CN103305023A - Triazine type azo dye and preparation method thereof - Google Patents
Triazine type azo dye and preparation method thereof Download PDFInfo
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- CN103305023A CN103305023A CN2012100728467A CN201210072846A CN103305023A CN 103305023 A CN103305023 A CN 103305023A CN 2012100728467 A CN2012100728467 A CN 2012100728467A CN 201210072846 A CN201210072846 A CN 201210072846A CN 103305023 A CN103305023 A CN 103305023A
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Abstract
The invention relates to a triazine type azo dye with the general formula (I) shown in the specification and a preparation method of the azo dye. A novel azo dye is obtained by introducing a chloro-s-triazine group into a general monoazo dye and performing a series of condensation reaction. The azo dye comprises a plurality of color-development groups, wherein the contained hindered amine is capable of adsorbing infrared, the DSD acid (namely 4,4'-diamino stilbestrol-2,2'-disulfonic acid) is capable of adsorbing the ultraviolet in the sunlight, and the azo dye is provided with good illumination resistance and sunshine resistance, can be singly or together used with other dyes, and can be applied to the aspects of textile, paper, leather, wood, ink-jet printing ink, and oil ink. The azo dye is a good energy transfer. By containing a plurality of functional groups, the azo dye provided by the invention has more excellent weather resistance than that of a general azo dye.
Description
Technical field
The present invention relates to a kind of Triazine azoic dyestuff and preparation method thereof.This Triazine azoic dyestuff is by cyanuric chloride and the first condensation reaction of DSD acid, and then respectively with hindered amine 4-Z-2,2,6,6-tetramethyl piperidine, 1-amino-8-naphthol-3,6-disulfonic acid (being the single sodium salt of H acid) or 2-amido-8-naphthol-6-sulfonic acid (being γ acid) carry out secondary and three condensation reactions with the coupling product of phenyl amines diazonium salt.This dyestuff is fast for the dyeing kinetics of paper, paper pulp, rate of dyeing is high, and the fast light and moistening colour fastness of product dyed thereby is outstanding.In addition, even by the material of the anionic property dyeings such as direct dyestuff or matching stain, for example, when using in the dyeing of the surface (chromatography) of wool, thin,tough silk, leather, kapok etc., compare with the situation of using general azoic dyestuff, find that its sun-resistant performance improves greatly.
Background technology
As everyone knows, in the molecular structure of dye, every contain azo-group (N=N-) be referred to as azoic dyestuff, wherein azo-group often links to each other with one or more aromatic nucleus system and consists of a conjugated system and as the color bodies of dyestuff, almost be distributed in all colors, be widely used in dyeing and the printing technologies such as textiles, leatherware.Yet, azoic dyestuff particularly when dyefastness is not good, or heat-resisting, when colour fastness to light is bad, under the effect of external environment, easily decompose, cause pollutant to fade etc., affect the dyeing behavior of azoic dyestuff.
In order to remedy defects, the applicant has researched and developed some particular dye, can improve the heat-resisting colour fastness to light of azoic dyestuff, so that the negative impact of azoic dyestuff reduces greatly.
Summary of the invention
One of purpose of the present invention provides a kind of Triazine azoic dyestuff with good colour fastness to light.This Triazine azoic dyestuff is by cyanuric chloride and the first condensation reaction of DSD acid, and then respectively with hindered amine 4-Z-2,2,6,6-tetramethyl piperidine, 1-amino-8-naphthol-3,6-disulfonic acid (being the single sodium salt of H acid) or 2-amido-8-naphthol-6-sulfonic acid (being γ acid) carry out secondary and three condensation reactions with the coupling product of phenyl amines diazonium salt.This azoic dyestuff contains multiple chromophoric group, the hindered amine that wherein contains can absorb infrared rays, DSD acid (namely 4,4 '-diamino Di-2,2 '-disulfonic acid) can absorb ultraviolet ray in the sunlight, have good fast light photograph, sun-resistant performance, can be separately or and other dyestuff use together, can be used in the aspects such as textiles, paper, leather, timber, ink-jet printing ink, printing ink, and be a kind of good energy transfer agent.This azoic dyestuff has the weathering resistance better with general azoic dyestuff because containing the several functions group.
Two of purpose of the present invention provides the preparation method of above-mentioned Triazine azoic dyestuff.
