CN104231659A - Red thiazole heterocyclic disperse dye compound containing benzoate group and preparation and application thereof - Google Patents

Red thiazole heterocyclic disperse dye compound containing benzoate group and preparation and application thereof Download PDF

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CN104231659A
CN104231659A CN201410350337.5A CN201410350337A CN104231659A CN 104231659 A CN104231659 A CN 104231659A CN 201410350337 A CN201410350337 A CN 201410350337A CN 104231659 A CN104231659 A CN 104231659A
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red
disperse dye
dye compound
phenylformic acid
ester group
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俞杏英
姚晨华
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Abstract

The invention relates to a red thiazole heterocyclic disperse dye compound containing benzoate group and preparation and an application thereof. The general formula of the disperse dye compound is shown in the specification. The compound is prepared by the following steps: dissolving a coupling component in acetic acid; then cooling to 0-5 DEG C; then, dropwise adding a diazo component; reacting at the temperature till the diazo component disappears; filtering; washing; and drying to obtain the compound. The compound is applied to a red disperse dye. The dye provided by the invention is simple in synthetic process and can be used for dyeing polyester fabrics in a pH range of 4-13, and the dyed fabric is full in color phase. The compound is excellent in color fastness to sunlight, color fastness to sublimation and color fastness to washing and is a high-fastness red disperse dye which can be suitable for wide pH dyeing.

Description

A kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group and Synthesis and applications thereof
Technical field
The invention belongs to disperse dye compound and Synthesis and applications field thereof, particularly a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group and Synthesis and applications thereof.
Background technology
At present, the Colour Difference of polyster fibre all adopts dispersed dye, dyes under slightly acidic (pH value is 4.5-5.5) condition.Under polyester piece good solutions of weak acidity, dyeing has many weak points, and as work flow is long, processing water consumption is large, and discharge amount of pollution is large; The oligopolymer of polyster fibre inside can not be removed, both affected the feel of product, easily cause again dyeing look flower.Especially in recent years along with the appearance of dacron ultrafine fiber or superfine composite fiber, for allowing ultra-fine fibre or superfine composite fiber thoroughly be separated, all need to process in the basic conditions.The subject matter that current red disperse dyes exists is: dyefastness is poor, especially sublimation fastness and washing fastness poor, the requirement to fastness on market can not be met, can adapt to the orchil that wide pH value dyes few simultaneously, such as in the scope of pH4 ~ 13 to the dyestuff wretched insufficiency that polyester piece good dyes.If the pH value that dispersed dye use is narrow, dyeing reappears just poor, and the color and luster of DYED FABRICS also can be caused to change.The key of alkali resistance poor solution problems is the dispersed dye that preparation adapts to the dyeing of wide pH value, and its alkali resistance is higher, and use range is wider.
General azo type disperse dyes is not alkaline-resisting, and especially unstable under strong basicity (if pH value is 10 ~ 13) condition, easily colour-change phenomena occurs, dyefastness is poor.Therefore, this type disperse dye is not suitable for the strong basicity bath dyeing of polyster fibre.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group and Synthesis and applications thereof, this structure Dyestuff synthesis technique is simple, dye terylene shows as bright-coloured redness, every colour fastness is excellent, especially there is excellent sublimation fastness and washing fastness, the dyeing of wide pH value can be adapted to, can dye to polyester piece good in the scope of pH4 ~ 13.
A kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group of the present invention, the general structure of described disperse dye compound is: wherein n=1,2,3,4,5 or 6;
R 1, R 2, R 3, R 4independent is hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, the one in kharophen;
R 5for the one in hydrogen, methyl, ethyl, benzyl, cyano group, ω-cyanoalkyl, phenylformic acid ester group;
R 6, R 7, R 8, R 9, R 10independent is hydrogen, methyl, ethyl, the one in methoxyl group, oxyethyl group, kharophen, nitro, cyano group.
