CN101092522A - Activated dye, prepartion method, and application - Google Patents
Activated dye, prepartion method, and application Download PDFInfo
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- CN101092522A CN101092522A CN 200610027959 CN200610027959A CN101092522A CN 101092522 A CN101092522 A CN 101092522A CN 200610027959 CN200610027959 CN 200610027959 CN 200610027959 A CN200610027959 A CN 200610027959A CN 101092522 A CN101092522 A CN 101092522A
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- 238000000034 method Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 238000004043 dyeing Methods 0.000 claims abstract description 25
- 239000000975 dye Substances 0.000 claims description 49
- 238000005859 coupling reaction Methods 0.000 claims description 34
- 230000008878 coupling Effects 0.000 claims description 32
- 238000010168 coupling process Methods 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012954 diazonium Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 238000006193 diazotization reaction Methods 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 6
- -1 sulfonic group Chemical group 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 229920003043 Cellulose fiber Polymers 0.000 abstract 2
- 239000002657 fibrous material Substances 0.000 abstract 2
- 239000002994 raw material Substances 0.000 description 52
- 239000000835 fiber Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 241000219146 Gossypium Species 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012928 buffer substance Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000004045 reactive dyeing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
This invention provides a high-performance active dye compound for dyeing and printing of cellulose fiber material. The dye compound has such advantages as high adhesiveness to cellulose fiber material, high light resistance, high water resistance, and high color fastness. Besides, the un-adhered part of the dye compound during dyeing can be easily removed by washing. This invention also provides a method for preparing the dye compound, and its applications.
Description
Technical field
The present invention relates to dye composition, Its Preparation Method And Use, relate to reactive dyestuffs, preparation method and its usage particularly.
Background technology
In recent years, in reactive dyeing was implemented, industry had proposed stricter requirement to the efficient of its dyeing quality and dyeing course.Therefore, be necessary to provide to have the new reactive dyestuffs of strengthening the property: the one,, this dyestuff is for treating that painted base material must have enough substantive dyeings, also has the performance that the dyestuff of not set is easily washed off simultaneously.The 2nd,, this dyestuff can provide good tinctorial yield, fixation rate and have high activity.Known dyestuff can not satisfy above-mentioned requirements at all, as the reactive dyestuffs of introducing among the Japanese Patent JP8120188, though some fastness ability is good, but still can't satisfy the demand fully.
In sum, this area lacks the new reactive dyestuffs that are used for cellulosic fibre material dyeing and stamp, therefore, this area presses for a kind of dyestuff of exploitation, this dyestuff has performances such as fixation rate height, the fiber combination stability is good, fast light, color fastness to water is good, in addition, during dyeing not fixing part be easy to eccysis.
Summary of the invention
The objective of the invention is to obtain reactive dye compound a kind of excellent property, that be used for cellulosic fibre material dyeing and stamp, this dyestuff has performances such as fixation rate height, the fiber combination stability is good, fast light, color fastness to water is good, in addition, during dyeing not fixing part be easy to eccysis.
Another object of the present invention is to provide the preparation method of dye composition of the present invention.
Another object of the present invention is to provide the another kind of preparation method of dye composition of the present invention.
The present invention has a purpose to be to provide the another kind of preparation method of dye composition of the present invention again.
The present invention has a purpose to be to provide the composition that contains dye composition of the present invention again.
A further object of the invention is to provide the purposes of dye composition of the present invention.
One aspect of the present invention provides a kind of dye composition, and the structural formula of described compound is four azo structures, shown in following general formula (I):
In the described general formula (I):
The C group is suc as formula (C1), (C2), (C3) or the group (C4):
Wherein: D be singly-bound ,-NH-CO-,-NH-SO
2-or-SO
2-NH-SO
2-; M is H or Na;
B is the group as shown in the formula structure shown in (B1), (B2), (B3), (B4),
And two B structures in the described general formula (I) can be same structure or different structure;
A is as shown in the formula the group shown in (A1),
Wherein R is hydrogen, sulfonic group, methyl or methoxy; X is as shown in the formula (X1) or (X2) group:
-SO
2-Y (X1)
-CONH(CH
2)n-SO
2-Y (X2)
Wherein n is the integer of 0-2, and Y is-CH=CH
2,-C
2H
4OSO
3M;
And two A structures in the described general formula (I) can be same structure or different structure.