Triazine azoic dyestuff provided by the invention has following general formula (1):
Wherein: D
1Group for following general formula (2):
D
2Group for following general formula (3) or general formula (4):
In described general formula (1), general formula (3), the general formula (4), M is that hydrogen, alkali metal lithium, sodium, potassium, organic amine compound, general formula are N (R
1R
2R
3) compound; General formula is N (R
1R
2R
3) in the compound, R
1, R
2, R
3Can be H ,-CH
3,-CH
2CH
3,-CH
2CH
2OH ,-[CH
2CH (CH
3) O] nH ,-(CH
2CH
2O) nH, n are natural number; Suitable n is the natural number between the 1-18 especially; R
1, R
2, R
3Can be simultaneously identical, also can part identical, also can be fully different simultaneously;
In the described general formula (1), X is
-CH=CH-,
Be preferably
-CH=CH-;
In described general formula (1), the general formula (2), Z is-NH-, O, S, methylene radical; Preferably-NH-, methylene radical;
In the described general formula (4), R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
Wherein Y is (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, carbonyl; R
4And R
5Can select independently or identical hydrogen, halogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) carboxyl, amino, amide group, urea groups, hydroxyl.
In the described general formula (1), M is preferably hydrogen, lithium or sodium, trolamine, diethanolamine, monoethanolamine, triethylamine.
The preferred hydrogen of R, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH.
The invention provides the preparation method of the Triazine azoic dyestuff of general formula (1), have following two kinds:
A kind of is by making amine compound for general formula (a), being the 1-amino-8-naphthol-3 of formula (b), 6-disulfonic acid (be H acid single sodium salt) or 2-amido-8-naphthol-6-sulfonic acid (being γ acid), for the cyanuric chloride of formula (c) or cyanuric fluoride, for the compound of general formula (e) and be a kind of piperylhydrazine in the formula (d), desirablely occur in sequence conventional diazotization, coupling and condensation reaction and obtain the Triazine azoic dyestuff of general formula of the present invention (1) with any;
Wherein, R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
Wherein Y is (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, carbonyl; R
4And R
5Can select independently or identical hydrogen, halogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) carboxyl, amino, amide group, urea groups, hydroxyl;
M is hydrogen, alkali metal lithium, sodium, potassium, and organic amine compound, general formula are N (R
1R
2R
3) compound; General formula is N (R
1R
2R
3) in the compound, R
1, R
2, R
3Can be H ,-CH
3,-CH
2CH
3,-CH
2CH
2OH ,-[CH
2CH (CH
3) O] nH ,-(CH
2CH
2O) nH, n are natural number; Suitable n is the natural number between the 1-18 especially; R
1, R
2, R
3Can be simultaneously identical, also can part identical, also can be fully different simultaneously;
X is
-CH=CH-,
Be preferably
-CH=CH-.
M is preferably hydrogen, lithium or sodium, Monoethanolamine MEA BASF, diethanolamine, triethylamine.
The preferred hydrogen of R, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH.
Concrete grammar has following several side by side:
1. get condenses A with for the first time condensation of general formula (e) first with formula (c), then carry out the condensation second time with formula (d) gets condenses B to condenses A, for the third time condensation of condenses B and formula (b) gets condenses C, condenses C diazonium salt last and general formula (a) amine compound carries out coupled reaction, can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
2. get condenses A with for the first time condensation of general formula (e) first with formula (c), then carrying out the condensation second time with formula (b) gets condenses D, for the third time condensation of condenses D and formula (d) gets condenses C, condenses C diazonium salt last and general formula (a) amine compound carries out coupled reaction, can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
3. get condenses E with for the first time condensation of formula (d) first with formula (c), then carry out the condensation second time with formula (b) gets condenses F to condenses E, for the third time condensation of condenses F and general formula (e) gets condenses C, condenses H diazonium salt last and general formula (a) amine compound carries out coupled reaction, can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
4. get condenses G with for the first time condensation of formula (b) first with formula (c), then carry out the condensation second time with formula (d) gets condenses F to condenses G, for the third time condensation of condenses F and general formula (e) gets condenses C, condenses C diazonium salt last and general formula (a) amine compound carries out coupled reaction, can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
5. get condenses E with for the first time condensation of formula (d) first with formula (c), then carry out the condensation second time with general formula (e) gets condenses H to condenses E, for the third time condensation of condenses H and formula (b) gets condenses C, condenses C diazonium salt last and general formula (a) amine compound carries out coupled reaction, can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
6. get condenses G with for the first time condensation of formula (b) first with formula (c), then carry out the condensation second time with general formula (e) gets condenses I to condenses G, for the third time condensation of condenses I and formula (d) gets condenses C, condenses C diazonium salt last and general formula (a) amine compound carries out coupled reaction, can obtain the Triazine azoic dyestuff of formula of the present invention (1).