The preparation method of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group of the present invention, comprising:
(1) under room temperature condition, the chloro-2-amino-benzothiazole of 5,6-bis-will be added in sulfuric acid, drip water, be cooled to less than 10 DEG C, be then added dropwise to nitrosyl sulfuric acid, after dropwising, stir and be added dropwise in the mixing solutions of the vitriol oil of 0 DEG C and water, reaction 2h, obtains diazo component; Wherein the ratio of 5,6-bis-chloro-2-amino-benzothiazoles, nitrosyl sulfuric acid, the vitriol oil and water is 0.035mol:0.035mol:40g:38g;
(2) by phenylformic acid or benzoic acid derivative, N-hydroxyalkyl substituted aniline or N-hydroxyalkyl substituted aniline derivative, solvent, catalyzer mixing, heating point water backflow, obtain coupling component, wherein reflux temperature is 110 DEG C, and return time is 3h;
(3) above-mentioned coupling component is dissolved in acetic acid, then 0-5 DEG C is cooled to, then step (1) diazo component is added dropwise to, under keeping this temperature, reaction is until diazo component disappears, filter, wash, dry, obtain the red thiazole heterocycle disperse dye compound containing phenylformic acid ester group; Wherein the proportionlity of coupling component, diazo component, acetic acid is 0.035mol:0.035mol:200ml.
In described step (1), the mass percentage concentration of sulfuric acid is 98%.
In described step (2), solvent is toluene.
In described step (2), catalyzer is tosic acid or the vitriol oil.
The proportionlity of phenylformic acid or benzoic acid derivative, N-hydroxyalkyl substituted aniline or N-hydroxyalkyl substituted aniline derivative, solvent, catalyzer is 0.035-0.07mol:0.035-0.07mol:100ml:0-1g in described step (2).
Coupling component adopts Benzoyl chloride and N-hydroxyalkyl substituted aniline or N-hydroxyalkyl substituted aniline derivative to react to prepare.
Described coupling component is:
In formula:
N=1,2,3,4,5 or 6.
R 1, R 2, R 3, R 4independent is hydrogen, alkyl, alkoxyl group, kharophen;
R 5independent is hydrogen, alkyl, cyano group, ω-cyanoalkyl;
R 6, R 7, R 8, R 9, R 10independent is hydrogen, alkyl, alkoxyl group, kharophen, nitro, cyano group.
The application of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group of the present invention, described disperse dye compound and auxiliary agent obtain red disperse dyes, and wherein auxiliary agent is sodium naphthalene sulfonate derivative.
Described auxiliary agent is one or more in dispersing agent NNO, Dispersant MF, modifiers dispersants MF.
Modifiers dispersants MF is the mixture of polyethers (L64) and Dispersant MF, and wherein polyethers concentration expressed in percentage by volume is 5%.
Thiazole heterocycle containing phenylformic acid ester group of the present invention red alkali resistance high fastness disperse dye compound can adopt existing commercialization of dyes technology, add conventional dispersing aids (sodium naphthalene sulfonate derivative, preferably one or both mixture following: dispersing agent NNO, Dispersant MF, modifiers dispersants MF), the compound of synthesis is made commercial red disperse dyes.
When using as dispersed dye, commodity red disperse dyes prepared by a kind of compound in general formula can be adopted, the mixture of two or more compound in general formula also can be adopted to prepare commercial red disperse dyes.No matter be red disperse dyes prepared by a kind of compound or the mixture of two or more compound, all there is excellent sun-resistant, resistance to distillation and washing fastness and good alkaline-resisting effect.
Red disperse dyes of the present invention, can dye to polyester piece good, can not cause the change of coloured light in the scope of pH4 ~ 13.Based on the feature of the present invention containing the thiazole heterocycle red alkali resistance high fastness dispersed dye of phenylformic acid ester group, this kind of red disperse dyes dyes under being used for the alkaline condition of polyster fibre, Woven Polyester Fabrics destarch, dyeing single stage method dyeing and printing process can be used for, the refining of polyester knitting thing, dyeing single stage method dyeing and printing process can be used for, also the fibrillation of dacron ultrafine fiber or terylene super fine compound fabric, the processing of dyeing single stage method can be used for, obviously can shorten the technical process of polyster fibre dyeing processing, reduce water consumption, reduce wastewater discharge.