In a preferred embodiment of the present invention, described C is as shown in the formula the group shown in (C1-1), (C2-1):
In preferred implementation of the present invention, described A is selected from following group:
In preferred implementation of the present invention,
Two B structures in the described general formula (I) are same structure, and/or
Two A structures in the described general formula (I) are same structure.
In preferred implementation of the present invention, the structure of described compound is as follows:
A kind of on the other hand preparation method that a kind of compound of the present invention is provided of the present invention,
When C be (C1), (C2) or (C4) shown in structure,
And B be (B1), (B2) or (B4) shown in during structural compounds:
Reaction comprises the steps:
(i-1) with A-NH
2Compound carries out diazotization, with the coupling of B ' compound, obtains coupling product,
Common 2 molfraction A-NH
2Compound carries out diazotization, and with 2 molfraction B ' compounds, ratio can change on this basis to some extent between its umber certainly again, and this all belongs to those skilled in the art's common practise,
B ' compound is a structural compounds shown in (B1 '), (B2 ') or (B4 ')
(i-2) in the above-mentioned coupled product of step (i-1), add through bis-diazotized H
2N-C-NH
2Carry out coupling, wherein C be (C1), (C2) or (C4) shown in structure, thereby the compound shown in the formula of making (I); Usually add 1 molfraction through bis-diazotized H
2N-C-NH
2, this umber can change on this basis to some extent certainly, and this all belongs to those skilled in the art's common practise.
A further aspect of the invention provides a kind of preparation method of compound of the present invention, when C is a structure shown in (C1), (C2), (C4),
And B be (B1), (B2) or (B4) shown in during structural compounds:
Reaction comprises the steps:
(m-1) with H
2N-C-NH
2Carry out dual nitrogenize,, obtain coupling product with the coupling of going ahead of the rest of the compound shown in the B ';
Wherein, C is a structure shown in (C1), (C2), (C4),
B ' compound is a structural compounds shown in (B1 '), (B2 ') or (B4 ')
Usually with 1 molfraction H
2N-C-NH
2Carry out dual nitrogenize, with the coupling of going ahead of the rest of the compound shown in the 2 molfraction B, obtain coupling product, its umber can change on this basis to some extent certainly, and this all belongs to those skilled in the art's common practise;
(m-2) in the coupling product that (m-1) step obtains, drip A-NH
2The further coupling of diazonium liquid, thereby the compound shown in the formula of making (I);
Usually drip 2 molfraction A-NH
2The further coupling of diazonium liquid, its umber can change on this basis to some extent certainly, this all belongs to those skilled in the art's common practise.
The present invention provides a kind of preparation method of compound of the present invention on the other hand,
As C when being (C3), B for the compound of structure shown in (B3):
Reaction comprises the steps:
(n-1) earlier will through diazotizing suc as formula the compound shown in (B3 ') with carry out coupling suc as formula the compound shown in (C3 '), obtain coupling product;
Common 2 molfractions are carried out coupling through diazotizing B compound and 1 molfraction C compound and are obtained coupling product, and its umber can change on this basis to some extent certainly, and this all belongs to those skilled in the art's common practise;
(n-2) in the coupling product that step (n-1) obtains, add A-NH
2Diazonium liquid carries out the secondary coupling, thereby makes the compound of above-mentioned formula (I);
Usually add 2 molfraction A-NH
2Diazonium liquid carries out the secondary coupling, and its umber can change on this basis to some extent certainly, and this all belongs to those skilled in the art's common practise.
A further aspect of the invention provides a kind of dye composite, contains the dye composition of the present invention of the significant quantity that dyes, and other dyestuff of surplus, carrier, auxiliary agent or its combination.
The present invention has an aspect that a kind of purposes of compound of the present invention is provided again, and it is used for the dyeing or the stamp of filamentary material.
In preferred implementation of the present invention, compound of the present invention is used for the dyeing or the stamp of nitrogenous or hydroxyl filamentary material.
In preferred implementation of the present invention, compound of the present invention is used for the dyeing or the stamp of cotton, fiber crops, silk, leather, wool, tynex.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, four azo structure compounds of brand new have been obtained, and be surprised to find that this compound has performances such as fixation rate height, the fiber combination stability is good, fast light, color fastness to water is good as dyestuff, in addition, during dyeing not fixing part be easy to eccysis, so be particularly suitable for the dyeing and the stamp of cotton, fiber crops, silk, leather, wool, tynex.