7. the diazonium salt with general formula (a) amine compound gets conjugates J with formula (b) coupling first, conjugates J then gets condenses K with for the first time condensation of formula (c), condenses K and formula (d) are carried out the condensation second time and are got condenses L, for the third time condensation of condenses L and general formula (e) can obtain the Triazine azoic dyestuff of formula of the present invention (1).
8. the diazonium salt with general formula (a) amine compound gets conjugates J with formula (b) coupling first, conjugates J then gets condenses K with for the first time condensation of formula (c), condenses K and general formula (e) carry out the condensation second time and get condenses M, for the third time condensation of condenses M and formula (d) can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
9. get condenses G with for the first time condensation of formula (b) first with formula (c), condenses G then gets conjugates K with the diazonium salt coupling of general formula (a) amine compound, conjugates K and formula (d) are carried out the condensation second time and are got condenses L, for the third time condensation of condenses L and general formula (e) can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
10. get condenses G with for the first time condensation of formula (b) first with formula (c), condenses G then gets conjugates K with the diazonium salt coupling of general formula (a) amine compound, conjugates K and general formula (e) carry out the condensation second time and get condenses N, for the third time condensation of condenses N and formula (d) can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
11. get condenses E with for the first time condensation of formula (d) first with formula (c), for the second time condensation of condenses E and general formula (e) gets condenses H, again and the conjugates J of the diazonium salt of general formula (a) amine compound and formula (b) carry out for the third time condensation, can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
12. get condenses A with for the first time condensation of general formula (e) first with formula (c), for the second time condensation of condenses A and formula (d) gets condenses B, condenses B again and the conjugates J of the diazonium salt of general formula (a) amine compound and formula (b) carry out for the third time condensation, can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
13. get condenses A with for the first time condensation of general formula (e) first with formula (c), condenses A again and the conjugates J of the diazonium salt of general formula (a) amine compound and formula (b) carry out the condensation second time and get condenses O, last and for the third time condensation of formula (d) of condenses O can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
14. get condenses E with for the first time condensation of formula (d) first with formula (c), condenses E again and the conjugates J of the diazonium salt of general formula (a) amine compound and formula (b) carry out the condensation second time and get condenses P, last and for the third time condensation of general formula (e) of condenses P can obtain the Triazine azoic dyestuff of general formula of the present invention (1).
In the method for the invention, the halo s-triazine of described formula (c) expression is selected from cyanuric chloride or cyanuric fluoride, preferred cyanuric chloride.
The cyanuric chloride or the cyanuric fluoride that adopt are very active chemical; a lot of nucleophilic reagents can replace its one, two or three chlorine or fluorine atom; meet water and be easy to hydrolysis, should remain on lower temperature during therefore with formula (b) condensation, the reaction medium water gets final product.Because cyanuric chloride or cyanuric fluoride are slightly soluble in water, generally should add on a small quantity at aqueous phase (generally is the dispersion agent that adds 0.4g～1.0g) in the 300mL solution.Dispersion agent described herein is selected Pluronic F-68.
During cyanuric chloride of the present invention and general formula (e) condensation, the mol ratio between cyanuric chloride and the general formula (e) is 1: 0.4～1: 0.5, and preferred mol ratio is 1: 0.4～1: 0.475, and optimum mole ratio is 1: 0.425.But consider that cyanuric chloride can be hydrolyzed, the actual cyanuric chloride that feeds intake should be suitably more excessive, but do not want excessive too many, in order to avoid affect dye shade even waste raw material.
4-Z-2 in the formula (d), during 2,6,6-tetramethyl piperidine amine and general formula (e) condensation, 4-Z-2, the mol ratio between 2,6,6-tetramethyl piperidine amine and the general formula (e) is 1: 1.