Red disperse dyes of the present invention dyes in the pH value range of 4 ~ 13, and DYED FABRICS form and aspect are full, and sun-resistant, resistance to distillation, the fastness properties such as water-fastness are given prominence to.
beneficial effect
The synthesis technique of disperse dye compound prepared by the present invention is simple, dye terylene shows as bright-coloured redness, and every colour fastness is excellent, especially has excellent sublimation fastness and washing fastness, the dyeing of wide pH value can be adapted to, can dye to polyester piece good in the scope of pH4 ~ 13.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra figure of embodiment 1 gained disperse dye compound;
Fig. 2 is the infrared spectrogram of embodiment 1 gained disperse dye compound;
Fig. 3 is embodiment 1 gained disperse dye compound 1h-NMR composes (DMSO-D6 makes solvent);
Fig. 4 is the uv-visible absorption spectra figure of embodiment 2 gained disperse dye compound;
Fig. 5 is the infrared spectrogram of embodiment 2 gained disperse dye compound;
Fig. 6 is embodiment 2 gained disperse dye compound 1h-NMR composes (DMSO-D6 makes solvent);
Fig. 7 is the infrared spectrogram of embodiment 3 gained disperse dye compound;
Fig. 8 is embodiment 3 gained disperse dye compound 1h-NMR composes (DMSO-D6 makes solvent);
Fig. 9 is the one bath dyeing of embodiment 1-6;
Figure 10 is the colouring rate curve of embodiment 1-6;
Figure 11 is the lifting force curve of embodiment 1-6;
Figure 12 is dyeing curve.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
The synthesis preparation of the disperse dye compound that molecular structure is following:
(1) preparation of diazonium salt:
In 100ml there-necked flask, add the vitriol oil 30g of 98%, add 5, the 6-bis-chloro-2-amino-benzothiazoles of 0.035mol under stirring, temperature controls at 10 DEG C, is then cooled to the nitrosyl sulfuric acid that less than 10 DEG C add 0.035mol.Separately get a there-necked flask, add 38g water, slowly add the vitriol oil 10g of 98%, ice bath is cooled to 0 DEG C, is then slowly dripped by the mixture in aforementioned there-necked flask so far in there-necked flask, maintains the temperature at 0 DEG C of reaction 2h, obtains diazo component.
(2) preparation of coupling component: in the there-necked flask that reflux exchanger, water trap and agitator are housed, add 0.035mol phenylformic acid, 0.035mol N-ethyl successively, N-β-anilino-ethanol and 100ml toluene, with 0.5g tosic acid for catalyzer, heating point water refluxes and steams solvent in 3 hours, obtained coupling component N-ethyl-N-benzoxy ethylaniline.
(3) coupled reaction
Glacial acetic acid 200ml is added in another 1000ml flask, add the N-ethyl-N-benzoxy ethylaniline of 0.035mol, ice bath is cooled to less than 5 DEG C, slowly in system, drip diazo component, control 0 ~ 5 DEG C of reaction until diazo component disappears, the obtained thiazole heterocycle compound containing phenylformic acid ester group, after filtration, washing, to dry, this compound sand milling together with diffusant is obtained the thiazole heterocycle red alkali resistance high fastness dispersed dye containing phenylformic acid ester group.
The disperse dye compound of synthesis, in dehydrated alcohol recrystallization, filters, dries to obtain dyestuff sterling.This dyestuff sterling is done following test and can determine its structure: adopt HIT U-3310 type ultraviolet-visible spectrophotometer to test its ultraviolet-visible spectrum absorption spectrum; U.S. Digital company FTS-25PC Fourier infrared spectrum determinator is used to test its infrared spectra; Bruker company AV400 nuclear magnetic resonance spectrometer is used to measure its hydrogen nuclear magnetic resonance spectrum; German Elmentar Vario EL III type elemental analyser is adopted to test C, the H of each dyestuff, the content of N element.More than test the exactness all indicating synthesized dye structure.Results of elemental analyses is as shown in table 1, and uv-visible absorption spectra, infrared spectra, hydrogen nuclear magnetic resonance spectrum are as illustrated in the accompanying drawings from 1 to 3.
