method of above-mentioned reactive azo dyes it is characterised in that comprising the steps:
1) arylamine a is dispersed in water, adds sodium nitrite in aqueous solution in acid condition, control 0 DEG C～10 DEG C of temperature
Carry out the first diazo-reaction, obtain arylamine a diazol；Described arylamine a is the arylamine containing formula (3) or (4) group；
2) dyestuff intermediate b is added to step 1) in a diazol that obtains, control ph1～5 to carry out the first coupling anti-
Should, obtain a coupling solution；
Described dyestuff intermediate b contains following construction unit:
Wherein, y is expressed as-ch2ch2oso3M ,-ch=ch2、-ch2ch2Oh or-ch2ch2opo3m；M is h, na, li or k；
3) arylamine c is dispersed in water, adds sodium nitrite in aqueous solution in acid condition, control 0 DEG C～10 DEG C of temperature
Carry out the second diazo-reaction, obtain arylamine c diazol；Described arylamine c is the arylamine containing formula (3), (4) or (11) group；
4) by step 3) the arylamine c diazol that obtains is added to step 2) in a coupling solution obtaining, control ph5～9
Carry out the second coupling reaction, obtain described reactive azo dyes.
In described diazo process, mineral acid and sodium nitrite consumption are typically slightly above arylamine；Preferably, mineral acid is
Hydrochloric acid, and consumption is hydrochloric acid: arylamine=2.5:1.0 (when arylamine contains more than one sulfonic acid group, hydrochloric acid consumption reduces on year-on-year basis), sub-
Sodium nitrate: arylamine=1.01:1.0.
The present invention also provide a kind of above-mentioned reactive azo dyes to dye on cellulose fibre or stamp application.Described work
Property azo dye is preferred for dyeing or the stamp of cotton, introduces-ch due on dyestuff intermediate2ch2oso3M ,-ch=ch2、-
ch2ch2Oh or-ch2ch2opo3M group, degree of fixation is higher than general reactive dye, and dyestuff can obtain after fabric face fixation
To more preferable color fastness.
Compared with the existing technology, beneficial effects of the present invention are embodied in:
(1) in the present invention, dyestuff intermediate process obtains formula (1) or (2) structure with coupling of diazol, secondary coupling
The reactive azo dyes of unit, introduce-ch due on dyestuff intermediate2ch2oso3M ,-ch=ch2、-ch2ch2Oh or-
ch2ch2opo3M group, dyestuff is combined more stable with cellulose fibre, and the color fastness on fabric is obviously improved.
(2) reactive azo dyes in the present invention are black with red, dark blue component dye spelling has splendid compatibility, compounds
Reactive black dye afterwards is obtained in that enough depth in fabric face, especially has splendid crow in fabric face containing gossypin
Blackness, excellent color fastness, there is good application performance.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
(1) sulfonation para-ester diazonium
Accurately weigh 36.1 grams of sulfonation para-ester of percentage amount in 1000ml four-hole boiling flask, ice mill making beating 30min, observes sulphur
Change para-ester beating resultses, granule uniformly tiny rear 12.78 grams of 30% hydrochloric acid of addition, stirs 10min, is added dropwise over thereto
30% 23.23 grams of sodium nitrite, first quick and back slow, sodium nitrite finishes rate of addition, controls temperature 8-10 DEG C, stirring reaction 1-
1.5h, obtains sulfonation para-ester diazol.
(2) couplings
Sulfonation para-ester diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, adds a little in diazol
Trash ice, 29.6 grams of 2,4- diaminourea of percentage amount-beta-hydroxyethyl sulfone sulfate pressed powder is quickly put into sulfonation para-ester diazonium
In salt, within controlling 10 DEG C of temperature, ph1-3, stirring reaction 4h.
(3) para-ester diazonium
Accurately weigh 28.1 grams of para-esters of percentage amount in 500ml four-hole boiling flask, ice mill making beating 30min, add 30% salt
Acid 12.78 grams, stir 10min, be added dropwise over 23.23 grams of 30% sodium nitrite thereto, rate of addition first quick and back slow, nitrous acid
Sodium finishes, and controls temperature 5-8 DEG C, stirring reaction 1-1.5h, obtains para-ester diazol.
