CN101143970A - Dye compound and its preparation method and application - Google Patents
Dye compound and its preparation method and application Download PDFInfo
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- CN101143970A CN101143970A CNA2006100310342A CN200610031034A CN101143970A CN 101143970 A CN101143970 A CN 101143970A CN A2006100310342 A CNA2006100310342 A CN A2006100310342A CN 200610031034 A CN200610031034 A CN 200610031034A CN 101143970 A CN101143970 A CN 101143970A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004043 dyeing Methods 0.000 claims abstract description 25
- 239000000975 dye Substances 0.000 claims description 92
- 238000005859 coupling reaction Methods 0.000 claims description 42
- 230000008878 coupling Effects 0.000 claims description 40
- 238000010168 coupling process Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012954 diazonium Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006193 diazotization reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000002131 composite material Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 4
- 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 15
- 239000000835 fiber Substances 0.000 abstract description 10
- 238000007639 printing Methods 0.000 abstract description 2
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 239000002657 fibrous material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 99
- 239000004744 fabric Substances 0.000 description 42
- 239000002932 luster Substances 0.000 description 27
- 239000011734 sodium Substances 0.000 description 10
- 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
- 238000000034 method Methods 0.000 description 7
- 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
- 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
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 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
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical group C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 2
- 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 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
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 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
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012928 buffer substance Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 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
- 239000000344 soap Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 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
- 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
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
The invention provides an active dye compound with good performance for dyeing and printing of cellulose fiber material, wherein the dye has high fixation rate, good fiber combination stability, light resistance, water resistance, and fine color fastness. Furthermore, the non-fixed part of the dye is easy to wash away during dyeing. The invention also provides preparation method and use of the dye compound.
Description
Technical field
The present invention relates to a kind of dye composition and its production and use.
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 JP8l20l88, 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 (worker):
The C group is suc as formula (C1), (C2), (C3) or the group (C4):
Wherein: D is a singly-bound ,-NH-CO-,-NH-SO
2-,-NH-CO-NH-or-NH-;
R
1, R
2Independently be-SO separately
3M or-COOH, M is H or Na;
B is the group as shown in the formula structure shown in (B1), (B2), (B3), (B4),
M is H or Na; 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; M is H or Na;
And two A structures in the described general formula (I) can be same structure or different structure.
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:
Wherein M is H or Na.
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,
Wherein: D is a singly-bound ,-NH-CO-,-NH-SO
2-,-NH-CO-NH-or-NH-;
R
1, R
2Independently be-SO separately
3M or-COOH, M is H or Na; 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 under acidic conditions,
Common 2 molfraction A-NH
2Compound carries out diazotization, and with 2 molfraction B ' compound couplings, 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, for example, and 2 molfraction A-NH
2Compound carries out diazotization, again with 2 ± 1 molfraction B ' compound couplings;
B ' compound is a structural compounds shown in (B1 '), (B2 ') or (B4 ')
(i-2) in the coupled product that above-mentioned steps (i-1) obtains, 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.For example, add 1 ± 0.5 molfraction through bis-diazotized H
2N-C-NH
2
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),
Wherein: D is a singly-bound ,-NH-CO-,-NH-SO
2-,-NH-CO-NH-or-NH-;
R
1, R
2Independently be-SO separately
3M or-COOH, M is H or Na; 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, under acidic conditions,, 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; 1 molfraction H for example
2N-C-NH
2With the compound coupling shown in 2 ± 0.5 molfraction B.
(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.For example, drip 2 ± 0.5 molfraction A-NH
2The further coupling of diazonium liquid.
The present invention provides a kind of preparation method of compound of the present invention on the other hand,
When (when C is (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; For example, 2 molfractions are carried out coupling through diazotizing B compound and 1 ± 0.5 molfraction C compound and are obtained 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);
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.For example, add 2 ± 1 molfraction A-NH
2Diazonium liquid carries out the secondary coupling.
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.For example, the dyestuff of the present invention that contains 0.1-99 weight % in the composition.