The C of table 1 embodiment 1, H, N content
? C H N
Theoretical content 58.48％ 4.29％ 10.92％
Actual content 58.11％ 4.39％ 10.72％
Embodiment 2
The synthesis preparation of the disperse dye compound that molecular structure is following:
(1) preparation of diazonium salt:
In 100ml there-necked flask, add the vitriol oil 30g of 98%, slowly add 5, the 6-bis-chloro-2-amino-benzothiazoles of 0.035mol under stirring, temperature controls at 20 DEG C, is then cooled to the nitrosyl sulfuric acid that less than 10 DEG C add 0.035mol.Separately get a there-necked flask, add 38g water, slowly add the vitriol oil 10g of 98%, ice bath is cooled to 0 DEG C, is then slowly dripped by the mixture in aforementioned there-necked flask so far in there-necked flask, maintains the temperature at 0 DEG C of reaction 2h, obtains diazo component.
(2) preparation of coupling component: in the 100ml there-necked flask that reflux exchanger, water trap and agitator are housed, add 0.035mol Benzoyl chloride, 0.035mol N-ethyl successively, N-hydroxyethyl meta-aminotoluene and 100ml toluene, heating point water refluxes 3 hours, steam solvent, obtained N-ethyl-N-benzoxy ethyl meta-aminotoluene.
(3) coupled reaction
Glacial acetic acid 200ml is added in another 1000ml flask, add the N-ethyl-N-benzoxy ethyl meta-aminotoluene of 0.035mol, ice bath is cooled to less than 5 DEG C, slowly in system, drip diazo component, control 0 ~ 5 DEG C of reaction until diazo component disappears, the obtained thiazole heterocycle compound containing phenylformic acid ester group, after filtration, washing, to dry, this compound sand milling together with diffusant is obtained the thiazole heterocycle red alkali resistance high fastness dispersed dye containing phenylformic acid ester group.
By the method identical with embodiment 1, above-mentioned synthesized disperse dye compound is purified and analytical test.Results of elemental analyses is as shown in table 2, and uv-visible absorption spectra, infrared spectra, hydrogen nuclear magnetic resonance spectrum are as shown in figs. 4 through 6.
The C of table 2 embodiment 2, H, N content
? C H N
Theoretical content 57.72％ 4.00％ 11.22％
Actual content 57.10％ 4.03％ 11.30％
Embodiment 3
The synthesis preparation of the disperse dye compound that molecular structure is following:
(1) preparation of diazonium salt:
In 100ml there-necked flask, add the vitriol oil 30g of 98%, slowly add 5, the 6-bis-chloro-2-amino-benzothiazoles of 0.035mol under stirring, temperature controls at 20 DEG C, is then cooled to the nitrosyl sulfuric acid that less than 10 DEG C add 0.035mol.Separately get a there-necked flask, add 38g water, slowly add the vitriol oil 10g of 98%, ice bath is cooled to 0 DEG C, is then slowly dripped by the mixture in aforementioned there-necked flask so far in there-necked flask, maintains the temperature at 0 DEG C of reaction 2h, obtains diazo component.
(2) preparation of coupling component: in the there-necked flask that reflux exchanger, water trap and agitator are housed, add 0.07mol phenylformic acid, 0.035mol N-N-dihydroxy ethyl aniline and 100ml toluene successively, with 0.5g tosic acid for catalyzer, heating point water refluxes and steams solvent in 3 hours, obtained coupling component N-N-dibenzoyl oxygen ethylaniline.
(3) coupled reaction
Glacial acetic acid 200ml is added in another 1000ml flask, add the N-ethyl-N-benzoxy ethylaniline of 0.035mol, ice bath is cooled to less than 5 DEG C, slowly in system, drip diazo component, control 0 ~ 5 DEG C of reaction until diazo component disappears, the obtained thiazole heterocycle compound containing phenylformic acid ester group, after filtration, washing, to dry, this compound sand milling together with diffusant is obtained the thiazole heterocycle red alkali resistance high fastness dispersed dye containing phenylformic acid ester group.
