CN103342901A - High-performance polyazo green reactive dye and synthesis and application of dye mixture - Google Patents
High-performance polyazo green reactive dye and synthesis and application of dye mixture Download PDFInfo
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- CN103342901A CN103342901A CN2013102873949A CN201310287394A CN103342901A CN 103342901 A CN103342901 A CN 103342901A CN 2013102873949 A CN2013102873949 A CN 2013102873949A CN 201310287394 A CN201310287394 A CN 201310287394A CN 103342901 A CN103342901 A CN 103342901A
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Abstract
The invention discloses a high-performance polyazo green reactive dye. The reactive dye contains polyazo dye shown in a formula I and is applied to cellulose fibers such as cotton and hemp and protein fibers such as wool and silk for dip dyeing, continuous dyeing and textile printing. The high-performance polyazo green reactive dye is green, has relatively high dye uptake and fixation rate and meanwhile has very high wet fastness such as wash well and perspiration resistance as well as light fastness. As the high-performance polyazo green reactive dye is a monogenetic dye, the monogenetic dyestuff has no disadvantages of poor head and tail and poor side and middle during continuous coloring.
Description
Technical field
The present invention relates to the synthetic of a kind of reactive polyazo dyes, and mixed thing and the application thereof of the green reactive dyestuffs of a kind of high property polyazo.
Background technology
Reactive dyestuffs claim chemically-reactive dyes again.Owing to contain in its structure can with native cellulose fibre or synthetic cellulose fibres in hydroxyl or the amino Activity of Chemical Reaction group that takes place gain the name.This class dyestuff when dyeing dyestuff and fiber react, form covalent linkage, thereby make the every fastness index of dyestuff especially wet colour fastness be improved, obtained development widely and used, becoming cellulose fiber Wesy first class dye activity dyestuff, is the second largest class dyestuff that is only second to dispersed dye.
Along with the raising day by day of standard of living, people begin more to value color, the style of dressing at ordinary times.Thereby it is more to fuller, the painted more firm clothes demand of color.
In the market Chang Yong dark series dyes for example green, brown, black generally all be that colorant match forms, green main yellow dyes, blue dyes are pieced together to mix and are formed, and black mainly contains blue dyestuff, orchil, yellow dyes or being pieced together to mix by blue dyes and orange dye forms.
Though aforesaid method can obtain lovely luster, well behaved green, black dyes, but because the structural difference of yellow dyes, orange dye and blue dyes causes its substantivity to fiber to differ greatly, make the speed of dying on the fiber inconsistent, cause occurring in the especially continuous dyeing process of dyeing course the look flower, it is poor also can to cause simultaneously in the poor and limit end to end of fiber, can not satisfy the needs in market.
Involved green of the present invention and blue dyes are the single structure dyestuffs, intramolecularly contains a plurality of color development group, have good depth and lifting force, have good level-dyeing property, very high dye uptake and degree of fixation simultaneously, and excellent wet colour fastness.Be specially adapted to continuous gadolinium dyeing, bright in colour full, overcome the shortcoming of colorant match dyestuff commonly used at present, improved the one-time success rate of dyeing.
Commercially available active green colouring material mainly is based on light green, blackish green at present, all form with blue, yellow colorant match, blackish green H-4BD is monogenetic dyestuff, it is not energy-conservation that but it belongs to the high temperature modification dyestuff, these dyestuffs all have above-mentioned poor, the easy defective of look flower etc. of level-dyeing property of mentioning, and are especially particularly outstanding under the condition of low temperature; Specially for this reason developed a series of excellent performances, good level-dyeing property, consistency is good, degree of fixation is high, can satisfy the green colouring material of monochrome of the environment-friendly type of market and environmental requirement, further colorant match goes out high performance black and active dye on this basis, make printing and dyeing enterprise one-time success rate height during continuous dyeing especially when using, reduce the printing and dyeing cost.
In view of this, outstanding the present invention.
Summary of the invention
The objective of the invention is to protect a kind of high-performance polyazo reactive dyestuffs; this dyestuff has unique homogencous dyes structure; be used for exhaust dyeing, continuous dyeing and stamp on cellulosic fibre such as cotton, fiber crops or the protein fibres such as hair, silk; be blue to green; can be red with other, Huang or orange dye obtain aterrimus series after mixing; its characteristics are not only have higher dye uptake and degree of fixation; also have wet colour fastness and light fastnesss such as very good washable, sweat proof simultaneously, have good easy detergency and higher lifting force.Owing to be monogenetic dyestuff, when continuous dyeing, there is not the shortcoming of difference in the poor and limit end to end.Simple to operate during application, save advantages such as the energy, no color differnece.