1-amino-8-naphthol-3 in the formula (b), when 6-disulfonic acid (single sodium salt) (being H acid) or 2-amido-8-naphthol-6-sulfonic acid (being γ acid) and general formula (e) condensation, the mol ratio between formula (b) and the general formula (e) is 1: 1.
The 1-amino-8-naphthol-3 of cyanuric chloride of the present invention and general formula (b), when 6-disulfonic acid (being the single sodium salt of H acid) or 2-amido-8-naphthol-6-sulfonic acid (being γ acid) condensation, first chlorine atom of cyanuric chloride is substituted at-5～5 ℃, preferred temperature is-1～3 ℃, and optimal reaction temperature is 0～1 ℃.PH＜3.0 when first chlorine atom is substituted, suitable pH value is 0.8～3.0, optimal ph is 2.7～3.0; When the pH value is higher, can increase the decomposition rate of cyanuric chloride.PH adjusting agent is selected soda or sodium salt usually; Be preferably a kind of in caustic alkali, sodium-acetate, yellow soda ash or the sodium bicarbonate, a kind of in sodium-acetate, yellow soda ash or the sodium bicarbonate more preferably, the best setting agent is sodium-acetate or sodium bicarbonate.
Second chlorine atom of cyanuric chloride is substituted at 15～50 ℃, and preferred temperature is 15～30 ℃, and optimum temps is 15～25 ℃; PH when second chlorine atom is substituted is between 3.0～5.0, and preferred pH is 3.5～4.5, and best pH is 3.8～4.1.Adopt pH adjusting agent still to select soda or sodium salt, be preferably a kind of in caustic alkali, sodium-acetate, yellow soda ash or the sodium bicarbonate, a kind of in sodium-acetate, yellow soda ash or the sodium bicarbonate more preferably, the best setting agent is sodium-acetate or sodium bicarbonate.The 3rd chlorine atom of cyanuric chloride is substituted at 70～100 ℃, and preferred temperature is 90～100 ℃; PH when second chlorine atom is substituted is between 5.0～7.0, and preferred pH is 6.0～7.0, and best pH is 6.5～7.0.Adopt pH adjusting agent still to select soda or sodium salt, be preferably a kind of in caustic alkali, sodium-acetate, yellow soda ash or the sodium bicarbonate, be preferably a kind of in sodium-acetate, yellow soda ash or the sodium bicarbonate, the best setting agent is sodium-acetate or sodium bicarbonate.
The method that another kind of the present invention prepares the Triazine azoic dyestuff is: at first the amine compound with general formula (a) carries out diazotization:
Then with the diazotization product of the amine compound of general formula (a) and the 1-amino-8-naphthol-3 of formula (b), 6-disulfonic acid (being the single sodium salt of H acid) or 2-amido-8-naphthol-6-sulfonic acid (being γ acid) are coupled to the azo component reaction product of following formula (5)
The azo component reaction product formula (5) that generates is carried out the Triazine azoic dyestuff that condensation reaction namely obtains formula (1) with cyanuric chloride or the cyanuric fluoride of formula (c);
Wherein, R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
Wherein Y is (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, carbonyl; R
4And R
5Can select independently or identical hydrogen, halogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) carboxyl, amino, amide group, urea groups, hydroxyl;
The diazotization of general formula (a) compound is undertaken by known method own, normally carries out with nitrite or mineral substance medium in acidic medium, but, also can carry out with other diazotization agent.But the most cheap with nitrite.Described nitrite is preferably alkali metal nitrites salts, more preferably Sodium Nitrite.Described acidic medium is selected a kind of in phosphoric acid, sulfuric acid, acetic acid, the hydrochloric acid or mixture that these are sour, is preferably the mixture of hydrochloric acid, sulfuric acid and phosphoric acid and acetic acid.Diazotizing temperature is generally at-10～40 ℃, and preferred temperature range is-10～5 ℃.
The coupling of azo component reaction product formula (5) is 3～7 by known method own in the pH value, and temperature range is carried out in-10～30 ℃ the environment.A kind of or its mixing in hydrochloric acid, sulfuric acid, acetic acid or the phosphoric acid is selected in used acid; Preferred temperature range is-10～10 ℃.
