CN102321386A - Pale purple active dye and preparation method thereof - Google Patents
Pale purple active dye and preparation method thereof Download PDFInfo
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- CN102321386A CN102321386A CN201110155536A CN201110155536A CN102321386A CN 102321386 A CN102321386 A CN 102321386A CN 201110155536 A CN201110155536 A CN 201110155536A CN 201110155536 A CN201110155536 A CN 201110155536A CN 102321386 A CN102321386 A CN 102321386A
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Abstract
The invention relates to a pale purple active dye and a preparation method thereof. The active dye has a general formula of a structure which is shown in the specification. The invention also provides the preparation method of the active dye. The dye is the monochromic pale purple active dye which is synthesized through design and adjustment in structure. A dyeing process has excellent repeatability and stability and superior fastness performance. Three wastes (waste water, waste gas and industrial residues) are not produced during production; and the environmental protection requirement is met.
Description
Technical field
The present invention relates to dye field, particularly be a kind of pale purple reactive dyestuffs and preparation method thereof.
Background technology
Reactive dyestuffs have been very universal for the dyeing of cellulosic fibre at present, and it has lovely luster.Characteristics such as fastness ability is good, easy to use.Though reactive dyestuffs can be risked colors such as green, purple, palm fibre through red, yellow, blue three-primary colours.But the colorant match process has received a series of control such as the coloured light intensity of former dyestuff and influence makes instability or process complicated.Form monogenetic dyestuff through structural adjustment and then avoided above-mentioned deficiency.Dyestuff of the present invention is the monochromatic pale purple reactive dyestuffs that synthesize from structure design adjustment.Dyeing course has good circulation ratio and stability, and fastness ability is superior.The preparation process does not have the three wastes and produces compliance with environmental protection requirements.
Summary of the invention
The purpose of this invention is to provide a kind of pale purple reactive dyestuffs and preparation method thereof, avoid some problems that run in the colorant match process.
The technical scheme that the present invention adopts is:
A kind of pale purple reactive dyestuffs, these reactive dyestuffs have the general formula of following structure (I):
R has a kind of in the following structure in the formula:
X is-F or-Cl;
M is-K or-Na.
The present invention also provides the preparation method of above-mentioned reactive dyestuffs, comprises the steps:
(a). para-ester is added to the water, and normal temperature is regulated pH=4.5～6.5 with 15% sodium carbonate solution down, treats condensation after complete the dissolving.
(b). cyanuric chloride joins in the frozen water, adds ice milling aid (volume percent consists of dioxane 30%, trolamine 30%, chloroform 30%, acetate 10%) again behind 0～10 ℃ of ice mill 5～30min, treats condensation.
(c). a step condensation: the solution of step (a) is joined in step (b) system with 5～10min; In 0～8 ℃; Keep between pH=2～5 with 97% sodium hydrogen carbonate solution, keep stirring 3.5～5 hours, thin-layer developing no para-ester under uv lamp is reaction end; The thing that contracts, treat that two contract.
(d). two step condensations: H acid powder is joined in the solution of step (c),, be warming up to 35～50 ℃ then, use 15%Na with 15% yellow soda ash adjustment pH=4.0～6.0
2CO
3Keep pH=4.0～6.0, keep to stir 5～10 hours, none thing that contracts of thin-layer developing is a terminal point, is cooled to 15～25 ℃, two things that contract, treat coupling.
(e). diazotization: midbody R ' is joined in the frozen water; The hydrochloric acid that adds 2.5～3.0 times of mol ratios; The sodium nitrite solution that adds 1.02 times of mol ratios fast keeps stirring 1.5～2 hours in 0～10 ℃, keeps nitrous acid little excessive, and reaction is removed excessive Sodium Nitrite with thionamic acid after accomplishing; Get diazonium salt, treat coupling.
(f). coupling: the diazonium salt of step (e) preparation is joined in step (d) solution, use 15%Na
2CO
3Solution transfers pH=5.0～6.5 to keep for 10～20 ℃ stirring 2～3 hours in this pH, temperature, and diazonium salt disappears and is terminal point, pH is adjusted to 5～5.5 treats that spraying is dry.
(g). the dye solution spraying drying that step (e) is made gets product.