Finished the present invention on this basis.
Dye composition of the present invention also can be called reactive dyestuffs.
The compound (or corresponding raw material) that has structure shown in A, B, the C among the present invention is known compound, maybe can make perhaps commercially available buying by known way easily.
Of the present invention-SO
3M among the M can be Na or H.When M is H, be sulfonic group.Sulfonic group of the present invention comprises free sulfonic, also comprises suitable salt or ester.For example, described salt is an alkali metal salt except Na salt.
Dye composite
Dye composite of the present invention contains the dye composition of the present invention of the significant quantity that dyes and other dyestuff of surplus, carrier, auxiliary agent or its combination.
Described dyeing significant quantity is added according to those skilled in the art's common practise.
" other dyestuff " of the present invention comprises other one or more dye compositions of the present invention.Because dye composition of the present invention comprises multiple structure, therefore can make up be mixed (for example purpose) mutually between the dye composition of the present invention of various structures in order to mix colours, obtain dye composite.
" other dyestuff " of the present invention also comprises the reactive dyestuffs that other is suitable for.Also promptly, can also add other reactive dyestuffs that are suitable for according to general knowledge and make up and be mixed, obtain dye composite.
" other dyestuff " of the present invention further can also comprise the dyestuff that other is suitable for.
Dye composition of the present invention exists as the form of solid or liquid usually.Can add various electrolyte salt in the described solid form, electrolyte salt commonly used in the particularly water miscible or fiber-reactive colorants is as NaCl, KCl and Na
2SO
4Can also further add the auxiliary agent that is common in the commercial dyestuff, for example pH value of aqueous solution can be stabilized in the buffer substance of 3-7, as acetate, borate, supercarbonate, dihydrogen phosphate, Citrate trianion and phosphoric acid hydrogen disalt (as described in salt for example be an alkali metal salt that comprises sodium salt and sylvite), and small quantity of drying.When existing, can add the material (for example mould inhibitor) of thickening material or prolongation storage life with liquid form or aqueous solution form.
In addition, conventional additives be can also add, for example variously carrier, auxiliary agent or combination well known to a person skilled in the art.For example, add dyeing and printing auxiliary, as mordant, levelling agent; Or the adding stablizer, as antioxidant; Or the adding dispersion agent, or the like.
The preparation method
Dye composition of the present invention also can pass through other conventional diazotization, couling process preparation.
Described diazo reagent includes but not limited to: nitrosyl sulfuric acid, Sodium Nitrite and hydrochloric acid or sulfuric acid.
Described coupling condition includes but not limited to: temperature is controlled to be 0～5 ℃, and pH value is controlled to be 3～7.
Purposes
The present invention is applicable to the dyeing or the stamp of the material of nitrogenous or hydroxyl.Also be applicable to the dyeing or the stamp of fibrous matter.Be specially adapted to the dyeing or the stamp of the fibrous matter of nitrogenous or hydroxyl.
Especially, compound of the present invention is used for the dyeing or the stamp of cotton, fiber crops, silk, leather, wool, tynex
Major advantage of the present invention comprises:
(a) this dyestuff has performances such as fixation rate height, the fiber combination stability is good, fast light, color fastness to water is good.
(b) the not fixing part of this dyestuff when dyeing is easy to eccysis.
(c) the dyeing and weaving thing that utilizes dyestuff of the present invention to obtain has colour fastness such as excellent fast light, water-fast, sweat proof, rub resistance.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
Embodiment 1
Raw material
Raw material 1:A1-NH
2A1=wherein
Raw material 2:NH
2-(C1-1)-NH
2Wherein (C1-1)=
Raw material 3:(B1) B1=wherein
Reactions steps
With 0.01mol formula A1-NH
2Compound in the water of ice cube is arranged, fully stir, add 31% hydrochloric acid 1.5ml, in 0～5 ℃ scope, drip the sodium nitrite in aqueous solution 5.5ml of 2mol/l gradually, carry out diazotization reaction, stir and reached home in about 1 hour, add thionamic acid and remove excessive nitrous acid, nondiscoloration to potassium iodide starch test paper 0.5～2s makes A1-NH
2Diazonium salt.