The disperse dye compound of synthesis, in dehydrated alcohol recrystallization, filters, dries to obtain dyestuff sterling.This dyestuff sterling is done following test and can determine its structure: use U.S. Digital company FTS-25PC Fourier infrared spectrum determinator to test its infrared spectra; Bruker company AV400 nuclear magnetic resonance spectrometer is used to measure its hydrogen nuclear magnetic resonance spectrum; More than test the exactness all indicating synthesized dye structure.Infrared spectra, hydrogen nuclear magnetic resonance spectrum as accompanying drawing 7, shown in 8.
Embodiment 4
The synthesis preparation of the disperse dye compound that molecular structure is following:
(1) preparation of diazonium salt:
In 100ml there-necked flask, add the vitriol oil 30g of 98%, slowly add 5, the 6-bis-chloro-2-amino-benzothiazoles of 0.035mol under stirring, temperature controls at 20 DEG C, is then cooled to the nitrosyl sulfuric acid that less than 10 DEG C add 0.035mol.Separately get a there-necked flask, add 38g water, slowly add the vitriol oil 10g of 98%, ice bath is cooled to 0 DEG C, is then slowly dripped by the mixture in aforementioned there-necked flask so far in there-necked flask, maintains the temperature at 0 DEG C of reaction 2h, obtains diazo component.
(2) preparation of coupling component: in the 100ml there-necked flask that reflux exchanger, water trap and agitator are housed, add 0.035mol p-methylbenzoic acid, 0.035mol N-ethyl successively, N-β-anilino-ethanol and 100ml toluene, take the vitriol oil as catalyzer, heating point water refluxes 3 hours, and obtained N-ethyl-N-is to toluyl oxygen ethylaniline.
(3) coupled reaction
Glacial acetic acid 200ml is added in another 1000ml flask, add the N-ethyl-N-of 0.035mol to toluyl oxygen ethylaniline, ice bath is cooled to less than 5 DEG C, slowly in system, drip diazo component, control 0 ~ 5 DEG C of reaction until diazo component disappears, the obtained thiazole heterocycle compound containing phenylformic acid ester group, after filtration, washing, to dry, this compound sand milling together with diffusant is obtained the thiazole heterocycle red alkali resistance high fastness dispersed dye containing phenylformic acid ester group.
Uv-visible absorption spectra, infrared spectra, hydrogen nuclear magnetic resonance spectrum and ultimate analysis demonstrate the exactness of this compound structure.
Embodiment 5
The synthesis preparation of the disperse dye compound that molecular structure is following:
(1) preparation of diazonium salt:
In 100ml there-necked flask, add the vitriol oil 30g of 98%, slowly add 5, the 6-bis-chloro-2-amino-benzothiazoles of 0.035mol under stirring, temperature controls at 20 DEG C, is then cooled to the nitrosyl sulfuric acid that less than 10 DEG C add 0.035mol.Separately get a there-necked flask, add 38g water, slowly add the vitriol oil 10g of 98%, ice bath is cooled to 0 DEG C, is then slowly dripped by the mixture in aforementioned there-necked flask so far in there-necked flask, maintains the temperature at 0 DEG C of reaction 2h, obtains diazo component.
(2) preparation of coupling component: in the 100ml there-necked flask that reflux exchanger, water trap and agitator are housed, add 0.035mol Benzoyl chloride, 0.035mol N-ethyl successively, N-hydroxyethyl meta-aminotoluene and 100ml toluene, heating point water refluxes 3 hours, steam solvent, obtained N-ethyl-N-is to toluyl oxygen ethyl meta-aminotoluene.
(3) coupled reaction
Glacial acetic acid 200ml is added in another 1000ml flask, add the N-ethyl-N-of 0.035mol to toluyl oxygen ethyl meta-aminotoluene, ice bath is cooled to less than 5 DEG C, slowly in system, drip diazo component, control 0 ~ 5 DEG C of reaction until diazo component disappears, the obtained thiazole heterocycle compound containing phenylformic acid ester group, after filtration, washing, to dry, this compound sand milling together with diffusant is obtained the thiazole heterocycle red alkali resistance high fastness dispersed dye containing phenylformic acid ester group.
