CN103044960A - Dye reactive blue and preparation method thereof - Google Patents
Dye reactive blue and preparation method thereof Download PDFInfo
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- CN103044960A CN103044960A CN2010102652938A CN201010265293A CN103044960A CN 103044960 A CN103044960 A CN 103044960A CN 2010102652938 A CN2010102652938 A CN 2010102652938A CN 201010265293 A CN201010265293 A CN 201010265293A CN 103044960 A CN103044960 A CN 103044960A
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Abstract
The invention relates to a dye reactive blue of dyeing pure cotton and a preparation method thereof. The dye reactive blue is a dye as shown in a structural formula (I). The dye is an extra-deep reactive dye and a leading product in present reactive dye. When the dye is used for dyeing a deep color, due to different chromophoric degrees of chromogens of the dye, the chromogens and active groups are adapted, and thus a chromophoric degree is high and a reaction degree with fibers is high.
Description
Technical field
The invention belongs to the reactive dyestuffs field, particularly relate to a kind of active orchid of reactive dyestuffs that is applicable to pure cotton dyeing and preparation method thereof.
Background technology
Cotton fibre is the textile fibres of output maximum in the world, and reactive dyestuffs are cotton fibre with the best dyestuff of dyeing behavior.Compare with other Dyestuffs Used for Cellulose Fibres, it is complete that reactive dyestuffs have chromatogram, lovely luster, and the advantage such as wet colour fastness is good, and application art is easy, and suitability is strong, and price is relatively cheap adds not contain carcinogenic aromatic amine in the structure relative environmental protection.The reactive dyestuffs base type of China's development and production has nearly 20 kinds of X-type, K type, KM type, KE type, KP type, KD type, KN type, M type, EF type, ME type, Type B etc.Reactive dyestuffs can replace part glacial dye, thioxine dyes and vat dyes, also are applicable to the printing and dyeing needs of novel cellulose fiber product.Although reactive dyestuffs history is of short duration, be expected most development prospect at present, become production and competitively develop, use expanding day, well received dye, it is taken the course of its own in Dyestuffs Used for Cellulose Fibres, is the emphasis of development and use.But reactive dyestuffs traditional dyeing technique mainly is to exhaust to dye dyeing and can cause serious environmental pollution, and its problem of environmental pollution all is common concern and problem inferior to be solved all the time.Exhaust and dye in the dyeing course, fiber immerses in the dye bath, relies on dyestuff that the avidity of fiber is adsorbed onto on the fiber, then to the fibrous inside diffusion, to the most of dye transfer of dye bath to fiber on till.
At present will be to all improving gradually, so need to constantly research and develop the high dissimilar reactive dyestuffs of performance to performance requriements and the environmental protection of dyestuff.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of novel dye activity orchid and preparation method thereof,
Active blue for having the dyestuff of following structural formula (I):
Wherein
R
1For-H ,-SO
3M ,-OCH
3Or-CH
3
R
2For-H ,-SO
3M ,-OCH
3Or-CH
3
Z be H or-SO
2CH
2CH
2SO
3M;
Any substituting group that X is following structural formula (X-1) to the structural formula (X-8):
M is-H or basic metal.
Preferably, R in the dyestuff of structural formula (I)
1For-H; R
2For-SO
3M; Z is-SO
2CH
2CH
2SO
3M; X is X-1, X-2, X-3, X-4, X-5, X-6, X-7 or X-8.
Preferably, R in the dyestuff of structural formula (I)
1Be R
1For-H; R
2For-OCH
3Z is-SO
2CH
2CH
2SO
3M; X is X-1, X-2, X-3, X-4, X-5, X-6, X-7 or X-8.
Preferably, R in the dyestuff of structural formula (I)
1Be R
1For-SO
3M; R
2For-SO
3M; Z is H; X is X-1, X-2, X-3, X-4, X-5, X-6, X-7 or X-8.
