CN101260246B - Conjugated cation dyestuff and preparation method thereof - Google Patents

Conjugated cation dyestuff and preparation method thereof Download PDF

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CN101260246B
CN101260246B CN2008100366648A CN200810036664A CN101260246B CN 101260246 B CN101260246 B CN 101260246B CN 2008100366648 A CN2008100366648 A CN 2008100366648A CN 200810036664 A CN200810036664 A CN 200810036664A CN 101260246 B CN101260246 B CN 101260246B
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acid
compound
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chemical general
dyestuff
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CN101260246A (en
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贾颂今
朱小兵
郭立俭
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Lianyungang Qingtai Chemical Co.,Ltd.
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LIANYUNGANG QINGTAI CHEMICAL CO Ltd
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Abstract

The invention provides conjugate cationic dye which has the following chemical structure general formula (I), wherein R1 is selected from -H, -Cl, -OCH3, -COOCH3 or -OCH2CH3; R2 is selected from -H, -CH3, -CH2CH3, -CH(CH3) 2 or phenyl; R3 is selected from -H, -CH3, -CH2CH3 or substituted phenyl; R4 is selected from -CH3, -CH2CH3 and -CH2CH2CONH2; R5 is selected from -H, C1 alkyl or alkoxyl, C2 alkyl or alkoxyl, C3 alkyl or alkoxyl and C4 alkyl or alkoxyl, -Cl and -Br; X<-> is selected from Cl<->, Br<->, I<->, ZnCl3<->, H2PO4<->, CH2COO<->, HCOO<->, oxalate radical, lactate radical, citrate radical, sorbate radical, glycollate radical or salicylate radical. The invention also discloses a preparation method of the chemical structure general formula (I).