For realizing purpose of the present invention, adopt following technical scheme:
A kind of high-performance polyazo reactive dyestuffs is characterized in that, described turquoise, navy dyestuff has following general formula and is: the polyazo dye structure of formula I:
In the above-mentioned general formula:
R
1Have following general formula II:
R
3, R
4Having nothing in common with each other, independently is hydrogen, methyl, methoxyl group, sulfonic group separately;
R
2Can with R
1Identical, also can have following general formula III;
R
1With R
2The position can exchange passable;
The structure that a general formula II must be arranged in the formula I;
Described R
1Have following formula II-1, II-2 structure:
R
3Be hydrogen, methoxyl group, sulfonic group; R
4Be hydrogen, methyl;
R
2With R
1Can have identical structure, or have following structure:
Described reactive polyazo dyes can monochromaticly use, and also can be combined into black with yellow, redness or orange dye and use, and it is 60%～70% that the assembly of formula I dyestuff mixes weight ratio.
Described reactive polyazo dyes can with reactive black KN-B(C.I. reactive black 5) colorant match uses, the mixed weight ratio of the assembly of reactive black KN-B and formula I dyestuff is 20:50～80:20.
Described reactive polyazo dyes and composition thereof carries out the application of exhaust dyeing, continuous dyeing and stamp at the cellulose materials that contains hydroxyl or amino.
Another object of the present invention is to provide a kind of preparation method of above-mentioned dyestuff, for realizing second purpose of the present invention, adopt following technical scheme:
The preparation method of above-mentioned reactive polyazo dyes, all cpds with the diazo coupling method composite structure (II) of routine, and then with (II) formula compound method diazotization with routine in sulfuric acid or hydrochloric acid, o'clock carry out acid coupling in pH2～3 with H acid, with the method for routine with (III) formula compound diazotization, carry out alkaline coupling with above-mentioned acid coupling thing in pH6～7 again, also can be earlier (III) formula compound diazotization and H acid o'clock be carried out acid coupling in pH2～3, carry out alkaline coupling in pH6～7 with diazotizing (II) formula compound again and obtain from blueness to green reactive dyestuffs (being I formula dyestuff); Formula I dyestuff and other are red, Huang or orange dye certain proportion in proportion wet and piece together mixedly, namely get the aterrimus series dyes.
The present invention also claimed above-mentioned reactive printing dyes carries out the application of exhaust dyeing, continuous dyeing and stamp at the cellulose materials that contains hydroxyl or amino.
Below the present invention is further detailed:
For example green, black generally all are that colorant match forms to Chang Yong dark series dyes in the market, green main yellow dyes, blue dyes are pieced together to mix and are formed, and black mainly contains blue dyestuff, orchil, yellow dyes or being pieced together to mix by blue dyes and orange dye forms.But because the structural difference of yellow dyes, orange dye and blue dyes causes its substantivity to fiber to differ greatly; make the speed of dying on the fiber inconsistent; cause occurring in the especially continuous dyeing process of dyeing course the look flower; it is poor also can to cause simultaneously in the poor and limit end to end of fiber; make the one-time success rate of printing and dyeing enterprise very low; also need to repair look when serious, this cost that will cause printing and dyeing increases considerably, and can't satisfy the needs of requirement and the environment protection of enterprise.
Involved new green colouring material of the present invention is the single structure dyestuff, can improve the above-mentioned shortcoming of dyestuff to a great extent, it is characterized in that using supramolecular chemistry theory and organic synthesis theory, with the emission system of dyestuff prolong the color red shift that makes dyestuff (wavelength increases, color increase deeply), to the substantivity increase of fiber, thereby make this class dyestuff have good depth and lifting force, have good level-dyeing property, very high dye uptake and degree of fixation simultaneously, and excellent wet colour fastness.Be specially adapted to continuous gadolinium dyeing, bright in colour full, overcome the shortcoming of colorant match dyestuff commonly used at present, improved the one-time success rate of dyeing, satisfy the requirement of enterprise.