Uv-visible absorption spectra, infrared spectra, hydrogen nuclear magnetic resonance spectrum and ultimate analysis demonstrate the exactness of this compound structure.
Embodiment 6
The synthesis preparation of the disperse dye compound that molecular structure is following:
(1) preparation of diazonium salt:
In 100ml there-necked flask, add the vitriol oil 30g of 98%, slowly add 5, the 6-bis-chloro-2-amino-benzothiazoles of 0.035mol under stirring, temperature controls at 20 DEG C, is then cooled to the nitrosyl sulfuric acid that less than 10 DEG C add 0.035mol.Separately get a there-necked flask, add 38g water, slowly add the vitriol oil 10g of 98%, ice bath is cooled to 0 DEG C, is then slowly dripped by the mixture in aforementioned there-necked flask so far in there-necked flask, maintains the temperature at 0 DEG C of reaction 2h, obtains diazo component.
(2) preparation of coupling component: in the 100ml there-necked flask that reflux exchanger, water trap and agitator are housed, add 0.035mol phenylformic acid, 0.035mol N-benzyl successively, N-β-anilino-ethanol and 100ml toluene, take tosic acid as catalyzer, heating point water refluxes 3 hours obtained N-benzyl-N-benzoxy ethylaniline.
(3) coupled reaction
Glacial acetic acid 200ml is added in another 1000ml flask, add the N-benzyl-N-benzoxy ethylaniline of 0.035mol, ice bath is cooled to less than 5 DEG C, slowly in system, drip diazo component, control 0 ~ 5 DEG C of reaction until diazo component disappears, the obtained thiazole heterocycle compound containing phenylformic acid ester group, after filtration, washing, to dry, this compound sand milling together with diffusant is obtained the thiazole heterocycle red alkali resistance high fastness dispersed dye containing phenylformic acid ester group.
Uv-visible absorption spectra, infrared spectra, hydrogen nuclear magnetic resonance spectrum and ultimate analysis demonstrate the exactness of this compound structure.
Embodiment 7
The synthesis preparation of the disperse dye compound that molecular structure is following:
(1) preparation of diazonium salt:
In 100ml there-necked flask, add the vitriol oil 30g of 98%, slowly add 5, the 6-bis-chloro-2-amino-benzothiazoles of 0.035mol under stirring, temperature controls at 20 DEG C, is then cooled to the nitrosyl sulfuric acid that less than 10 DEG C add 0.035mol.Separately get a there-necked flask, add 38g water, slowly add the vitriol oil 10g of 98%, ice bath is cooled to 0 DEG C, is then slowly dripped by the mixture in aforementioned there-necked flask so far in there-necked flask, maintains the temperature at 0 DEG C of reaction 2h, obtains diazo component.
(2) preparation of coupling component: in the 100ml there-necked flask that reflux exchanger, water trap and agitator are housed, add 0.035mol Benzoyl chloride, 0.035mol N-ethyl successively, N-hydroxyethyl meta-aminotoluene and 100ml toluene, heating point water refluxes 3 hours, steam solvent, obtained N-benzyl-N-benzoxy ethyl meta-aminotoluene.
(3) coupled reaction
Glacial acetic acid 200ml is added in another 1000ml flask, add the N-benzyl-N-benzoxy ethyl meta-aminotoluene of 0.035mol, ice bath is cooled to less than 5 DEG C, slowly in system, drip diazo component, control 0 ~ 5 DEG C of reaction until diazo component disappears, the obtained thiazole heterocycle compound containing phenylformic acid ester group, after filtration, washing, to dry, this compound sand milling together with diffusant is obtained the thiazole heterocycle red alkali resistance high fastness dispersed dye containing phenylformic acid ester group.
Uv-visible absorption spectra, infrared spectra, hydrogen nuclear magnetic resonance spectrum and ultimate analysis can demonstrate the exactness of this compound structure.