Description

A kind of conjugated cation dyestuff and preparation method thereof
Technical field
The present invention relates to a kind of dye well preparation, particularly a kind of conjugated cation dyestuff and preparation method.
Background technology
Cationic dyestuff is that kind is more widely used in present dyestuff market, in the aqueous solution, be ionized into the colored ion and the negatively charged ion of positive charge, the colored ion of this positive charge can combine with the 3rd monomeric acid group in the acrylic fibers, thereby realizes painted to fiber.Cationic dyestuff has good dye uptake to polyacrylonitrile, also can be used for the dyeing of modified dacron.According to the position difference of positively charged ion group in dyestuff, can be divided into two kinds of isolated form (or localization type) and conjugated types (or moving the territory type) to cationic dyestuff, the dyestuff of conjugated type has series of advantages such as dye uptake height, lovely luster, and product involved in the present invention is exactly the conjugated cation dyestuff that belongs to the heterocycle azo structure.Product has good applicability energy and stability.
Summary of the invention
First purpose of the present invention is to provide a kind of conjugated cation dyestuff.
Another object of the present invention is to provide the preparation method of above-mentioned conjugated cation dyestuff.
A kind of conjugated cation dyestuff has the structure shown in the following chemical structure of general formula (I):
Figure S2008100366648D00011
Wherein, R 1:-H ,-Cl ,-OCH 3,-COOCH 3Or-OCH 2CH 3
R 2:-H ,-CH 3,-CH 2CH 3,-CH (CH 3) 2Or phenyl;
R 3:-H ,-CH 3,-CH 2CH 3Or
Figure S2008100366648D00021
(being phenyl or substituted-phenyl);
R 4:-CH 3,-CH 2CH 3Or-CH 2CH 2CONH 2
R 5:-H ,-Cl ,-alkyl or the alkoxyl group of Br, C1-C4;
X -: Cl -, Br -, I -, ZnCl 3 -, H 2PO 4 -, CH 2COO -, HCOO -, oxalate, lactate, citrate, sorb acid group, ethanol acid group or salicylate.
The conjugated cation dyestuff of above-mentioned chemical structure of general formula (I) can be prepared from by the following method:
The method of the conjugated cation dyestuff of a kind of preparation chemical structure of general formula (I) is that compound with the compound of chemical general formula (II) and chemical general formula (III) carries out condensation reaction and obtains in organic acid,
Setting-up point is 25-30 ℃, and the reaction times is 20-24h.Wherein mol ratio is 1: 0.95～1: 1.05 between the compound of the compound of chemical general formula (II) and chemical general formula (III).
Organic acid is acetic acid, formic acid, oxalic acid, lactic acid or citric acid.Be preferably acetic acid.
The compound of chemical general formula (II) and organic acid mol ratio are 1: 1.2-1: 2.
The method of the conjugated cation dyestuff of a kind of preparation chemical structure of general formula (I) is that compound with the compound of chemical general formula (II) and chemical general formula (III) carries out condensation reaction and obtains in mineral acid,
Setting-up point is 50-60 ℃, and the reaction times is 4-5h.Wherein mol ratio is 1: 0.95～1: 1.05 between the compound of the compound of chemical general formula (II) and chemical general formula (III).
Mineral acid is selected from hydrochloric acid, phosphoric acid or sulfuric acid.Be preferably hydrochloric acid.
The compound of chemical general formula (II) and the mol ratio of mineral acid are 1: 1.2-1: 6.
The mass ratio of organic solvent and solid reactant is 2: 1-5: 1.
The method of the conjugated cation dyestuff of another kind of preparation chemical structure of general formula (I), the step that comprises has: the compound of the compound of chemical general formula (II) and chemical general formula (III) is carried out condensation reaction obtain in organic solvent in the presence of mineral acid, setting-up point is 60-100 ℃, and the reaction times is 3-4h.
Figure S2008100366648D00031
Wherein mol ratio is 1: 0.95～1: 1.05 between the compound of the compound of chemical general formula (II) and chemical general formula (III).
Organic solvent is selected from ethanol, methyl alcohol, butanols or Virahol.Organic solvent is preferably methyl alcohol or ethanol, and mineral acid is preferably phosphoric acid.The compound of chemical general formula (II) and the mol ratio of mineral acid are 1: 1.2-1: 2.
The product that aforesaid method obtains can further carry out negatively charged ion to be replaced, and obtains conjugated cation dyestuff.
Conjugated cation dyestuff of the present invention has bright-coloured coloured light, and technology is simple, convenient production; Product solvability for preparing and stability are better, and close with a series of product performance, consistency is fine, and can use with the dyestuff of similar or other types, can be used for colorant match, and is easy to use.This type of dyestuff can be used for polyacrylonitrile and with the dyeing and the stamp of other fabric blending product, have very high avidity and good vividness, and have the better fastness performance: as light fastness, washing fastness, crock fastness, soaping fastness and sublimation fastness etc.
Embodiment
Below in conjunction with embodiment the present invention is further elaborated.Protection domain of the present invention is not limited thereto.