Among the preparation method of above-mentioned reactive dyestuffs,
The para-ester chemistry is by name: to (beta-hydroxyethyl sulfone sulfate) aniline, structural formula is as follows:
The structural formula of cyanuric chloride is:
H acid is 1-amino-8-naphthol-3, the abbreviation of 6-disulfonate sodium, and its structural formula is following:
Midbody R ' is selected from 1 in the step (e), 4-sodium salt, 1, and 5-1-naphthlamine-6-sulfonic acid, 1,6-1-naphthlamine-6-sulfonic acid, 1, any in 7-1-naphthlamine-6-sulfonic acid, the Schollkopf acid, wherein
1,4-sodium salt chemistry naphthalidine by name-4-sodium sulfonate, structural formula is:
1,5-1-naphthlamine-6-sulfonic acid chemical name naphthalidine-5 sulfonic acid.Structural formula is:
1,6-1-naphthlamine-6-sulfonic acid chemical name naphthalidine-6-sulfonic acid.Structural formula is:
1,7-1-naphthlamine-6-sulfonic acid chemical name Cleve.Structural formula is:
Schollkopf acid chemical name naphthalidine-8-sulfonic acid.Structural formula is:
The beneficial effect that the present invention had:
Dyestuff of the present invention is the monochromatic pale purple reactive dyestuffs that synthesize from structure design adjustment.Dyeing course has good circulation ratio and stability, and fastness ability is superior.The preparation process does not have the three wastes and produces compliance with environmental protection requirements.
Embodiment
In order to understand the present invention, further specify the present invention with embodiment below, but do not limit the present invention.
Embodiment 1
The preparation of the pale purple reactive dyestuffs of formula (II) compound
The preparation process of the pale purple reactive dyestuffs of formula (II) compound is following
(a). in beaker, add water 200ml, add 100% amount para-ester 28.94g, regulate pH=4.5～6.5 with 15% sodium carbonate solution down, treat condensation after complete the dissolving at 5 ℃～15 ℃.
(b) the 18.45g cyanuric chloride of .100% amount joins in the 150g frozen water, adds ice milling aid (volume percent consists of dioxane 30%, trolamine 30%, chloroform 30%, acetate 10%) 4 again, behind 0～10 ℃ of ice mill 5～30min, treats condensation.
(c). a step condensation: the solution of step (a) is joined in step (b) system with 5～10min; In 0～8 ℃; Keep between pH=2～5 with 97% sodium hydrogen carbonate solution, keep stirring 3.5～5 hours, thin-layer developing no para-ester under uv lamp is reaction end; The thing that contracts, treat that two contract.
(d). two step condensations: 100% amount 33.08g H acid powder is joined in the solution of step (c),, be warming up to 35～40 ℃ then, use 15%Na with 15% yellow soda ash adjustment pH=4.0～6.0
2CO
3Keep pH=4.0～6.0, keep to stir 5～10 hours, none thing that contracts of thin-layer developing is a terminal point, is cooled to 15～25 ℃, two things that contract, treat coupling.
(e). diazotization: 1 of 100% amount, 4-sodium salt 24.5g joins in the frozen water, adds 30% hydrochloric acid 26.5ml; The Sodium Nitrite 7.32g of quick adding 96%; Solution keeps stirring 1.5～2 hours in 0～10 ℃, keeps nitrous acid little excessive, and reaction is removed excessive Sodium Nitrite with thionamic acid after accomplishing; Get diazonium salt, treat coupling.
(f). coupling: the diazonium salt of step (e) preparation is joined in step (d) solution, use 15%Na
2CO
3Solution transfers pH=5.0～6.5 to keep for 10～20 ℃ stirring 2～3 hours in this PH, temperature, and diazonium salt disappears and is pH to be adjusted to reaction end 5～5.5 to be equipped with spraying drying.
(g). the dye solution spraying drying that step (f) is made gets product.
Embodiment 2
The preparation of the pale purple reactive dyestuffs of formula (III) compound
The preparation process of the pale purple reactive dyestuffs of formula (III) compound is following
(a). in beaker, add water 200ml, add 100% amount para-ester 28.94g, regulate pH=4.5～6.5 with 15% sodium carbonate solution down, treat condensation after complete the dissolving at 5 ℃～15 ℃.
(b) the 18.45g cyanuric chloride of .100% amount joins in the 150g frozen water, adds ice milling aid (volume percent consists of dioxane 30%, trolamine 30%, chloroform 30%, acetate 10%) 4 again, behind 0～10 ℃ of ice mill 5～30min, treats condensation.