(4) secondary coupling
Para-ester diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, by reach home coupling solution
Adjust ph to 4 with sodium bicarbonate, by para-ester diazol to entering in a coupling solution, finish, adjust ph5.5- with the sodium bicarbonate of technique amount
8.0, control temperature 8-12 DEG C, stirring reaction 3h, obtain azo dye oleo stock.
The structural formula of the reactive azo dyes that embodiment 1 obtains is as follows:
Embodiment 2
(1) 2- amino naphthalenes -1,5- disulfonic acid diazonium
Accurately weigh 30.33 grams of 2- amino naphthalenes -1 of percentage amount, 5- disulfonic acid in 1000ml four-hole boiling flask, pull an oar by ice mill
30min, observes 2- amino naphthalenes -1,5- disulfonic acid beating resultses, granule uniformly tiny rear 12.78 grams of 30% hydrochloric acid of addition, stirring
10min, is added dropwise over 23.23 grams of 30% sodium nitrite thereto, and first quick and back slow, sodium nitrite finishes rate of addition, controls temperature
3-5 DEG C of degree, stirring reaction 1-1.5h, obtain 2- amino naphthalenes -1,5- disulfonic acid diazol.
(2) couplings
2- amino naphthalenes -1,5- disulfonic acid diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, in diazol
Add a little trash ice, 19.8 grams of 2,4- diaminourea-β of percentage amount-hydroxyalkyl vinyl sulfone pressed powder is quickly put into 2- amino naphthalenes -1,5-
In disulfonic acid diazol, control temperature 5-10 DEG C, ph1-3, stirring reaction 4h.
(3) para-ester diazonium
Accurately weigh 28.1 grams of para-esters of percentage amount in 500ml four-hole boiling flask, ice mill making beating 30min, add 30% salt
Acid 12.78 grams, stir 10min, be added dropwise over 23.23 grams of 30% sodium nitrite thereto, rate of addition first quick and back slow, nitrous acid
Sodium finishes, and controls temperature 5-8 DEG C, stirring reaction 1-1.5h, obtains para-ester diazol.
(4) secondary coupling
Para-ester diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, by reach home coupling solution
Adjust ph to 4 with sodium bicarbonate, by para-ester diazol to entering in a coupling solution, finish, adjust ph5.5- with the sodium bicarbonate of technique amount
8.0, control temperature 8-10 DEG C, stirring reaction 3h, obtain azo dye oleo stock.
The structural formula of the reactive azo dyes that embodiment 2 obtains is as follows:
Embodiment 3
(1) 2- amino naphthalenes -1,5- disulfonic acid diazonium
Accurately weigh 30.33 grams of 2- amino naphthalenes -1 of percentage amount, 5- disulfonic acid in 1000ml four-hole boiling flask, pull an oar by ice mill
30min, observes 2- amino naphthalenes -1,5- disulfonic acid beating resultses, granule uniformly tiny rear 12.78 grams of 30% hydrochloric acid of addition, stirring
10min, is added dropwise over 23.23 grams of 30% sodium nitrite thereto, and first quick and back slow, sodium nitrite finishes rate of addition, controls temperature
3-5 DEG C of degree, stirring reaction 1-1.5h, obtain 2- amino naphthalenes -1,5- disulfonic acid diazol.
(2) couplings
2- amino naphthalenes -1,5- disulfonic acid diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, in diazol
Add a little trash ice, 29.6 grams of 2,4- diaminourea of percentage amount-beta-hydroxyethyl sulfone sulfate pressed powder is quickly put into 2- amino
Naphthalene -1, in 5- disulfonic acid diazol, within controlling 10 DEG C of temperature, ph1-3, stirring reaction 4h.
(3) para-ester diazonium
Accurately weigh 28.1 grams of para-esters of percentage amount in 500ml four-hole boiling flask, ice mill making beating 30min, add 30% salt
Acid 12.78 grams, stir 10min, be added dropwise over 23.23 grams of 30% sodium nitrite thereto, rate of addition first quick and back slow, nitrous acid
Sodium finishes, and controls temperature 5-8 DEG C, stirring reaction 1-1.5h, obtains para-ester diazol.