Embodiment 1
In reaction flask, add 120g water, 14g acetic acid and 20.8g (0.12mol) formula (IIa) compound, stir and be warming up to the product dissolving, drop to room temperature then, add 25g (0.124mol) formula (IIIa) compound;
Figure S2008100366648D00041
Insulation reaction 20h under 25-30 ℃ condition filters the precipitation that generates then; Filter cake fully washs with sodium chloride solution, oven dry, and the cationic dyestuff of (Ia) structure that obtains having formula is the xanchromatic solid dye, with thinner dyestuff is carried out stdn then, reaches intensity general on the market.
Figure S2008100366648D00042
Embodiment 2
Adding 72g concentration is 36% hydrochloric acid and 20.8g (0.12mol) formula (IIa) compound in reaction flask, stirs to add 24g (0.119mol) formula (IIIa) compound down;
Figure S2008100366648D00043
Be warming up to 50-60 ℃, insulation reaction 4.5h under this temperature, be cooled to room temperature, then the precipitation that generates is filtered, filter cake fully washs with sodium chloride solution, oven dry, the cationic dyestuff of (Ia) structure that obtains having formula, be the xanchromatic solid dye, with thinner dyestuff carried out stdn then, reach intensity general on the market.
Figure S2008100366648D00051
Embodiment 3
Add 200ml ethanol and 20.8g (0.12mol) formula (IIa) compound in reaction flask, stirring is warming up to about 30 ℃, adds 25g (0.124mol) formula (IIIa) compound again;
Figure S2008100366648D00052
Add 16g phosphoric acid after stirring 30min, this moment, temperature can rise, continue slowly to be heated to 80-85 ℃ and carry out back flow reaction, be cooled to 40-50 ℃ with chilled brine after the backflow 3h, and then the water cool to room temperature, the precipitation that generates is filtered, oven dry, the cationic dyestuff of (Ib) structure that obtains having formula is the xanchromatic solid dye, with thinner dyestuff is carried out stdn then, reach intensity general on the market.
Embodiment 4
In reaction flask, add 120g water, 14g acetic acid and 22.5g (0.12mol) formula (IId) compound, stirring is warming up to the product dissolving, drop to room temperature then, add the compound of 28.6g (0.124mol) formula (IIId), insulation reaction 24h under 25-30 ℃ condition;
Figure S2008100366648D00062
Then the precipitation that generates is filtered, filter cake fully washs with sodium chloride solution, oven dry, and the cationic dyestuff of (Id) structure that obtains having formula is the xanchromatic solid dye, with thinner dyestuff is carried out stdn then, reaches intensity general on the market.
Figure S2008100366648D00063
Embodiment 5
Adding 36g concentration is 36% hydrochloric acid and 22.5g (0.12mol) formula (IIe) compound in reaction flask, stirs to add 36.5g (0.125mol) formula (IIIe) compound down;
Figure S2008100366648D00071
Be warming up to 50-60 ℃, insulation reaction 5h under this temperature, be cooled to room temperature, then the precipitation that generates is filtered, filter cake fully washs with sodium chloride solution, oven dry, the cationic dyestuff of (Ie) structure that obtains having formula, be the xanchromatic solid dye, with thinner dyestuff carried out stdn then, reach intensity general on the market.
Figure S2008100366648D00072
Embodiment 6
Add 200ml ethanol and 31.7g (0.12mol) formula (IIf) compound in reaction flask, stirring is warming up to about 30 ℃, adds 32g (0.123mol) formula (IIIf) compound again; Add 20g phosphoric acid after stirring 30min, this moment, temperature can rise, continue slowly to be heated to 80-85 ℃ and carry out back flow reaction, be cooled to 40-50 ℃ with chilled brine after the backflow 3.5h, and then the water cool to room temperature, the precipitation that generates is filtered, oven dry, the cationic dyestuff of (If) structure that obtains having formula is the xanchromatic solid dye, with thinner dyestuff is carried out stdn then, reach intensity general on the market.
Figure S2008100366648D00081
Embodiment 7
Adding 72g concentration is 36% hydrochloric acid and 28.3g (0.12mol) formula (IIa) compound in reaction flask, adds 25g (0.124mol) formula (IIIa) compound under stirring and is warming up to 50-60 ℃, and insulation reaction 5h under this temperature is cooled to room temperature.
Then the precipitation that generates is filtered, filter cake fully washs with sodium chloride solution, adds acetic acid and water and makes it dissolving, obtains following cationic dyestuff with formula (Ig) structure, is the xanchromatic liquid dye.And regulate intensity dyestuff is carried out stdn, reach intensity general on the market.
Figure S2008100366648D00091
Embodiment 8
Adding 72g concentration is 36% hydrochloric acid and 20.8g (0.12mol) formula (IIa) compound in reaction flask, stirs to add 25g (0.124mol) formula (IIIa) compound down;
Be warming up to 50-60 ℃, insulation reaction 4h is cooled to room temperature under this temperature, then the precipitation that generates is filtered, filter cake fully washs with sodium chloride solution, adds lactic acid and water and makes it dissolving, obtain following cationic dyestuff, be the xanchromatic liquid dye with formula (Ig) structure.And regulate intensity dyestuff is carried out stdn, reach intensity general on the market.
Figure S2008100366648D00093