The preparation of the compound of said structure formula (I) comprises the steps:
(a) diazotization reaction:
The compound dissolution of following structural formula (II) in water, is stirred, 30% quantitative hydrochloric acid soln is added, add rubble ice, make that mass/volume concentration is 10-15% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＜2.0, after soaking, starch potassium iodide paper is little blueness, T=0-5 ℃, reacted 2 hours, eliminate excessive nitrous acid with thionamic acid, get diazo liquid
R wherein
1, R
2, Z implication cotype (I) in implication;
(b) acid coupling reaction
The sour sodium hydroxide solution with 20%-40% of H is neutralized to PH=6.0-7.0, makes its whole dissolvings, join in the diazo liquid of step (a) acquisition, control T=0-5 ℃, reacted 6-10 hour, get acid coupling liquid.
(c) diazotization reaction:
Any compound in the following structural formula (X '-1) to (X '-8) is dissolved in water, then add 30% hydrochloric acid soln, add rubble ice, make that mass/volume concentration is 10-15% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＜2, be little blueness after potassium iodide starch paper soaks, T=0-5 ℃, reacted 2 hours, eliminate excessive nitrous acid with thionamic acid, get diazo liquid;
The O-methoxy para-ester
Position ester between O-methoxy
The Ke Lixiding para-ester
(d) alkaline coupling reaction
The acid coupling liquid that step (b) is obtained is adjusted into 20-25 ℃, and the diazo liquid that step (c) is obtained joins in this acid coupling liquid, and the PH=6.5-7.0 with soda ash accent solution is incubated 2.0-3.0 hour, gets alkaline coupling liquid;
(e) rubble ice is joined in the alkaline coupling liquid, adjusting temperature is 10-15 ℃, adds 30% sodium hydroxide solution, adjusts pH=9-9.5, keeps reaction 1-3 hour, then adjusts pH=6-7 with 30% hydrochloric acid soln;
(f) remove insolubles: the solution that will (e) step obtains joins and separates in the solid-liquid separator, removes waste residue, and collection filtrate is carried out spraying drying, namely obtains the dye composition of structural formula (I).
In the aforesaid method, the compound of structural formula (II) is preferably position ester, aniline-2 between sulfonation para-ester, meta-methoxy, the 5-disulfonic acid, and specifying information is as follows:
The chemistry of sulfonation para-ester is called 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, and its structural formula is as follows:
The meta-methoxy para-ester, its structural formula is as follows:
Aniline-2, the structural formula of 5-disulfonic acid is as follows:
Above-claimed cpd all is compounds well known in the prior art, and that can buy from the market obtains.
It is a kind of for the textile composition of dyeing that the present invention also provides, and said composition comprises dye composition and the dyestuff carrier of formula (I).
The present invention also provides the dye composition of above-mentioned formula (I) to be used for the textile purposes of dyeing.
The above-mentioned dyestuff that the present invention develops is the dark type reactive dyestuffs of a kind of spy, is the frontier nature product of current reactive dyestuffs.When above-mentioned dyes is dark, because the color development degree of its color bodies is different, adapt between color bodies and the active group, the color development degree is high, and is high with the fiber-reactive degree.
Embodiment
In order to understand the present invention, the below further specifies the present invention with embodiment, but does not limit the present invention.
The preparation of embodiment 1 formula (III) dye composition
A. meta-methoxy para-ester diazotization reaction:
In reactor, add end water, add 225 kilograms of meta-methoxy para-esters, stirring and dissolving, quantitative 30% hydrochloric acid soln is added, add rubble ice, make that mass/volume concentration is 15% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＞2.0, be little blueness after starch potassium iodide paper soaks, T=0-5 ℃, reacted 2 hours, eliminate excessive nitrous acid with thionamic acid, treat acid coupling, get diazo liquid;
B. acid coupling reaction
With 258.8 kilograms of H acid, with in 30% the sodium hydroxide solution and PH=6.0-7.0, make its whole dissolvings.In the ester diazo liquid of position, control T=0-5 ℃ between joining, reacted 7 hours, get acid coupling liquid;
C. the diazotization reaction of Sulpho Tobias Acid:
In reactor, add end water, add 300 kilograms of dissolvings of Sulpho Tobias Acid, 30% quantitative hydrochloric acid soln adds, and adds rubble ice, make that mass/volume concentration is 15% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＜2, be little blueness after potassium iodide starch paper soaks, T=0-5 ℃, reacted 2 hours, and eliminated excessive nitrous acid with thionamic acid, get diazo liquid;
D. alkaline coupling reaction
Acid coupling liquid is adjusted 25 ℃ of temperature, and in the diazo liquid adding acid coupling liquid with Sulpho Tobias Acid, the PH=6.5-7.0 with soda ash accent solution is incubated 2 hours.Terminal point with its reaction of TCL plate analysis.