(c). a step condensation: the solution of step (a) is joined in step (b) system with 5～10min; In 0～8 ℃; Keep between pH=2～5 with 97% sodium hydrogen carbonate solution, keep stirring 3.5～5 hours, thin-layer developing no para-ester under uv lamp is reaction end; The thing that contracts, treat that two contract.
(d). two step condensations: 100% amount 33.08g H acid powder is joined in the solution of step (c),, be warming up to 35～40 ℃ then, use 15%Na with 15% yellow soda ash adjustment pH=4.0～6.0
2CO
3Keep pH=4.0～6.0, keep to stir 5～10 hours, none thing that contracts of thin-layer developing is a terminal point, is cooled to 15～25 ℃, two things that contract, treat coupling.
(e). diazotization: 1 of 100% amount, 5-1-naphthlamine-6-sulfonic acid 22.3g joins in the frozen water, adds 30% hydrochloric acid 26.5ml; The Sodium Nitrite 7.32g of quick adding 96%; Solution keeps stirring 1.5～2 hours in 0～10 ℃, keeps nitrous acid little excessive, and reaction is removed excessive Sodium Nitrite with thionamic acid after accomplishing; Get diazonium salt, treat coupling.
(f). coupling: the diazonium salt of step (e) preparation is joined in step (d) solution, use 15%Na
2CO
3Solution transfers pH=5.0～6.5 to keep for 10～20 ℃ stirring 2～3 hours in this PH, temperature, and diazonium salt disappears and is pH to be adjusted to reaction end 5～5.5 to be equipped with spraying drying.
(g). the dye solution spraying drying that step (f) is made gets product.
Embodiment 3
The preparation of the pale purple reactive dyestuffs of formula (IV) compound
The preparation process of the pale purple reactive dyestuffs of formula (IV) compound is following
(a). in beaker, add water 200ml, add 100% amount para-ester 28.94g, regulate pH=4.5～6.5 with 15% sodium carbonate solution down, treat condensation after complete the dissolving at 5 ℃～15 ℃.
(b) the 18.45g cyanuric chloride of .100% amount joins in the 150g frozen water, adds ice milling aid (volume percent consists of dioxane 30%, trolamine 30%, chloroform 30%, acetate 10%) 4 again, behind 0～10 ℃ of ice mill 5～30min, treats condensation.
(c). a step condensation: the solution of step (a) is joined in step (b) system with 5～10min; In 0～8 ℃; Keep between pH=2～5 with 97% sodium hydrogen carbonate solution, keep stirring 3.5～5 hours, thin-layer developing no para-ester under uv lamp is reaction end; The thing that contracts, treat that two contract.
(d). two step condensations: 100% amount 33.08g H acid powder is joined in the solution of step (c),, be warming up to 35～40 ℃ then, use 15%Na with 15% yellow soda ash adjustment pH=4.0～6.0
2CO
3Keep pH=4.0～6.0, keep to stir 5～10 hours, none thing that contracts of thin-layer developing is a terminal point, is cooled to 15～25 ℃, two things that contract, treat coupling.
(e). diazotization: 1 of 100% amount, 6-1-naphthlamine-6-sulfonic acid 22.3g joins in the frozen water, adds 30% hydrochloric acid 26.5ml; The Sodium Nitrite 7.32g of quick adding 96%; Solution keeps stirring 1.5～2 hours in 0～10 ℃, keeps nitrous acid little excessive, and reaction is removed excessive Sodium Nitrite with thionamic acid after accomplishing; Get diazonium salt, treat coupling.
(f). coupling: the diazonium salt of step (e) preparation is joined in step (d) solution, use 15%Na
2CO
3Solution transfers pH=5.0～6.5 to keep for 10～20 ℃ stirring 2～3 hours in this PH, temperature, and diazonium salt disappears and is pH to be adjusted to reaction end 5～5.5 to be equipped with spraying drying.
(g). the dye solution spraying drying that step (f) is made gets product.
Embodiment 4
The preparation of the pale purple reactive dyestuffs of formula V compound
The preparation process of the pale purple reactive dyestuffs of formula V compound is following
(a). in beaker, add water 200ml, add 100% amount para-ester 28.94g, regulate pH=4.5～6.5 with 15% sodium carbonate solution down, treat condensation after complete the dissolving at 5 ℃～15 ℃.