Claims (10)

1. conjugated cation dyestuff has the structure of following chemical structure of general formula (I):
Figure S2008100366648C00011
Wherein,
R 1Be selected from-H ,-Cl ,-OCH 3,-COOCH 3Or-O CH 2CH 3
R 2Be selected from-H ,-CH 3,-CH 2CH 3,-CH (CH 3) 2Or phenyl;
R 3Be selected from-H ,-CH 3,-CH 2CH 3Or
Figure S2008100366648C00012
R 4Be selected from-CH 3,-CH 2CH 3,-CH 2CH 2CONH 2
R 5Be selected from-H ,-Cl ,-alkyl or the alkoxyl group of Br, C1-C4;
X -Be selected from Cl -, Br -, I -, ZnCl 3 -, H 2PO 4 -, CH 2COO -, HCOO -, oxalate, lactate, citrate, sorb acid group, ethanol acid group or salicylate.
2. one kind prepares the method for conjugated cation dyestuff according to claim 1, it is characterized in that, comprise the steps: the compound of following chemical general formula (II) and the compound of chemical general formula (III) are carried out condensation reaction in organic acid,
Figure S2008100366648C00013
Setting-up point is 25-30 ℃, and the reaction times is 20-24h.
3. one kind prepares the method for conjugated cation dyestuff according to claim 1, it is characterized in that, may further comprise the steps: the compound of chemical general formula (II) and the compound of chemical general formula (III) are carried out condensation reaction in mineral acid, setting-up point is 50-60 ℃, and the reaction times is 4-5hr.
4. one kind prepares the method for conjugated cation dyestuff according to claim 1, it is characterized in that, comprise the steps: be compound with the compound of chemical general formula (II) and chemical general formula (III) in organic solvent and mineral acid in the presence of carry out condensation reaction and obtain, setting-up point is 60-100 ℃, and the reaction times is 3-4hr.
5. the preparation method of conjugated cation dyestuff as claimed in claim 2 is characterized in that, the compound of chemical general formula (II) and organic acid mol ratio are 1: 1.2-1: 2, and described organic acid is acetic acid, formic acid, oxalic acid, lactic acid or citric acid.
6. the preparation method of conjugated cation dyestuff as claimed in claim 3 is characterized in that, the compound of chemical general formula (II) and the mol ratio of mineral acid are 1: 1.2-1: 6, and described mineral acid is hydrochloric acid, sulfuric acid or phosphoric acid.
7. the preparation method of conjugated cation dyestuff as claimed in claim 4, it is characterized in that, the compound of chemical general formula (II) and the mol ratio of mineral acid are 1: 1.2-1: 2, and described mineral acid is a phosphoric acid, described organic solvent is ethanol, methyl alcohol, butanols or Virahol.
8. the preparation method of conjugated cation dyestuff as claimed in claim 4 is characterized in that, the mass ratio of described organic solvent and solid reactant is 2: 1-5: 1.
9. as each described conjugated cation dyestuff of claim 2-4, it is characterized in that mol ratio is 1: 0.95～1: 1.05 between the compound of the compound of described chemical general formula (II) and chemical general formula (III).
10. as each described conjugated cation dyestuff of claim 2-4, it is characterized in that, the product that obtains is carried out negatively charged ion replace.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1431963A (en) * 1972-09-06 1976-04-14 Bayer Ag Cationic dyestuffs
CN1048744C (en) * 1993-07-16 2000-01-26 上海染料化工三厂 Methine style fluorescent red cation dye and its preparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1431963A (en) * 1972-09-06 1976-04-14 Bayer Ag Cationic dyestuffs
CN1048744C (en) * 1993-07-16 2000-01-26 上海染料化工三厂 Methine style fluorescent red cation dye and its preparation

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