E. rubble ice is joined in the alkaline coupling thing, adjusts 10-15 ℃ of temperature, add 30% sodium hydroxide solution, adjust pH=9-9.5, kept 2 hours, then adjust pH=6-7 with 30% hydrochloric acid soln,
F. remove insolubles: the solution of e step is joined in the solid-liquid separator separate, remove waste residue, collect filtrate, carry out the dyestuff that spraying drying gets top formula (III), obtain 1300 kilograms of dyestuff finished products.
The preparation of embodiment 2 formulas (IV) dye composition
A. the diazotization reaction of sulfonation para-ester
In reactor, add end water, add 350 kilograms of sulfonation para-ester, stirring and dissolving, add quantitative 30% hydrochloric acid, add rubble ice, make that mass/volume concentration is 10% in its solution, add again 30% sodium nitrite solution, PH in reaction soln＞2.0 are little blueness, T=0-5 ℃ after starch potassium iodide paper soaks, reacted 1 hour, eliminate excessive nitrous acid with thionamic acid, treat acid coupling, get diazo liquid
B. acid coupling reaction
With 270 kilograms of H acid, join in the diazo liquid of sulfonation para-ester, control T=18-20 ℃, reacted 8 hours, get acid coupling liquid;
C. sulfonated naphthalene para-ester diazotization reaction:
In reactor, add end water, add 340 kilograms of sulfonated naphthalene para-esters, stirring and dissolving, quantitative 30% hydrochloric acid soln is added, add rubble ice, make that mass/volume concentration is 10% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＞2.0, be little blueness after starch potassium iodide paper soaks, T=5-10 ℃, reacted 3 hours hours, eliminate excessive nitrous acid with thionamic acid, treat acid coupling, get diazo liquid
D. alkaline coupling reaction
Acid coupling liquid is adjusted 15-25 ℃ of temperature, and sulfonated naphthalene para-ester diazo liquid is added drop-wise in the acid coupling liquid, transfers pH=5.5-7.0 with soda ash in the dropping, drips to finish to keep 2 hours, and the TLC plate determines, treats aftertreatment after qualified.
E. adjust coloured light and intensity: the feed liquid of d step is dry with the small spraying tower, and the adjustment of coloured light and intensity is carried out in dyeing again according to coloration result,
F. dry: as the look liquid of e step to be joined in the feed liquid preheating container, adjust 210 ℃ of inlet temperatures, carry out spraying drying with 95-100 ℃ temperature out, get the dyestuff shown in the top formula (IV).Obtain 1600 kilograms of dyestuff finished products.