With 0.005mol formula NH
2-(C1-1)-NH
2Compound in the water of ice cube is arranged, fully stir, the hydrochloric acid 5ml of adding 31%, after being cooled to 0 ℃, the sodium nitrite in aqueous solution 5.5ml that drips 2mol/l gradually carries out dual nitrogenizing reaction, eliminate excessive nitrous acid with thionamic acid after reaction is finished and to potassium iodide starch test paper 0.5～2s, do not develop the color, make its dual nitride.
With above-mentioned A1-NH
2Diazonium salt in add 2 of 0.01mol, 4-diamino benzene sulfonic acid sodium solid, 0～5 ℃ of controlled temperature stirs down and carries out linked reaction, reacts to finish in 2 hours slow dropping formula NH in above-mentioned coupled reaction mixture
2-(C1-1)-NH
2Tetrazo compound, the secondary coupling takes place down in stirring, regulating pH value with sodium bicarbonate then is 3～4, until reacting completely, promptly gets the yellowish-orange dyestuff of following formula.
Embodiment 2
Raw material
Raw material 1:A1-NH
2A1=
Raw material 2: γ acid (B3)
Raw material 3:(C3): promptly
(wherein M=Na)
The A1-NH for preparing 0.01mol by the method for example 1
2Diazonium salt adds it in γ acid shown in 0.01mol formula (B3) to, in 0～5 ℃, regulates pH value 4～6 with sodium bicarbonate, carries out linked reaction under stirring.
The hydrochloric acid 0.04mol of adding 31% in above-mentioned coupled product, 0～5 ℃ of controlled temperature stirs the sodium nitrite solution 5.5ml that drips 2mol/L down, carries out diazotization reaction.After reaction is finished, be added into 2 shown in the formula (C3), in the suspension of 4-diamino benzene sulfonic acid sodium, regulate pH value 4～6, under 0～5 ℃ condition, carry out the secondary coupled reaction, stir reaction in 2 hours and finish, make the orange dye of formula (Ib) with sodium bicarbonate.
Embodiment 3～15
The preparation method of the compound of embodiment 3～15 is according to example 1 described preparation method, and difference is that A, B, the C component in the raw material changes.
Embodiment 3
Difference is:
In the raw material 3, C=
Obtain:
Embodiment 4
Difference is:
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 5
Difference is:
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 6
Difference is:
In the raw material 1, A=
In the raw material 2, B=
Obtain:
Embodiment 7
Difference is:
In the raw material 1, A=
In the raw material 3, C:
Obtain:
Embodiment 8
Difference is:
In the raw material 1, A=
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 9
Difference is:
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 10
Difference is:
In the raw material 1, A=
In the raw material 2, B=
Obtain:
Embodiment 11
Difference is:
In the raw material 1, A=
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 12
Difference is:
In the raw material 1, A=
In the raw material 3, C=
Obtain:
Embodiment 13
Difference is:
In the raw material 1, A=
In the raw material 3, C=
Obtain:
Embodiment 14
Difference is:
In the raw material 1, A=
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 15
Difference is:
In the raw material 1, A=
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 16
According to example 1 described method, different is, dual nitride and the formula B with formula C carries out coupling earlier, and the diazonium salt with this conjugates and formula A carries out the secondary coupling again, can make following Tetrakisazo dyes.
In the raw material 1, A=
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 17
According to the preparation method of embodiment 16, different is:
In the raw material 1, A=
In the raw material 3, C=
Obtain:
Embodiment 18
Embodiment 18 is according to the preparation method of embodiment 16, and different is:
In the raw material 3, C=
Obtain:
Embodiment 19
Embodiment 19 is according to the preparation method of embodiment 16, and different is:
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 20
Embodiment 20 is according to the preparation method of embodiment 16, and different is:
In the raw material 2, B=
In the raw material 3, C=
Obtain:
Embodiment 21
Embodiment 21 is according to the preparation method of embodiment 16, and different is:
In the raw material 1, A=
In the raw material 2, B=
And
In the raw material 3, C=
Obtain:
Dyeing procedure:
With the 4 parts of weight parts of dyestuff that make in the foregoing description 1～21, join in 1000 parts of water, add 30 parts of sodium sulfate solids, after the dissolving back adds 50 parts of cottons immersion 10min, dye bath is warmed up to 60 ℃ in 20min, add 15 parts of yellow soda ash solids after keeping 30min, behind the continuation insulation dyeing 30min, take out cloth specimen, behind the cold water washing loose colour, join 60 ℃ of rinsing 10min in the neutral soap lye (the antifouling soaping agent of for example commercially available BF-201) of 30 grams per liters, take out cloth specimen, dry.Test its colour fastness to rubbing, colour fastness to perspiration, color fastness to water by the method for determining among GB/T3920-1997, GB/T3922-1997 and the GB/T5713-1997 respectively, test result sees the following form 4.