" 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 diazotization condition includes but not limited to: temperature is controlled to be 0～10 ℃, preferred 0～5 ℃.PH value is controlled to be 3～7.Diazotization reaction of the present invention can also be undertaken by other conventional coupling condition.For example, 1 mole aromatic amine uses 2.5～3 moles mineral acid.
Described coupling condition includes but not limited to: temperature is controlled to be 0～10 ℃, preferred 0～5 ℃.PH value is controlled to be acidic conditions, and for example 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 1: compd A-NH
2Wherein
Raw material 2: compd B wherein
Raw material 3: compound N H
2-C-NH
2Wherein
Reactions steps
With 0.01mol formula A-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/1 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 A-NH
2Diazonium salt.
With 0.005mol formula NH
2-C-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/1 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 A-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-C-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 dyestuff of the orange color and luster of offered fabric of following formula,
The uv-absorbing wavelength is λ after measured
Max=450nm.
Uv-absorbing wavelength measuring method of the present invention is as follows:
1, suitably prepare dye solution and select cuvette for use with distilled water, the peak value that makes dilution back solution absorbance to be measured is as far as possible about 1.0;
2, on UV330 type ultraviolet spectrophotometer, with purified distilled water as reference;
3, on UV330 type ultraviolet spectrophotometer, put into the dyestuff sample for preparing, (380～700nm) measure absorbancy and maximum absorption wavelength (as there not being opposite explanation, the measuring method of other embodiment is identical with embodiment 1) in visible spectrum range.
Embodiment 2
Raw material 1: compd A-NH
2 
Raw material 2:B is γ acid
Raw material 3: Compound C
The Al-NH for preparing 0.01mol by the method for example 1
2Diazonium salt adds it in γ acid shown in 0.01mol formula B 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 C, in the suspension of 4-diamino benzene sulfonic acid sodium, regulate pH value 4～6 with sodium bicarbonate, under 0～5 ℃ condition, carry out the secondary coupled reaction, stir reaction in 2 hours and finish, make the dyestuff of the orange color and luster of offered fabric of following formula, go into
Max=480nm.
Embodiment 3～24
The preparation method of compound carries out according to example 1 described preparation method among the embodiment 3～24, and difference is that A, B, the C component in the raw material changes, and as identical with feed composition in the example 1, then structure is omitted.
Embodiment 3
Difference is: in the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm.
Embodiment 4
Difference is:
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm
Embodiment 5
Difference is:
In the raw material 2,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=598nm.
Embodiment 6
Difference is:
In the raw material 1,
In the raw material 2,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=450nm
Embodiment 7
Difference is:
In the raw material 1,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm.
Embodiment 8
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=465nm.
Embodiment 9
Difference is:
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm
Embodiment 10
Difference is:
In the raw material 1,
In the raw material 2,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm.
Embodiment 11
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm.
Embodiment 12
Difference is:
In the raw material 1,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm.
Embodiment 13
Difference is:
In the raw material 1,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm.
Embodiment 14
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=605nm.
Embodiment 15
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of orange color and luster of the offered fabric of following formula, λ
Max=450nm.
Embodiment 16
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 17
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 18
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 19
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 20
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 21
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 22
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 23
Different is:
In the raw material 2,
In the raw material 3,
Obtain the atroceruleous dyestuff of offered fabric of following formula, λ
Max=600nm.
Embodiment 24
Different is:
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 25
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,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=450nm.
Embodiment 26～40
According to the preparation method of embodiment 25, the substituting group of A, B, C is as giving a definition, and what wherein substituting group was identical omits.
Embodiment 26
Difference is:
In the raw material 1,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=445nm.
Embodiment 27
Difference is:
In the raw material 1,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=445nm.
Embodiment 28
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the offered fabric black hues of following formula, λ
Max=605nm.
Embodiment 29
Difference is
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the offered fabric black hues of following formula, λ
Max=605nm.
Embodiment 30
Difference is:
In the raw material 1,
In the raw material 2,
And
In the raw material 3,
Obtain the dyestuff of the offered fabric black hues of following formula, λ
Max=605nm.