One kettle way is generally adopted in diazotization of the present invention and coupling, namely adopts identical reaction medium.
Triazine azoic dyestuff of the present invention is powdery or is water-soluble liquid state or the liquid state that is dissolved in alcoholic solvent.This Triazine azoic dyestuff can be separately or with the use that is mixed of other dyestuff.This Triazine azoic dyestuff can be used in the dyeing of textiles, paper, leather, timber and the application in ink-jet printing ink, printing ink.
The Triazine azoic dyestuff of general formula of the present invention (1) is fit to the known method particularly filamentary material of nitrogenous or cyano group of printing and dyeing, such as Mierocrystalline cellulose, silk, the sponge of wool and synthesizing polyamides particularly, the natural or synthetic polyamide fiber material of preferably printing and dyeing.
General formula of the present invention (1) if Triazine azoic dyestuff suitably prepd words in advance, generally the form of routine is used for printing and dyeing, can obtain good all round properties, particularly the level dyeing of good light fastness, crock fastness, wet processing fastness, fastness to wet rubbing and light fastness.In addition, Triazine azoic dyestuff of the present invention is soluble in water, can use with other dye combinations.The above-mentioned fabrics material can be various form processings, such as fiber, yarn, woven fabrics or knitted fabrics.
This Triazine azoic dyestuff is to import 4-Z-2 in the dye matrix of selecting the component that forms from azoic dyestuff, substantive dyestuff and reactive dyestuffs, 2,6,6-tetramethyl piperidine and similar structures, dyeing kinetics for paper, paper pulp is fast, rate of dyeing is high, and the fast light and moistening colour fastness of product dyed thereby is outstanding; In addition, because 4-Z-2,2,6,6-tetramethyl piperidine is good photostabilizer, even by the material of the anionic property dyeings such as direct dyestuff or matching stain, for example, when using in the dyeing of the surface (chromatography) of wool, thin,tough silk, leather, kapok etc., compare with the situation of using general azoic dyestuff, find that its sun-resistant performance improves greatly, can obtain high gloss and the outstanding product dyed thereby of fast light and moistening colour fastness.
Embodiment
For the purpose of conveniently further specifying, will enumerate without limitation following examples as more detailed description.Wherein, except as otherwise noted, all materials all by weight.
Embodiment 1
A) in the 500mL reaction flask, add 40g water, 0.8g wetting agent and 60g ice, bathe the control temperature at 0～1 ℃ with cryosel, rapid stirring; Add 18.6g cyanuric chloride (99%, MW=184.5,0.10mol), rapid stirring 30 minutes grinds cyanuric chloride in mixture of ice and water again, and the control temperature is at 0～1 ℃.Product is white suspension.
B) in the beaker of 100mL, add 27.5g water, 1.8g NaHCO
3With 16.3g DSD acid (96.68%, MW=370.41,0.0425mol), stir; Add carefully again NaHCO
3Regulate pH to 6.5～6.8, stir until DSD acid is dissolved fully, a small amount of defoamer froth breaking of middle adding; Be cooled to 0～5 ℃, pH=6.5～7.0 to wherein adding 20g ice.
C) with above-mentioned second step b) in the DSD acid solution be added drop-wise to and carry out the condensation reaction first time in the cyanuric chloride solution, time for adding is controlled at about 1h, bathes the control temperature of reaction at 0～3 ℃ with cryosel simultaneously, pH＜3.0; After the DSD acid solution drips off, in 1h, pass through sodium acetate soln (or 20% the Na of adding 30%
2CO
3/ NaHCO
3Solution) regulate pH 2.7～3.0, add simultaneously 30g ice control T=0～3 ℃.For the first time condensation obtains following structural formula:
D) after for the first time condensation is finished, carry out the condensation reaction second time to wherein adding 13.3g 4-amino-2,2,6,6-tetramethylpiperidine (TEMP) (100%, MW=156.27,0.085mol), during add NaHCO
3Regulate pH=3.9～4.1, control foam with a small amount of Surfynol 104E, T=3～8 ℃; Stir two condensation reaction materials, 12～16h, temperature of reaction can be controlled between 15～20 ℃.For the second time condensation obtains following structural formula:
E) after for the second time condensation is finished, carry out for the third time condensation reaction to wherein adding the 29.0g H single sodium salt of acid (100%, MW=341.31,0.085mol), during add NaHCO
3Regulate pH=3.9～4.1, control foam with a small amount of Surfynol 104E, T=70～80 ℃; Stir three condensation reaction materials, 8～12h, temperature of reaction can be controlled at about 75 ℃.For the third time condensation obtains following structural formula:
F) in the 500mL beaker, add 50g water, 70g ice and 7.9g aniline (100%, MW=93.128,0.085mol) stir, the hydrochloric acid that adds again 25.2g 36% is bathed the control temperature at 0～2 ℃ with cryosel, slowly adds the inferior sodium water solution (100% of 18g again, MW=69.0,0.085mol), 0～5 ℃ with thionamic acid or urea excessive nitrous acid is destroyed after continue stirring 1 hour after, diazotization is finished.