(4) secondary coupling
Para-ester diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, by reach home coupling solution
Adjust ph to 4 with sodium bicarbonate, by para-ester diazol to entering in a coupling solution, pot is finished, adjusted with the sodium bicarbonate of technique amount
Ph5.5-8.0, controls temperature 8-12 DEG C, stirring reaction 3h, obtains azo dye oleo stock.
The structural formula of the reactive azo dyes that embodiment 3 obtains is as follows:
Embodiment 4
(1) sulfonation para-ester diazonium
Accurately weigh 72.2 grams of sulfonation para-ester of percentage amount in 1000ml four-hole boiling flask, ice mill making beating 30min, observes sulphur
Change para-ester beating resultses, granule uniformly tiny rear 25.56 grams of 30% hydrochloric acid of addition, stirs 10min, is added dropwise over thereto
30% 46.46 grams of sodium nitrite, first quick and back slow, sodium nitrite finishes rate of addition, controls temperature 8-10 DEG C, stirring reaction 1-
1.5h, obtains sulfonation para-ester diazol.
(2) couplings
Sulfonation para-ester diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, adds a little in diazol
Trash ice, 59.2 grams of 2,4- diaminourea of percentage amount-beta-hydroxyethyl sulfone sulfate pressed powder is quickly put into sulfonation para-ester diazonium
In salt, within controlling 10 DEG C of temperature, ph1-3, stirring reaction 4h.
(3) 4,4 '-diamino-diphenylamine diazonium
Accurately weigh percentage amount 19.93 gram 4,4 '-diamino-diphenylamine in 500ml four-hole boiling flask, pull an oar by ice mill
30min, adds 25.56 grams of 30% hydrochloric acid, stirs 10min, is added dropwise over 46.46 grams of 30% sodium nitrite, Deca speed thereto
First quick and back slow, sodium nitrite finishes degree, controls temperature 5-8 DEG C, stirring reaction 1-1.5h, obtains 4,4 '-diamino-diphenylamine weight
Nitrogen salt.
(4) secondary coupling
4,4 '-diamino-diphenylamine diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, by reach home
One time coupling solution adjusts ph to 4 with sodium bicarbonate, by 4,4 '-diamino-diphenylamine diazol to entering in a coupling solution, finishes, recruitment
The sodium bicarbonate of skill amount adjusts ph5.5-8.0, controls temperature 8-12 DEG C, stirring reaction 3h, obtains azo dye oleo stock.
The structural formula of the reactive azo dyes that embodiment 4 obtains is as follows:
Embodiment 5
(1) sulfonation para-ester diazonium
Accurately weigh 72.2 grams of sulfonation para-ester of percentage amount in 1000ml four-hole boiling flask, ice mill making beating 30min, observes sulphur
Change para-ester beating resultses, granule uniformly tiny rear 25.56 grams of 30% hydrochloric acid of addition, stirs 10min, is added dropwise over thereto
30% 46.46 grams of sodium nitrite, first quick and back slow, sodium nitrite finishes rate of addition, controls temperature 8-10 DEG C, stirring reaction 1-
1.5h, obtains sulfonation para-ester diazol.
(2) couplings
Sulfonation para-ester diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, adds a little in diazol
Trash ice, 39.8 grams of 2,4- diaminourea-β of percentage amount-hydroxyalkyl vinyl sulfone pressed powder is quickly put in sulfonation para-ester diazol, control
Within 10 DEG C of temperature processed, ph1-3, stirring reaction 4h.
(3) 4,4 '-diaminobenzene Formanilide diazonium
Accurately weigh percentage amount 22.73 gram 4,4 '-diaminobenzene Formanilide in 500ml four-hole boiling flask, beat by ice mill
Slurry 30min, adds 25.56 grams of 30% hydrochloric acid, stirs 10min, is added dropwise over 46.46 grams of 30% sodium nitrite, Deca thereto
First quick and back slow, sodium nitrite finishes speed, controls temperature 5-8 DEG C, stirring reaction 1-1.5h, obtains 4,4 '-diaminobenzene formyl
For diazonium salt of aniline.