Embodiment 8 ~ 15
In embodiments, 5, the concentration of the chloro-2-amino-benzothiazole of 6-bis-is 0.035mol, with the proportioning of other material (mol than) and operate with embodiment 1, obtain a series of thiazole heterocycle containing phenylformic acid ester group red alkali resistance high fastness dispersed dye, the structure of each coupling component is in table 3.
Table 3 is containing the coupling component in the thiazole heterocycle red alkali resistance high fastness dispersed dye of phenylformic acid ester group
Embodiment n R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10
8 2 -H -H -H -CH 3 Benzyl -H -H -H -H -CH 3
9 2 -H -H -H -CH 3 -C 2H 4CN -H -H -H -H -H
10 3 -H -CH 3 -H -H -C 2H 5 -CH 3 -H -H -H -H
11 3 -H -H -H -CH 3 -C 2H 4CN -H -OCH3 -H -H -H
12 3 -H -H -H -CH 3 -C 2H 5 -H -H -NO 2 -H -H
13 4 -CH 3 -H -H -CH 3 -C 2H 4CN -H -H -H -C 2H 5 -H
14 4 -H -CH 3 -H -CH 3 -C 2H 5 -H -H -H -H -CH 3
15 4 -H -H -H -CH 3 -C 2H 4CN -OCH 3 -H -H -H -H
Embodiment 16
The thiazole heterocycle containing phenylformic acid ester group obtained by embodiment 1-6 red alkali resistance high fastness disperse dye compound mixes with dispersing agent NNO, and sand milling is dry, obtains red disperse dyes.
On intermittent type dyeing installation, as HTHP Jet Dyeing Machine, polyester piece good through destarch is put into acid dyeing bath (bath raio 1:10), directly add 2% (o.w.f) dispersed dye and with 0.1% high temperature levelling agent, adding proper amount of acetic acid regulates dye liquor pH value to be 4-5, by dyeing shown in Figure 12, obtain bright-coloured red dyeing terylene fabric.The dye uptake of test dye and dye uptake curve, respectively as shown in accompanying drawing 9,10.
Embodiment 17
The thiazole heterocycle containing phenylformic acid ester group obtained by embodiment 1-6 red alkali resistance high fastness disperse dye compound mixes with modifiers dispersants MF, and sand milling is dry, obtains red disperse dyes.
On intermittent type dyeing installation, as HTHP Jet Dyeing Machine, polyester piece good through destarch is put into acid dyeing bath (bath raio 1:10), directly add the dispersed dye of 0.5%, 1%, 2%, 3%, 5%, 8%, 10% (o.w.f) and appropriate high temperature levelling agent, adding proper amount of acetic acid regulates dye liquor pH value to be 4-5, by the dyeing of embodiment 16, and the lifting force curve of test dye, as shown in Figure 11, dyeing curve is shown in Figure 12 to result.
Embodiment 18
The thiazole heterocycle containing phenylformic acid ester group obtained by embodiment 7-12 red alkali resistance high fastness disperse dye compound mixes with Dispersant MF, and sand milling is dry, obtains red disperse dyes.
On intermittent type dyeing installation, as HTHP Jet Dyeing Machine, polyester piece good is put into dye bath (bath raio 1:10), directly add the dispersed dye of 2% (o.w.f) and the high temperature levelling agent of 0.1%, adding proper amount of acetic acid or sodium hydroxide regulates dye liquor pH value to be 4,6,8,10,11,12,13, respectively by the dyeing in embodiment 16, after washing, all obtain bright-coloured red dyeing terylene fabric.The K/S value of test fabric and L*, a*, b* value, result is as shown in table 4 below.
Table 4 embodiment 7-12 is the K/S value of DYED FABRICS and L*, a*, b* value at various ph values
Embodiment 19
Respectively according to GB/T3920-2008 " textile color stability test colour fastness to rubbing ", AATCC61/2003 " the resistance to family expenses of test procedure 1A and 2A and 3A and commercial laundering colour fastness: acceleration ", the colour fastness to rubbing of the relevant regulations testing example 1-10 of GB/T8427-2008 " textile color stability tests the colour fastness of resistance to artificial light: xenon arc " and GB/T6152-1997 " textile color stability experiment color fastness to hot pressing ", water-fastness colour fastness, colour fasteness to sunlight and color fastness to sublimation.Result is as shown in table 5, table 6.