A kind of high-performance polyazo reactive dyestuffs is characterized in that, described turquoise, navy dyestuff has following general formula and is: the polyazo dye structure of formula I:
In the above-mentioned general formula:
R
1Have following general formula II:
R
3, R
4Having nothing in common with each other, independently is hydrogen, methyl, methoxyl group, sulfonic group separately;
R
2Can with R
1Identical, also can have following general formula III;
R
1With R
2The position can exchange passable;
The structure that a general formula II must be arranged in the formula I;
Described R
1Have following formula II-1, II-2 structure:
R
3Be hydrogen, methoxyl group, sulfonic group; R
4Be hydrogen, methyl;
R
2With R
1Can have identical structure, or have following structure:
As preferred implementation of the present invention, turquoise, the navy dye structure of preferred formula I is as shown in the formula (I-1～I-10):
The polyazo dye of formula I can get with common diazonium coupling method, and the compound that is about to general formula II and III carries out diazotization respectively with Sodium Nitrite in sulfuric acid or hydrochloric acid, carry out acidity, alkaline coupling with H acid then.
The monoazo-dyes of general formula II also is to get with common diazonium coupling method, and namely just the compound of general formula III carries out diazotization with Sodium Nitrite in hydrochloric acid, carries out coupling with 2-amino-4-kharophen Phenylsulfonic acid then.
Described reactive polyazo dyes can monochromaticly use, and also can be combined into black with yellow, redness or orange dye and use, and it is 60%～70% that the assembly of formula I dyestuff mixes weight ratio.
Described reactive polyazo dyes can with reactive black KN-B(C.I. reactive black 5) colorant match uses, the mixed weight ratio of the assembly of reactive black KN-B and formula I dyestuff is 20:50～80:20.
Reactive polyazo dyes of the present invention and composition thereof can be that dry powder piece together to mix also can be to mix wet the assembly, pieces together with wet that to mix the dyestuff performance that obtains better especially, and this dyestuff is applicable on the filamentary material of hydroxyl and nitrogen and carries out exhaust dyeing, continuous dyeing and stamp.For example cotton, viscose glue, fiber crops, silk, etc. and BLENDED FABRIC.
Reactive polyazo dyes of the present invention and composition thereof is for the application of carrying out exhaust dyeing, continuous dyeing and stamp on the cellulosic fibre.Continuous dyeing, form the gadolinium dye liquor with an amount of dyestuff, adding levelling agent etc., again caustic soda, soda ash, salt are made into fixation liquid, through soaking the gadolinium dye liquor, drying, soak technologies such as gadolinium fixation liquid, decatize, washing, drying, can obtain the product of excellent property, not only have higher dye uptake and degree of fixation, also have wet colour fastness and light fastnesss such as very good washable, sweat proof simultaneously, have good easy detergency and higher lifting force.The shortcoming of not having difference in the poor and limit end to end.Simple to operate during application, the saving energy.
Following example is used for explanation content of the present invention, and except as otherwise noted, temperature be degree centigrade, part and per-cent be weight part and weight percent, the relation of weight part and parts by volume with kilogram and the relationship consistency of liter.
Embodiment
The preparation of embodiment 1 polyazo dark blue dye I-1
In 1000 milliliters beaker, add 150 parts of water, 28.1 parts of para-esters, 0.1 part of dispersion agent, stirring to pulp 2h adds 30 part 30% hydrochloric acid, carried out diazotization reaction 2 hours at 0～5 ℃ of sodium nitrite solution that adds 23 part 30% down, behind terminal point, add the excessive nitrous acid of thionamic acid destruction, add 341 parts of H acid then, be warming up to 10～15 ℃, sodium acetate soln with 15% is regulated pH=2～2.5, reacted 4～6 hours, and be terminal point during no diazonium salt, standby.
In 1000 milliliters beaker, add 350 parts of water, 52.3 parts of formula II-1 compound (R
3, R
4Be hydrogen), 0.1 part of dispersion agent, be stirred to molten entirely, the sulfuric acid that adds 30 part 50%, carried out diazotization reaction 2 hours at 0～5 ℃ of sodium nitrite solution that adds 23 part 30% down, behind terminal point, add the excessive nitrous acid of thionamic acid destruction, join in the above-mentioned acid coupling thing, sodium carbonate solution with 20% is regulated pH=6.5～7.0 and is carried out alkaline coupling 2～3h, be terminal point during no diazonium salt, convection drying obtains dyestuff I-1.