(4) secondary coupling
4,4 '-diaminobenzene Formanilide diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, will reach
Coupling solution of terminal adjusts ph to 4 with sodium bicarbonate, by 4,4 '-diaminobenzene Formanilide diazol to entering a coupling solution
In, finish, adjust ph5.5-8.0 with the sodium bicarbonate of technique amount, control temperature 8-12 DEG C, stirring reaction 3h, obtain azo dye former
Slurry.
The structural formula of the reactive azo dyes that embodiment 5 obtains is as follows:
Embodiment 6
(1) para-ester diazonium
Accurately weigh 56.2 grams of para-esters of percentage amount in 1000ml four-hole boiling flask, ice mill making beating 30min, observes sulfonation pair
Position ester beating resultses, granule uniformly tiny rear 38 grams of 30% hydrochloric acid of addition, stirs 10min, is added dropwise over 30% nitrous thereto
46.46 grams of sour sodium, first quick and back slow, sodium nitrite finishes rate of addition, controls temperature 8-10 DEG C, stirring reaction 1-1.5h, obtains
Para-ester diazol.
(2) couplings
Para-ester diazonium terminal arrives, and eliminates excessive sodium nitrite with sulfamic acid, adds a little trash ice in diazol,
59 grams of 2,4- diaminourea of percentage amount-beta-hydroxyethyl sulfuryl phosphate ester pressed powder is quickly put in para-ester diazol, controls temperature
Within 10 DEG C of degree, ph1-3, stirring reaction 4h.
(3) 4,4 '-diaminobenzils -2,2 '-disulfonic acid diazonium
Accurately weighing 370.02 grams of 4,4 '-diaminobenzils -2,2 of percentage amount '-disulfonic acid is in 500ml four-hole boiling flask
In, ice mill making beating 30min, add 25.56 grams of 30% hydrochloric acid, stir 10min, be added dropwise over 30% sodium nitrite thereto
46.46 grams, first quick and back slow, sodium nitrite finishes rate of addition, controls temperature 5-8 DEG C, stirring reaction 1-1.5h, obtain 4,4 '-
Diaminobenzil -2,2 '-disulfonic acid diazol.
(4) secondary coupling
4,4 '-diaminobenzil -2,2 '-disulfonic acid diazonium terminal arrives, and eliminates excessive nitrous acid with sulfamic acid
Sodium, reach home coupling solution sodium bicarbonate is adjusted ph to 4, by 4,4- diaminobenzene Formanilide diazol to entering one
In secondary coupling solution, finish, adjust ph5.5-8.0 with the sodium bicarbonate of technique amount, control temperature 8-12 DEG C, stirring reaction 3h, obtain idol
Nitrogen dyestuff oleo stock.
The structural formula of the reactive azo dyes that embodiment 6 obtains is as follows:
Application examples 1
Traditional activated azo dye 1～6: preparation method respectively as embodiment 1～6, using formula during synthetically produced
(15) general structure in alternate embodiment (13), you can obtain traditional activated para-dye 1～6.
The reactive azo dyes that the embodiment of the present invention 1～6 synthesis is obtained and the dyestuff quality of traditional activated azo dye
And parachloroanilinum content carries out contrast experiment in dyestuff.
As can be seen from Table 1, in the reactive azo dyes that the present invention obtains, parachloroanilinum residual quantity is more traditional averagely low
47.5%, degree of fixation and dissolubility improve 8.14% and 22.23% compared with conventional dyes respectively.
Table 1, embodiment 1～6 and traditional activated azo dye 1～6 quality contrast
Application examples 2
The reactive azo dyes that the embodiment of the present invention 1～6 synthesis is obtained and traditional activated azo dye 1～6 and redness
Spell black color fastness contrast experiment with dark blue component.
As can be seen from Table 2, the composite reactive black obtaining after embodiment 1～6 and red and dark blue component colorant match is in antifriction
It is respectively provided with clear superiority compared with conventional dyes in rubbing fastness, fastness to perspiration and soaping fastness.