G) this diazonium salt is joined previously prepared three condenses e) in carry out coupling, the Triazine azoic dyestuff that obtains has following formula:
Step e) in the single sodium salt of H acid change γ acid (following examples with) into, the Triazine azoic dyestuff that can obtain having the following formula structure:
Embodiment 2
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride successively respectively with 16.3g DSD acid, the 29.0g H single sodium salt of acid and 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) condensation, three condensess are carried out coupling with the 7.9g diazonium salt of aniline again, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 3
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride successively respectively with 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP), the 29.0g H single sodium salt of acid and 16.3g DSD acid condensation, three condensess are carried out coupling with the 7.9g diazonium salt of aniline again, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 4
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride successively respectively with the single sodium salt of 29.0g H acid, 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) and 16.3g DSD acid condensation, three condensess are carried out coupling with the 7.9g diazonium salt of aniline again, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 5
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride successively respectively with 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP), 16.3g DSD acid and the single sodium salt condensation of 29.0g H acid, three condensess are carried out coupling with the 7.9g diazonium salt of aniline again, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 6
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride successively respectively with the single sodium salt of 29.0g H acid, 16.3g DSD acid and 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) condensation, three condensess are carried out coupling with the 7.9g diazonium salt of aniline again, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Comparative Examples 1～6
The azoic dyestuff that all can synthesize formula of the present invention (1) according to the prescription in the example 1～6 and condition.But because cyanuric chloride is different from the condensation order of DSD acid, the sour single sodium salt of H and three kinds of compounds of 4-amino-2,2,6,6-tetramethylpiperidine (TEMP), condition control sequence is also different, therefore speed of response and the degree of each condensation are also different.
Embodiment 7
Such as embodiment 1, take by weighing 7.9g aniline and carry out diazotization, then the single sodium salt coupling of elder generation and 29.0g H acid, then with for the first time condensation of 18.6g cyanuric chloride, again successively with 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) and 16.3g DSD acid condensation namely obtains the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 8
Such as embodiment 1, take by weighing 7.9g aniline and carry out diazotization, then the single sodium salt coupling of elder generation and 29.0g H acid, then with for the first time condensation of 18.6g cyanuric chloride, again successively with 16.3g DSD acid and 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) condensation namely obtains the Triazine azoic dyestuff of general formula of the present invention (1).
Comparative Examples 1～8
Example 7～8 is with the difference of example 1～6, example 7～8th, the diazonium salt elder generation of aniline and the single sodium salt coupling of H acid, again respectively with cyanuric chloride, DSD acid and 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) condensation, example 1～6 then is cyanuric chloride elder generation and the single sodium salt of H acid, DSD acid and 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) is pressed the different order condensation, last and diazonium salt of aniline coupling, play the same tune on different musical instruments, finally all obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 9
Such as embodiment 1, take by weighing 18.6g cyanuric chloride elder generation and the single sodium salt condensation of 29.0g H acid, then carry out coupling with the 7.9g diazonium salt of aniline, then successively with 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) and 16.3g DSD acid condensation namely obtains the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 10
Such as embodiment 1, take by weighing 18.6g cyanuric chloride elder generation and the single sodium salt condensation of 29.0g H acid, then carry out coupling with the 7.9g diazonium salt of aniline, then successively with 16.3g DSD acid and 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) condensation namely obtains the Triazine azoic dyestuff of general formula of the present invention (1).