Embodiment 2-5 polyazo is dark blue, the preparation of green colouring material I-2～I-5
Method with reference to embodiment 1 can obtain dyestuff I-2～I-5, compares with example 1, and distinctive points only is the formula II in the reaction process different with the substituting group of III formula compound.
The preparation of embodiment 6-11 polyazo green colouring material I-6～I-11
With embodiment 1 similar method the diazonium compound of formula II and formula and the coupling of H acid are changed in proper order, the diazonium compound that is the II formula earlier carries out acid coupling with H acid, and then carries out alkaline coupling with III formula diazonium compound and obtain polyazo green colouring material I-6～I-11.
Only exemplified the part dyestuff of formula I herein, those skilled in the art will envision that and adopt dyestuff I that different reactants can obtain having different substituents with final realization the present invention, length is limit herein, repeats no more.
Embodiment 12
Getting 70 parts of examples, 6 synthetic formula I-6 dyestuff and 15 parts of reactive orange 6R, 15 parts of active deep red B dyestuffs mixes, the adding proper assistant is carried out commercialization and is obtained commercial dye, get 5 parts of addings of this mixture 2 parts of wetting agent B, 13 parts of dyeing accelerant PT and be made into dye liquor, again 6 parts of caustic soda, 20 portions of soda ash, 250 salt are made into fixation liquid.Carry out continuous dyeing with pure cotton fabric: soak the gadolinium dye liquor, dry, soak gadolinium fixation liquid, decatize, washing, oven dry, obtain the aterrimus fabric.
Embodiment 22 active pitch black preparations
Embodiment 13
Getting 30 parts of examples, 11 synthetic formula I-11 dyestuff and 35 parts of reactive black KN-B, 20 parts of reactive orange 6R, 10 parts of active deep red B dyestuffs mixes, the adding proper assistant is carried out commercialization and is obtained commercial dye, get 5 parts of addings of this mixture 2 parts of wetting agent B, 13 parts of dyeing accelerant PT and be made into dye liquor, again 6 parts of caustic soda, 20 portions of soda ash, 250 salt are made into fixation liquid.Carry out continuous dyeing with pure cotton fabric: soak the gadolinium dye liquor, dry, soak gadolinium fixation liquid, decatize, washing, oven dry, obtain the aterrimus fabric.
The application of embodiment 14 high-performance polyazo navy dyestuff I
Get 5 parts of above-mentioned dyestuff I-1, add 2 parts of wetting agent B, 13 parts of dyeing accelerant PT and be made into dye liquor, again 6 parts of caustic soda, 20 portions of soda ash, 250 salt are made into fixation liquid.Carry out continuous dyeing with pure cotton fabric: soak the gadolinium dye liquor, dry, soak gadolinium fixation liquid, decatize, washing, oven dry, obtain the navy fabric.
The application of embodiment 15 high-performance polyazo green colouring material I
Get 5 parts of above-mentioned dyestuff I-6, add 2 parts of wetting agent B, 13 parts of dyeing accelerant PT and be made into dye liquor, again 6 parts of caustic soda, 20 portions of soda ash, 250 salt are made into fixation liquid.Carry out continuous dyeing with pure cotton fabric: soak the gadolinium dye liquor, dry, soak gadolinium fixation liquid, decatize, washing, oven dry, obtain green-fabrics.
The application of embodiment 16 high-performance polyazo black dyess
Get the aterrimus dyestuff of 5 parts of examples 12, add 2 parts of wetting agent B, 13 parts of dyeing accelerant PT and be made into dye liquor, again 6 parts of caustic soda, 20 portions of soda ash, 250 salt are made into fixation liquid.Carry out continuous dyeing with pure cotton fabric: soak the gadolinium dye liquor, dry, soak gadolinium fixation liquid, decatize, washing, oven dry, obtain the aterrimus fabric.
Claims (5)
1. the green reactive dyestuffs of a high-performance polyazo is characterized in that, described turquoise, navy dyestuff general formula is: the polyazo dye structure of formula I:
In the above-mentioned general formula:
R
1Have following general formula II:
R
3, R
4Having nothing in common with each other, independently is hydrogen, methyl, methoxyl group, sulfonic group separately;
R
2Can with R
1Identical, also can have following general formula III;
R
1With R
2The position can exchange passable;
The structure that a general formula II must be arranged in the formula I.