Table 2, embodiment 1～6 and traditional activated azo dye 1～6 and red, dark blue dye spell black color fastness contrast
Claims (7)
1. a kind of reactive azo dyes are it is characterised in that the construction unit containing formula (1) or (2),
Wherein, y1、y2And y3It is expressed as-ch independently of each other2ch2oso3M ,-ch=ch2、-ch2ch2Oh or-ch2ch2opo3m；m
For h, na, li or k；
d1、d2、d4And d5It is expressed as one of group of benzene or naphthalene system diazo component independently of each other；
d3It is expressed as the group of aromatics bisazo component.
2. reactive azo dyes according to claim 1 are it is characterised in that described d1、d2、d4And d5Represent independently of each other
For the group of formula (3) or (4),
Wherein, r1-r6It is expressed as hydrogen, hydroxyl, amino, carboxyl, methyl, ethyl, methoxyl group, acetylamino, nitre independently of each other
Base, beta-hydroxyethyl sulfuryl sulfate group, β-hydroxyalkyl vinyl sulfuryl, propionamido-, urea groups, sulfonic group, sulphur methyl, halogen atom, c1-c4
Alkyl, c1-c4Alkoxyl or c2-c4Alkanoylamino；
In formula (3), phenyl ring contains one or more r1-r3Substituent group, and at least contain an active group, described active group
For-so2ch2ch2oso3m、-so2Ch=ch2、-so2ch2ch2Oh or-so2ch2ch2opo3m；M is h, na, li or k；
In formula (4), naphthalene nucleus contains one or more r4-r6Substituent group, and at least contain a sulfonic group.
3. reactive azo dyes according to claim 1 are it is characterised in that described d1、d2、d4And d5Represent independently of each other
It is such as the group of following formula (5)～(10),
Wherein, formula (8) is expressed as one of o-, m-, p-aminobenzene sulfonic acid.
4. reactive azo dyes according to claim 1 are it is characterised in that described d3It is expressed as such as the group of formula (11),
Wherein, r7And r8It is expressed as c independently of each other1-c4Alkyl, c1-c4Alkoxyl, c2-c4Alkanoyl sulfonic group, halogen or carboxylic
Base；
r9It is expressed as-ch=ch- ,-nh- ,-co- ,-nh-co- ,-nh-so2- ,-nh-co-nh- ,-o- ,-s- or-so2-.
5. reactive azo dyes according to claim 1 are it is characterised in that described d3Be expressed as formula (12), (13) or
(14) group,
6. a kind of preparation method of described reactive azo dyes as arbitrary in Claims 1 to 5 is it is characterised in that include as follows
Step:
1) arylamine a is dispersed in water, adds sodium nitrite in aqueous solution in acid condition, control 0 DEG C～10 DEG C of temperature to carry out
First diazo-reaction, obtains arylamine a diazol；Described arylamine a is the arylamine containing formula (3) or (4) group；
2) dyestuff intermediate b is added to step 1) in a diazol that obtains, control ph1～5 to carry out the first coupling reaction, obtain
To a coupling solution；
Described dyestuff intermediate b contains following construction unit:
Wherein, y is expressed as-ch2ch2oso3M ,-ch=ch2、-ch2ch2Oh or-ch2ch2opo3m；M is h, na, li or k；
3) arylamine c is dispersed in water, adds sodium nitrite in aqueous solution in acid condition, control 0 DEG C～10 DEG C of temperature to carry out
Second diazo-reaction, obtains arylamine c diazol；Described arylamine c is the arylamine containing formula (3), (4) or (11) group；
4) by step 3) the arylamine c diazol that obtains is added to step 2) in a coupling solution obtaining, control ph5～9 to carry out
Second coupling reaction, obtains described reactive azo dyes.
7. a kind of reactive azo dyes as claimed in claim 1 dye on cellulose fibre or stamp application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610734390.4A CN106349745A (en) | 2016-08-25 | 2016-08-25 | Activated azo dye and preparation method and application thereof |
Applications Claiming Priority (1)
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