(b) the 18.45g cyanuric chloride of .100% amount joins in the 150g frozen water, adds ice milling aid (volume percent consists of dioxane 30%, trolamine 30%, chloroform 30%, acetate 10%) 4 again, behind 0～10 ℃ of ice mill 5～30min, treats condensation.
(c). a step condensation: the solution of step (a) is joined in step (b) system with 5～10min; In 0～8 ℃; Keep between pH=2～5 with 97% sodium hydrogen carbonate solution, keep stirring 3.5～5 hours, thin-layer developing no para-ester under uv lamp is reaction end; The thing that contracts, treat that two contract.
(d). two step condensations: 100% amount 33.08g H acid powder is joined in the solution of step (c),, be warming up to 35～40 ℃ then, use 15%Na with 15% yellow soda ash adjustment pH=4.0～6.0
2CO
3Keep pH=4.0～6.0, keep to stir 5～10 hours, none thing that contracts of thin-layer developing is a terminal point, is cooled to 15～25 ℃, two things that contract, treat coupling.
(e). diazotization: 1 of 100% amount; 7-1-naphthlamine-6-sulfonic acid 22.3g joins in the frozen water, adds 30% hydrochloric acid 26.5ml, adds 96% Sodium Nitrite 7.32g. solution fast and keeps stirring 1.5～2 hours in 0～10 ℃; Keep nitrous acid little excessive; Reaction is removed excessive Sodium Nitrite with thionamic acid after accomplishing, and gets diazonium salt, treats coupling.
(f). coupling: the diazonium salt of step (e) preparation is joined in step (d) solution, use 15%Na
2CO
3Solution transfers pH=5.0～6.5 to keep for 10～20 ℃ stirring 2～3 hours in this PH, temperature, and diazonium salt disappears and is pH to be adjusted to reaction end 5～5.5 to be equipped with spraying drying.
(g). the dye solution spraying drying that step (f) is made gets product.
The preparation of the pale purple reactive dyestuffs of embodiment 5 formulas (VI) compound
The preparation process of the pale purple reactive dyestuffs of formula (VI) compound is following
(a). in beaker, add water 200ml, add 100% amount para-ester 28.94g, regulate pH=4.5～6.5 with 15% sodium carbonate solution down, treat condensation after complete the dissolving at 5 ℃～15 ℃.
(b) the 18.45g cyanuric chloride of .100% amount joins in the 150g frozen water, adds ice milling aid (volume percent consists of dioxane 30%, trolamine 30%, chloroform 30%, acetate 10%) 4 again, behind 0～10 ℃ of ice mill 5～30min, treats condensation.
(c). a step condensation: the solution of step (a) is joined in step (b) system with 5～10min; In 0～8 ℃; Keep between pH=2～5 with 97% sodium hydrogen carbonate solution, keep stirring 3.5～5 hours, thin-layer developing no para-ester under uv lamp is reaction end; The thing that contracts, treat that two contract.
(d). two step condensations: 100% amount 33.08g H acid powder is joined in the solution of step (c),, be warming up to 35～40 ℃ then, use 15%Na with 15% yellow soda ash adjustment pH=4.0～6.0
2CO
3Keep pH=4.0～6.0, keep to stir 5～10 hours, none thing that contracts of thin-layer developing is a terminal point, is cooled to 15～25 ℃, two things that contract, treat coupling.
(e). diazotization: the Schollkopf acid 22.3g of 100% amount joins in the frozen water; The hydrochloric acid 26.5ml of adding 30%; The Sodium Nitrite 7.32g. solution of adding 96% keeps stirring 1.5～2 hours in 0～10 ℃ fast, keeps nitrous acid little excessive, removes excessive Sodium Nitrite with thionamic acid after the reaction completion; Get diazonium salt, treat coupling.
(f). coupling: the diazonium salt of step (e) preparation is joined in step (d) solution, use 15%Na
2CO
3Solution transfers pH=5.0～6.5 to keep for 10～20 ℃ stirring 2～3 hours in this PH, temperature, and diazonium salt disappears and is pH to be adjusted to reaction end 5～5.5 to be equipped with spraying drying.
(g). the dye solution spraying drying that step (f) is made gets product.
The performance table of the pale purple Dyeing of Cotton Fabric with Reactive Dyes of embodiment 1 preparation is following:
Pale purple reactive dyestuffs of the present invention and preparation method thereof are described through concrete embodiment.Those skilled in the art can use for reference links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other purpose; Its relevant change does not all break away from content of the present invention; All similar replacements and change will become apparent to those skilled in the art that all to be regarded as and are included within the scope of the present invention.