Table 4
| Embodiment | Rub resistance | Perspiration resistance | Water-fast soaking | Color |
| Embodiment 1 | 4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 2 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 3 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 4 | 3～4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 5 | 4 grades | 4～5 grades | 4～5 grades | Blue |
| Embodiment 6 | 3～4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 7 | 4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 8 | 3～4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 9 | 4 grades | 4～5 grades | 4～5 grades | Blue |
| Embodiment 10 | 3～4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 11 | 4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 12 | 3～4 grades | 4～5 grades | 4～5 grades | Orange |
| Embodiment 13 | 3～4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 14 | 4 grades | 4～5 grades | 4～5 grades | Blue |
| Embodiment 15 | 3～4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 16 | 3～4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 17 | 4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 18 | 4 grades | 4～5 grades | 4～5 grades | Yellowish-orange |
| Embodiment 19 | 4 grades | 4～5 grades | 4～5 grades | Blue |
| Embodiment 20 | 4 grades | 4～5 grades | 4～5 grades | Blue |
| Embodiment 21 | 4 grades | 4～5 grades | 4～5 grades | Blue |
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a dye composition is characterized in that, the structural formula of described compound is four azo structures, shown in following general formula (I):
A——N＝N——B——N＝N——C——N＝N——B——N＝N——A
(I)
In the described general formula (I):
The C group is suc as formula (C1), (C2), (C3) or the group (C4):
Wherein: D be singly-bound ,-NH-CO-,-NH-SO
2-or-SO
2-NH-SO
2-; M is H or Na; B is the group as shown in the formula structure shown in (B1), (B2), (B3), (B4),
And two B structures in the described general formula (I) can be same structure or different structure;
A is as shown in the formula the group shown in (A1),
Wherein R is hydrogen, sulfonic group, methyl or methoxy; X is as shown in the formula (X1) or (X2) group:
-SO
2-Y (X1)
-CONH(CH
2)n-SO
2-Y (X2)
Wherein n is the integer of 0-2, and Y is-CH=CH
2,-C
2H
4OSO
3M;
And two A structures in the described general formula (I) can be same structure or different structure.
2. compound as claimed in claim 1 is characterized in that, described C is as shown in the formula the group shown in (C1-1), (C2-1):
3. compound as claimed in claim 1 is characterized in that, described A is selected from following group:
4. compound as claimed in claim 1 is characterized in that,
Two B structures in the described general formula (I) are same structure, and/or
Two A structures in the described general formula (I) are same structure.
5. as claim 1 or 3 described compounds, it is characterized in that the structure of described compound is as follows:
6. the preparation method of a compound as claimed in claim 1 is characterized in that, when C be (C1), (C2) or (C4) shown in structure,
And B be (B1), (B2) or (B4) shown in during structural compounds:
Reaction comprises the steps:
(i-1) with A-NH
2Compound carries out diazotization, with the coupling of B ' compound, obtains coupling product, wherein, A as defined in claim 1,
B ' compound is a structural compounds shown in (B1 '), (B2 ') or (B4 ')
(i-2) in the above-mentioned coupled product of step (i-1), add through bis-diazotized H
2N-C-NH
2Carry out coupling,
Wherein C be (C1), (C2) or (C4) shown in structure, thereby the compound shown in the formula of making (I).
7. the preparation method of a compound as claimed in claim 1 is characterized in that, when C is a structure shown in (C1), (C2), (C4),
And B be (B1), (B2) or (B4) shown in during structural compounds:
Reaction comprises the steps:
(m-1) with H
2N-C-NH
2Carry out dual nitrogenize,, obtain coupling product with the coupling of going ahead of the rest of the compound shown in the B ';
Wherein, C is a structure shown in (C1), (C2), (C4),
B ' compound is a structural compounds shown in (B1 '), (B2 ') or (B4 ')
(m-2) in the coupling product that (m-1) step obtains, drip A-NH
2The further coupling of diazonium liquid, thereby the compound shown in the formula of making (I), wherein, A is as defined in claim 1.