Comparative Examples 9～10
Embodiment 9～10th, and cyanuric chloride carries out coupling with diazonium salt of aniline first with after the single sodium salt condensation of H acid, this product again with DSD acid and 4-amino-2,2,6,6-tetramethylpiperidine (TEMP) condensation.
Embodiment 11
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride first successively with 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) and 16.3g DSD acid condensation, carry out for the third time condensation with the coupling product of the 29.0g H single sodium salt of acid and 7.9g diazonium salt of aniline again, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 12
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride first successively with 16.3g DSD acid and 13.3g 4-amino-2,2,6,6-tetramethyl piperidine (TEMP) condensation, carry out for the third time condensation with the coupling product of the 29.0g H single sodium salt of acid and 7.9g diazonium salt of aniline again, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 13
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride and carry out condensation with the coupling product of 16.3g DSD acid and the 29.0g H single sodium salt of acid and 7.9g diazonium salt of aniline successively first, again with 13.3g 4-amino-2,2,6, for the third time condensation of 6-tetramethyl piperidine (TEMP) namely obtains the Triazine azoic dyestuff of general formula of the present invention (1).
Embodiment 14
Such as embodiment 1, take by weighing the 18.6g cyanuric chloride first successively with 13.3g 4-amino-2,2,6, the coupling product of 6-tetramethyl piperidine (TEMP) and the 29.0g H single sodium salt of acid and 7.9g diazonium salt of aniline is carried out condensation, with for the third time condensation of 16.3g DSD acid, namely obtain the Triazine azoic dyestuff of general formula of the present invention (1) again.
Comparative Examples 11～14
Embodiment 11～14th, cyanuric chloride and DSD acid, 4-amino-2,2, the coupling product amine different order of 6,6-tetramethyl piperidine (TEMP) and the H single sodium salt of acid and diazonium salt of aniline is carried out condensation reaction, all obtains at last the Triazine azoic dyestuff of general formula of the present invention (1).
When dying paper or going up the surface (chromatography) of dyeing wool, thin,tough silk, leather, kapok etc. with the resulting azoic dyestuff of aforesaid method, irradiation a couple of days does not have significantly and fades under high light, compare with the situation of using general azoic dyestuff, its light fastness has obviously improved; Second, above-mentioned dyestuff can be deposited about pH=7.5 1 year even the longer time, and pH value or coloured light do not have obvious change, and dihalo-s-triazine type dye is only deposited under identical condition Precipitation is just arranged several weeks, and the pH value can descend a lot, very unstable.Therefore, Triazine azoic dyestuff of the present invention has better weathering resistance and light stability than general azoic dyestuff, has greatly widened the range of application of azoic dyestuff.
Claims (9)
1. Triazine azoic dyestuff has following general formula (1):
Wherein, D
1The group of general formula (2):
D
2Group for following general formula (3) or general formula (4):
In described general formula (1), general formula (3), the general formula (4), M is hydrogen, alkali metal lithium, sodium, potassium, organic amine compound, and general formula is N (R
1R
2R
3) compound; General formula is N (R
1R
2R
3) in the compound, R
1, R
2, R
3Be H ,-CH
3,-CH
2CH
3,-CH
2CH
2OH ,-[CH
2CH (CH
3) O] nH ,-(CH
2CH
2O) nH, n are natural number;
In the described general formula (1), X is
-CH=CH-,
In described general formula (1), the general formula (2), Z is NH, O, S, methylene radical;
In the described general formula (4), R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
Wherein, Y is (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, carbonyl; R
4And R
5Can select independently or identical hydrogen, halogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) carboxyl, amino, amide group, urea groups, hydroxyl.
2. Triazine azoic dyestuff as claimed in claim 1 is characterized in that, M is hydrogen, lithium or sodium, trolamine, diethanolamine, monoethanolamine, triethylamine; R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH; X is
-CH=CH-.