The preparation of embodiment 3 formulas (V) dye composition
A aniline 2.5 disulfonic acid diazotization reactions
In reactor, add end water, add aniline-2,210 kilograms of 5-disulfonic acids, stirring and dissolving adds quantitative 30% hydrochloric acid, adds rubble ice, make that mass/volume concentration is 10% in its solution, add again 30% sodium nitrite solution, the PH in reaction soln＞2.0, after soaking, starch potassium iodide paper is little blueness, T=0-5 ℃, reacted 3 hours, eliminate excessive nitrous acid with thionamic acid, treat acid coupling, get diazo liquid
B. acid coupling reaction
With 265.8 kilograms of H acid, use in the sodium hydroxide solution of 20%-40% and PH=6.0-7.0, make its whole dissolvings.Be added dropwise to aniline-2, in the 5-disulfonic acid diazo liquid, control T=0-5 ℃, reacted 6 hours, get acid coupling liquid;
C. Ke Lixiding para-ester diazotization reaction:
In reactor, add end water, add 300 kilograms of gram Li Xiding para-esters, stirring and dissolving, 30% quantitative hydrochloric acid soln is added, add rubble ice, make that mass/volume concentration is 13% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＞2.0, be little blueness after starch potassium iodide paper soaks, T=0-5 ℃, reacted 1 hour hour, eliminate excessive nitrous acid with thionamic acid, get diazo liquid;
D. alkaline coupling reaction
Acid coupling liquid is adjusted 5-10 ℃ of temperature, and gram Li Xiding para-ester diazo liquid is added drop-wise in the acid coupling liquid, transfers pH=5.5-7.0 with soda ash in the dropping, drips to finish to keep 2 hours, gets alkaline coupling liquid;
E. adjust coloured light and intensity: (d) step material is dry with the small spraying tower, and the adjustment of coloured light and intensity is carried out in dyeing again according to coloration result,
F. dry: as the look liquid of (e) step to be joined in the feed liquid preheating container, adjust 210 ℃ of inlet temperatures, carry out spraying drying with 95-100 ℃ temperature out, get the dyestuff of top structure formula V.Obtain 1100 kilograms of dyestuff finished products.
The application performance table of the textile cotton of the dyeing of embodiments of the invention 1:
Method of the present invention is described by specific embodiment.Those skilled in the art can use for reference the 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 and all be deemed to be included within the scope of the present invention.
Claims (8)
1. the dyestuff of a following structural formula (I):
Wherein
R
1For-H ,-SO
3M ,-OCH
3Or-CH
3
R
2For-H ,-SO
3M ,-OCH
3Or-CH
3
Z be H or-SO
2CH
2CH
2SO
3M;
Any substituting group that X is following structural formula (X-1) to the structural formula (X-8):
M is-H or basic metal.Basic metal is preferably Na.
2. the preparation method of dyestuff claimed in claim 1, the method comprises the steps:
(a) diazotization reaction:
The compound dissolution of following structural formula (II) in water, is stirred, 30% quantitative hydrochloric acid soln is added, add rubble ice, make that mass/volume concentration is 10-15% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＜2.0, after soaking, starch potassium iodide paper is little blueness, T=0-5 ℃, reacted 2 hours, eliminate excessive nitrous acid with thionamic acid, get diazo liquid
R wherein
1, R
2, Z implication cotype (I) in implication;
(b) acid coupling reaction
The sour sodium hydroxide solution with 20%-40% of H is neutralized to PH=6.0-7.0, makes its whole dissolvings, join in the diazo liquid of step (a) acquisition, control T=0-5 ℃, reacted 6-10 hour, get acid coupling liquid,
(c) diazotization reaction:
Any compound in the following structural formula (X '-1) to (X '-8) is dissolved in water, then add 30% hydrochloric acid soln, add rubble ice, make that mass/volume concentration is 10-15% in its solution, add again 30% sodium nitrite solution, make PH in the reaction soln＜2, be little blueness after potassium iodide starch paper soaks, T=0-5 ℃, reacted 2 hours, eliminate excessive nitrous acid with thionamic acid, get diazo liquid;
2-amino naphthalenes-3,6, the 8-trisulfonic acid
(d) alkaline coupling reaction
The acid coupling liquid that step (b) is obtained is adjusted into 20-25 ℃, and the diazo liquid that step (c) is obtained joins in this acid coupling liquid, and the PH=6.5-7.0 with soda ash accent solution is incubated 2.0-3.0 hour, gets alkaline coupling liquid;
(e) rubble ice is joined in the alkaline coupling liquid, adjusting temperature is 10-15 ℃, adds 30% sodium hydroxide solution, adjusts pH=9-9.5, keeps reaction 1-3 hour, then adjusts pH=6-7 with 30% hydrochloric acid soln;
(f) remove insolubles: the solution that will (e) step obtains joins and separates in the solid-liquid separator, removes waste residue, and collection filtrate is carried out spraying drying, namely obtains the dye composition of structural formula (I).