The rub resistance of table 5 DYED FABRICS, Washing
Sun-resistant, the sublimation fastness of table 6 DYED FABRICS

Claims (9)

1., containing a red thiazole heterocycle disperse dye compound for phenylformic acid ester group, it is characterized in that: the general structure of described disperse dye compound is: wherein n=1,2,3,4,5 or 6;
R 1, R 2, R 3, R 4independent is hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, the one in kharophen;
R 5for the one in hydrogen, methyl, ethyl, benzyl, cyano group, cyanogen alkane, phenylformic acid ester group;
R 6, R 7, R 8, R 9, R 10it is independently the one in hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, kharophen, nitro, cyano group.
2. a preparation method for the red thiazole heterocycle disperse dye compound containing phenylformic acid ester group as claimed in claim 1, comprising:
(1) under room temperature condition, the chloro-2-amino-benzothiazole of 5,6-bis-will be added in sulfuric acid, drip water, be cooled to less than 10 DEG C, be then added dropwise to nitrosyl sulfuric acid, after dropwising, stir and be added dropwise in the mixing solutions of the vitriol oil of 0 DEG C and water, reaction 2h, obtains diazo component; Wherein the ratio of 5,6-bis-chloro-2-amino-benzothiazoles, nitrosyl sulfuric acid, the vitriol oil and water is 0.035mol:0.035mol:40g:38g;
(2) by phenylformic acid or benzoic acid derivative, N-hydroxyalkyl substituted aniline or N-hydroxyalkyl substituted aniline derivative, solvent, catalyzer mixing, heating point water backflow, obtain coupling component, wherein reflux temperature is 110 DEG C, and return time is 2-3h;
(3) above-mentioned coupling component is dissolved in acetic acid, then 0-5 DEG C is cooled to, then step (1) diazo component is added dropwise to, under keeping this temperature, reaction is until diazo component disappears, filter, wash, dry, obtain the red thiazole heterocycle disperse dye compound containing phenylformic acid ester group; Wherein the proportionlity of coupling component, diazo component, acetic acid is 0.035mol:0.035mol:200ml.
3. the preparation method of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group according to claim 2, is characterized in that: in described step (1), the mass percentage concentration of sulfuric acid is 98%.
4. the preparation method of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group according to claim 2, is characterized in that: in described step (2), solvent is toluene.
5. the preparation method of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group according to claim 2, is characterized in that: in described step (2), catalyzer is tosic acid or the vitriol oil.
6. the preparation method of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group according to claim 2, is characterized in that: in described step (2), the proportionlity of phenylformic acid or benzoic acid derivative, N-hydroxyalkyl substituted aniline or N-hydroxyalkyl substituted aniline derivative, solvent, catalyzer is 0.035-0.07mol:0.035-0.07mol:100ml:0-1g.
7. the preparation method of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group according to claim 2, is characterized in that: coupling component adopts Benzoyl chloride and N-hydroxyalkyl substituted aniline or N-hydroxyalkyl substituted aniline derivative to react to prepare.
8. an application for the red thiazole heterocycle disperse dye compound containing phenylformic acid ester group as claimed in claim 1, it is characterized in that: described disperse dye compound and auxiliary agent obtain red disperse dyes, wherein auxiliary agent is sodium naphthalene sulfonate derivative.
9. the application of a kind of red thiazole heterocycle disperse dye compound containing phenylformic acid ester group according to claim 8, is characterized in that: described auxiliary agent is one or more in dispersing agent NNO, Dispersant MF, modifiers dispersants MF.
CN201410350337.5A 2014-07-22 2014-07-22 Red thiazole heterocyclic disperse dye compound containing benzoate group and preparation and application thereof Pending CN104231659A (en)

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Application publication date: 20141224