3. one kind prepares the described Triazine azoic dyestuff of claim 1～2, it is characterized in that, by making the amine compound for general formula (a), 1-amino-8-naphthol-3 for formula (b), 6-disulfonic acid (being the single sodium salt of H acid) or 2-amido-8-naphthol-6-sulfonic acid (being γ acid), cyanuric chloride or cyanuric fluoride for formula (c), for the compound of general formula (e) and be a kind of piperylhydrazine in the formula (d), with any desirable conventional diazotization that occurs in sequence, coupling and condensation reaction and obtain the Triazine azoic dyestuff of described general formula (1);
Wherein, R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
Wherein Y is (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, carbonyl; R
4And R
5To select independently or identical hydrogen, halogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) carboxyl, amino, amide group, urea groups, hydroxyl;
M is that hydrogen, alkali metal lithium, sodium, potassium, organic amine compound, general formula are N (R
1R
2R
3) compound; General formula is N (R
1R
2R
3) in the compound, R
1, R
2, R
3Be H ,-CH
3,-CH
2CH
3,-CH
2CH
2OH ,-[CH
2CH (CH
3) O] nH ,-(CH
2CH
2O) nH, n are natural number;
X is
-CH=CH-,
4. method as claimed in claim 3 is characterized in that, M is hydrogen, lithium or sodium, trolamine, diethanolamine, monoethanolamine, triethylamine; R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH; X is
-CH=CH-.
5. method as claimed in claim 3, it is characterized in that, the 1-amino-8-naphthol-3 of the cyanuric chloride in the described formula (c) and general formula (b), when 6-disulfonic acid or the condensation of 2-amido-8-naphthol-6-sulfonic acid, the substitution reaction temperature of first chlorine atom of cyanuric chloride is-5～5 ℃, pH value＜3.0; The substitution reaction temperature of second chlorine atom of cyanuric chloride is 15～50 ℃, and the pH value is at 3.0-5.0; The substitution reaction temperature of the 3rd chlorine atom of cyanuric chloride is 70～100 ℃, and the pH value is at 5.0-7.0.
6. one kind prepares the described Triazine azoic dyestuff of claim 1～2, it is characterized in that, at first the amine compound with general formula (a) carries out diazotization:
Then with the diazotization product of the amine compound of general formula (a) and the 1-amino-8-naphthol-3 of formula (b), 6-disulfonic acid or 2-amido-8-naphthol-6-sulfonic acid are coupled to the azo component reaction product of following formula (5),
The azo component reaction product formula (5) that generates is carried out the Triazine azoic dyestuff that condensation reaction namely obtains general formula (1) with cyanuric chloride or the cyanuric fluoride of formula (c);
Wherein, D
1The group of general formula (2):
D
2Group for following general formula (3) or general formula (4):
Wherein, in described general formula (1), general formula (3), the general formula (4), M is hydrogen, alkali metal lithium, sodium, potassium, organic amine compound, and general formula is N (R
1R
2R
3) compound; General formula is N (R
1R
2R
3) in the compound, R
1, R
2, R
3Be H ,-CH
3,-CH
2CH
3,-CH
2CH
2OH ,-[CH
2CH (CH
3) O] nH ,-(CH
2CH
2O) nH, n are natural number;
In the described general formula (1), X is
-CH=CH-,
In described general formula (1), the general formula (2), Z is NH, O, S, methylene radical;
In the described general formula (4), R is hydrogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
(R in the formula
1, R
2Please be revised as respectively R
4, R
5), wherein, Y is (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) alkylthio, amino, amide group, urea groups, carbonyl; R
4And R
5Independently or identical hydrogen, halogen, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group, (C
1-C
4) carboxyl, amino, amide group, urea groups, hydroxyl.
7. Triazine azoic dyestuff as claimed in claim 1 is characterized in that, described Triazine azoic dyestuff is powdery or is water-soluble liquid state or the liquid state that is dissolved in alcoholic solvent.
8. such as the described Triazine azoic dyestuff of claim 1～2, it is characterized in that, described Triazine azoic dyestuff can be separately or and other dyestuff be mixed and use together.
9. the purposes of the described Triazine azoic dyestuff of claim 1-2 is characterized in that, is used in textiles, the dyeing of paper, leather, timber and the application in ink-jet printing ink, printing ink.
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| CN2012100728467A CN103305023A (en) | 2012-03-16 | 2012-03-16 | Triazine type azo dye and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100728467A CN103305023A (en) | 2012-03-16 | 2012-03-16 | Triazine type azo dye and preparation method thereof |
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| CN115612308A (en) * | 2022-09-08 | 2023-01-17 | 浙江闰土染料有限公司 | Preparation method and application of yellow direct blending dye |
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