8. the preparation method of a compound as claimed in claim 1 is characterized in that,
As C when being (C3), B for the compound of structure shown in (B3):
Reaction comprises the steps:
(n-1) earlier will through diazotizing suc as formula the compound shown in (B3 ') with carry out coupling suc as formula the compound shown in (C3 '), obtain coupling product;
(n-2) in the coupling product that step (n-1) obtains, add A-NH
2Diazonium liquid carries out the secondary coupling, thereby makes the compound of above-mentioned formula (I); Wherein, A as defined in claim 1.
9. a dye composite is characterized in that, contains the dye composition as claimed in claim 1 of the significant quantity that dyes, and other dyestuff of surplus, carrier, auxiliary agent or its combination.
10. the purposes of a compound as claimed in claim 1 is characterized in that, is used for the dyeing or the stamp of filamentary material.
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|---|---|---|---|
| CN 200610027959 CN101092522A (en) | 2006-06-22 | 2006-06-22 | Activated dye, prepartion method, and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610027959 CN101092522A (en) | 2006-06-22 | 2006-06-22 | Activated dye, prepartion method, and application |
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Family
ID=38990968
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| CN 200610027959 Pending CN101092522A (en) | 2006-06-22 | 2006-06-22 | Activated dye, prepartion method, and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2457956A1 (en) * | 2010-11-30 | 2012-05-30 | Kemira Oyj | Azo dyes |
| CN101531831B (en) * | 2009-04-07 | 2012-05-30 | 吴江梅堰三友染料化工有限公司 | Production method of direct blended brown D-RS dye |
| CN101544848B (en) * | 2008-12-12 | 2013-01-16 | 天津德凯化工股份有限公司 | Activated dye composition and preparation method thereof |
| CN101481544B (en) * | 2008-12-12 | 2013-01-16 | 天津德凯化工股份有限公司 | Reactive dye composition and preparation thereof |
| CN101544849B (en) * | 2008-12-12 | 2013-03-20 | 天津德凯化工股份有限公司 | Activated dye composition and preparation method thereof |
| CN112111174A (en) * | 2020-09-27 | 2020-12-22 | 苏州澳缘盛新材料科技有限公司 | Preparation method of reactive dye blue |
| CN112175413A (en) * | 2020-09-27 | 2021-01-05 | 苏州澳缘盛新材料科技有限公司 | Reactive dye blue and application thereof |
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2006
- 2006-06-22 CN CN 200610027959 patent/CN101092522A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544848B (en) * | 2008-12-12 | 2013-01-16 | 天津德凯化工股份有限公司 | Activated dye composition and preparation method thereof |
| CN101481544B (en) * | 2008-12-12 | 2013-01-16 | 天津德凯化工股份有限公司 | Reactive dye composition and preparation thereof |
| CN101544849B (en) * | 2008-12-12 | 2013-03-20 | 天津德凯化工股份有限公司 | Activated dye composition and preparation method thereof |
| CN101531831B (en) * | 2009-04-07 | 2012-05-30 | 吴江梅堰三友染料化工有限公司 | Production method of direct blended brown D-RS dye |
| EP2457956A1 (en) * | 2010-11-30 | 2012-05-30 | Kemira Oyj | Azo dyes |
| WO2012072634A1 (en) * | 2010-11-30 | 2012-06-07 | Kemira Oyj | Azo dyes |
| CN103228739A (en) * | 2010-11-30 | 2013-07-31 | 凯米拉公司 | Azo dyes |
| US8734532B2 (en) | 2010-11-30 | 2014-05-27 | Kemira Oyj | Azo dyes |
| CN112111174A (en) * | 2020-09-27 | 2020-12-22 | 苏州澳缘盛新材料科技有限公司 | Preparation method of reactive dye blue |
| CN112175413A (en) * | 2020-09-27 | 2021-01-05 | 苏州澳缘盛新材料科技有限公司 | Reactive dye blue and application thereof |
| CN112175413B (en) * | 2020-09-27 | 2022-05-06 | 苏州澳缘盛新材料科技有限公司 | Reactive dye blue and application thereof |
| CN112111174B (en) * | 2020-09-27 | 2022-05-31 | 苏州澳缘盛新材料科技有限公司 | Preparation method of reactive dye blue |
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