3. dyestuff according to claim 1, wherein R in the dyestuff of structural formula (I)
1For-H; R
2For-SO
3M; Z is-SO
2CH
2CH
2SO
3M; X is X-1, X-2, X-3, X-4, X-5, X-6, X-7 or X-8.
4. dyestuff according to claim 1, wherein R in the dyestuff of structural formula (I)
1Be R
1For-H; R
2For-OCH
3Z is-SO
2CH
2CH
2SO
3M; X is X-1, X-2, X-3, X-4, X-5, X-6, X-7 or X-8.
5. dyestuff according to claim 1, wherein R in the dyestuff of structural formula (I)
1Be R
1For-SO
3M; R
2For-SO
3M; Z is H; X is X-1, X-2, X-3, X-4, X-5, X-6, X-7 or X-8.
6. method according to claim 2, wherein the compound of structural formula (II) is position ester and aniline-2 between sulfonation para-ester, meta-methoxy, the 5-disulfonic acid.
7. one kind is used for the textile composition of dyeing, and said composition comprises claim 1,3,4 or 5 described dye compositions and dyestuff carrier.
8. claim 1,3,4 or 5 described dyestuffs are used for the textile purposes of dyeing.
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|---|---|---|---|
| CN2010102652938A CN103044960A (en) | 2010-08-27 | 2010-08-27 | Dye reactive blue and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327543A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Navy blue nylon reactive dye |
| CN104327544A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Navy blue reactive dye and its preparation method |
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|---|---|---|---|---|
| US4530996A (en) * | 1981-06-15 | 1985-07-23 | Sumitomo Chemical Company, Limited | Bisazo blue-black dye having vinylsulfone type fiber-reactive group |
| CN1163909A (en) * | 1996-03-13 | 1997-11-05 | 巴斯福股份公司 | Reactive disazo dyes having naphthalenesulfonic acid coupling component |
| CN1195678A (en) * | 1997-04-07 | 1998-10-14 | 希巴特殊化学控股公司 | Mixtures of reactive dyes and their use |
| CN1912014A (en) * | 2006-08-15 | 2007-02-14 | 大连华成中瑞科技有限公司 | Dark black active dyestuff having high colour fixing rate |
| CN101283054A (en) * | 2005-10-05 | 2008-10-08 | 德意志戴斯达纺织品及染料两合公司 | Azo reactive dyes and mixtures of fiber-reactive azo dyes, their preparation and their use |
-
2010
- 2010-08-27 CN CN2010102652938A patent/CN103044960A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530996A (en) * | 1981-06-15 | 1985-07-23 | Sumitomo Chemical Company, Limited | Bisazo blue-black dye having vinylsulfone type fiber-reactive group |
| CN1163909A (en) * | 1996-03-13 | 1997-11-05 | 巴斯福股份公司 | Reactive disazo dyes having naphthalenesulfonic acid coupling component |
| CN1195678A (en) * | 1997-04-07 | 1998-10-14 | 希巴特殊化学控股公司 | Mixtures of reactive dyes and their use |
| CN101283054A (en) * | 2005-10-05 | 2008-10-08 | 德意志戴斯达纺织品及染料两合公司 | Azo reactive dyes and mixtures of fiber-reactive azo dyes, their preparation and their use |
| CN1912014A (en) * | 2006-08-15 | 2007-02-14 | 大连华成中瑞科技有限公司 | Dark black active dyestuff having high colour fixing rate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327543A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Navy blue nylon reactive dye |
| CN104327544A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Navy blue reactive dye and its preparation method |
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Application publication date: 20130417 |