2. reactive polyazo dyes according to claim 1 is characterized in that: described R
1Have following formula II-1, II-2 structure:
R
3Be hydrogen, methoxyl group, sulfonic group; R
4Be hydrogen, methyl;
R
2With R
1Can have identical structure, or have following structure:
3. reactive polyazo dyes according to claim 1 is characterized in that: described reactive polyazo dyes can monochromaticly use, and also can be combined into black with yellow, redness or orange dye and use, and it is 60%～70% that the assembly of formula I dyestuff mixes weight ratio.
4. reactive polyazo dyes according to claim 3 is characterized in that: described reactive polyazo dyes can with reactive black KN-B(C.I. reactive black 5) colorant match uses, the mixed weight ratio of the assembly of reactive black KN-B and formula I dyestuff is 20:50～80:20.
5. described reactive polyazo dyes of claim 1-4 and composition thereof carries out the application of exhaust dyeing, continuous dyeing and stamp at the cellulose materials that contains hydroxyl or amino.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176141A (en) * | 2015-05-26 | 2015-12-23 | 浙江龙盛集团股份有限公司 | Activated dark blue to black dye compositioncombination and dye product |
| CN105199427A (en) * | 2014-12-19 | 2015-12-30 | 浙江科永化工有限公司 | Polyazo reactive dye compound and preparation method therefor |
| CN105400234A (en) * | 2015-11-20 | 2016-03-16 | 浙江龙盛集团股份有限公司 | Poly-azo reactive black dye composition, dye product and application of dye product |
| CN108530941A (en) * | 2017-03-01 | 2018-09-14 | 湖北丽源科技股份有限公司 | A kind of dark blue reactive dye and application thereof |
| CN108530946A (en) * | 2017-03-01 | 2018-09-14 | 湖北丽源科技股份有限公司 | A kind of black reactive dye mixture and its application |
| CN108530943A (en) * | 2017-03-01 | 2018-09-14 | 湖北丽源科技股份有限公司 | A kind of black reactive dye mixture and its application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60130652A (en) * | 1983-12-16 | 1985-07-12 | Mitsui Toatsu Chem Inc | Trisazo reactive dye |
| US5964900A (en) * | 1997-06-24 | 1999-10-12 | Ciba Specialty Chemicals Corporation | Process for dyeing or printing cellulosic fibre materials and novel reactive dyes |
-
2013
- 2013-07-09 CN CN2013102873949A patent/CN103342901A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60130652A (en) * | 1983-12-16 | 1985-07-12 | Mitsui Toatsu Chem Inc | Trisazo reactive dye |
| US5964900A (en) * | 1997-06-24 | 1999-10-12 | Ciba Specialty Chemicals Corporation | Process for dyeing or printing cellulosic fibre materials and novel reactive dyes |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199427A (en) * | 2014-12-19 | 2015-12-30 | 浙江科永化工有限公司 | Polyazo reactive dye compound and preparation method therefor |
| CN105199427B (en) * | 2014-12-19 | 2019-09-03 | 浙江科永化工有限公司 | A kind of polyazo reactive dye compound and preparation method thereof |
| CN105176141A (en) * | 2015-05-26 | 2015-12-23 | 浙江龙盛集团股份有限公司 | Activated dark blue to black dye compositioncombination and dye product |
| CN105400234A (en) * | 2015-11-20 | 2016-03-16 | 浙江龙盛集团股份有限公司 | Poly-azo reactive black dye composition, dye product and application of dye product |
| CN105400234B (en) * | 2015-11-20 | 2018-02-13 | 浙江龙盛集团股份有限公司 | A kind of polyazo active black dye composition and dye preparations and its application |
| CN108530941A (en) * | 2017-03-01 | 2018-09-14 | 湖北丽源科技股份有限公司 | A kind of dark blue reactive dye and application thereof |
| CN108530946A (en) * | 2017-03-01 | 2018-09-14 | 湖北丽源科技股份有限公司 | A kind of black reactive dye mixture and its application |
| CN108530943A (en) * | 2017-03-01 | 2018-09-14 | 湖北丽源科技股份有限公司 | A kind of black reactive dye mixture and its application |
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Application publication date: 20131009 |