Embodiment 31
Difference is:
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 32
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 33
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 34
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 35
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 36
Difference is:
In the raw material 1,
And
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 37
Difference is:
In the raw material 1,
And
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the offered fabric black hues of following formula, λ
Max=602nm.
Embodiment 38
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the dark blue color and luster of offered fabric of following formula, λ
Max=600nm.
Embodiment 39
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the offered fabric black hues of following formula, λ
Max=602nm.
40
Difference is:
In the raw material 1,
In the raw material 2,
In the raw material 3,
Obtain the dyestuff of the orange color and luster of offered fabric of following formula, λ
Max=460nm.
Dyeing procedure:
With 4 parts of the dyestuffs (weight part) that make in the foregoing description 1～40, join in 1000 parts of water, add 30 parts of sodium sulfate (solid), 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 (solid) 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 soap lye (the antifouling soaping agent of BF-201) of 30 grams per liters, take out cloth specimen, dry.Testing its colour fastness to rubbing by the method for determining among GB/T3920-1997, GB/T3922-1997 and the GB/T5713-1997 respectively is that 3～4 grades, 4 grades, colour fastness to perspiration are 4～5 grades of 4～5 grades, color fastness to water, and colourability is good.
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 is a singly-bound ,-NH-CO-,-NH-SO
2-,-NH-CO-NH-or-NH-;
R
1, R
2Independently be-SO separately
3M or-COOH, M is H or Na;
B is the group as shown in the formula structure shown in (B1), (B2), (B3), (B4),
M is H or Na; 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; M is H or Na;
And two A structures in the described general formula (I) can be same structure or different structure.
2. dye composition as claimed in claim 1 is characterized in that, described C group is suc as formula the group shown in (C1):
Wherein: D is a singly-bound ,-NH-CO-,-NH-SO
2-,-NH-CO-NH-or-NH-;
R
1, R
2Independently be-SO separately
3M or-COOH, M is H or Na.
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:
Wherein A as defined in claim 1.
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 coupled product that above-mentioned steps (i-1) obtains, 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, carry out coupling, obtain coupling product with the compound shown in the B ';
Wherein, C is a structure shown in (C1), (C2), (C4),
And 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 obtaining (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,
When C is (C3), B during for structure shown in (B3):
Reaction comprises the steps:
(n-1) 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;
Wherein M is H or Na;
(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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|---|---|---|---|
| CN2006100310342A CN101143970B (en) | 2006-09-12 | 2006-09-12 | Dye compound and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100310342A CN101143970B (en) | 2006-09-12 | 2006-09-12 | Dye compound and its preparation method and application |
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| Publication Number | Publication Date |
|---|---|
| CN101143970A true CN101143970A (en) | 2008-03-19 |
| CN101143970B CN101143970B (en) | 2011-11-16 |
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ID=39206713
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2015527420A (en) * | 2012-06-18 | 2015-09-17 | ダイスター・カラーズ・ディストリビューション・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Reactive dyes containing no metal atoms, methods for producing them and their use |
| CN105051116A (en) * | 2013-03-26 | 2015-11-11 | 日本化药株式会社 | Tetrakis-azo compound for black, dye composition including same, and usage therefor |
| EP3296363A1 (en) * | 2010-11-30 | 2018-03-21 | Kemira Oyj | Azo dyes |
-
2006
- 2006-09-12 CN CN2006100310342A patent/CN101143970B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP3296363A1 (en) * | 2010-11-30 | 2018-03-21 | Kemira Oyj | Azo dyes |
| JP2015527420A (en) * | 2012-06-18 | 2015-09-17 | ダイスター・カラーズ・ディストリビューション・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Reactive dyes containing no metal atoms, methods for producing them and their use |
| CN105051116A (en) * | 2013-03-26 | 2015-11-11 | 日本化药株式会社 | Tetrakis-azo compound for black, dye composition including same, and usage therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101143970B (en) | 2011-11-16 |
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