Claims (2)
1. pale purple reactive dyestuffs, it is characterized in that: these reactive dyestuffs have the general formula of following structure (I):
R has a kind of in the following structure in the formula:
X is-F or-Cl;
M is-K or-Na.
2. the preparation method of the said pale purple reactive dyestuffs of claim 1 is characterized in that: comprise the steps:
(a). para-ester is added to the water, and normal temperature is regulated pH=4.5～6.5 with 15% sodium carbonate solution down, treats condensation after complete the dissolving;
(b). cyanuric chloride joins in the frozen water, adds ice milling aid (volume percent consists of dioxane 30%, trolamine 30%, chloroform 30%, acetate 10%) again behind 0～10 ℃ of ice mill 5～30min, treats condensation;
(c). a step condensation: the solution of step (a) is joined in step (b) system with 5～10min; In 0～8 ℃; Keep between pH=2～5 with 97% sodium hydrogen carbonate solution, keep stirring 3.5～5 hours, thin-layer developing no para-ester under uv lamp is reaction end; The thing that contracts, treat that two contract;
(d). two step condensations: H acid powder is joined in the solution of step (c),, be warming up to 35～50 ℃ then, use 15%Na with 15% yellow soda ash adjustment pH=4.0～6.0
2CO
3Keep pH=4.0～6.0, keep to stir 5～10 hours, none thing that contracts of thin-layer developing is a terminal point, is cooled to 15～25 ℃, two things that contract, treat coupling;
(e). diazotization: midbody R ' is joined in the frozen water; The hydrochloric acid that adds 2.5～3.0 times of mol ratios; The sodium nitrite solution that adds 1.02 times of mol ratios fast keeps stirring 1.5～2 hours in 0～10 ℃, keeps nitrous acid little excessive, and reaction is removed excessive Sodium Nitrite with thionamic acid after accomplishing; Get diazonium salt, treat coupling; Described midbody R ' is selected from 1,4-sodium salt, 1,5-1-naphthlamine-6-sulfonic acid, 1,6-1-naphthlamine-6-sulfonic acid, 1, any in 7-1-naphthlamine-6-sulfonic acid, the Schollkopf acid;
(f). coupling: the diazonium salt of step (e) preparation is joined in step (d) solution, use 15%Na
2CO
3Solution transfers pH=5.0～6.5 to keep for 10～20 ℃ stirring 2～3 hours in this pH, temperature, and diazonium salt disappears and is terminal point, pH is adjusted to 5～5.5 treats that spraying is dry;
(g). the dye solution spraying drying that step (e) is made gets product.
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| CN201110155536A CN102321386A (en) | 2011-06-10 | 2011-06-10 | Pale purple active dye and preparation method thereof |
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| CN201110155536A CN102321386A (en) | 2011-06-10 | 2011-06-10 | Pale purple active dye and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299253A (en) * | 2018-02-11 | 2018-07-20 | 郑州轻工业学院 | Azo-compound with nonlinear optical properties and its synthetic method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018767A1 (en) * | 1994-12-13 | 1996-06-20 | Hoechst Celanese Corporation | A process for dyeing polyester/cotton blends |
| CN101874080A (en) * | 2007-11-26 | 2010-10-27 | 巴斯夫欧洲公司 | Improved shading process |
-
2011
- 2011-06-10 CN CN201110155536A patent/CN102321386A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018767A1 (en) * | 1994-12-13 | 1996-06-20 | Hoechst Celanese Corporation | A process for dyeing polyester/cotton blends |
| CN101874080A (en) * | 2007-11-26 | 2010-10-27 | 巴斯夫欧洲公司 | Improved shading process |
Non-Patent Citations (1)
| Title |
|---|
| 王德云 等: "含N-乙基桥一氯三嗪/乙烯砜双活性基染料性能研究", 《大连理工大学学报》, vol. 40, no. 4, 31 July 2000 (2000-07-31), pages 420 - 424 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299253A (en) * | 2018-02-11 | 2018-07-20 | 郑州轻工业学院 | Azo-compound with nonlinear optical properties and its synthetic method |
| CN108299253B (en) * | 2018-02-11 | 2019-10-08 | 郑州轻工业学院 | Azo-compound and its synthetic method with nonlinear optical properties |
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Application publication date: 20120118 |